CN109790195A - Iridium complex compound, composition containing the same, organic electroluminescent element, display device, and lighting device - Google Patents

Abstract

The present invention aims to provide an iridium complex compound which emits red phosphorescence and has a long maximum emission wavelength and a high emission quantum yield, a composition containing the compound, an organic electroluminescent element having a long maximum emission wavelength and a high emission efficiency, and a display device and an illumination device using the organic electroluminescent element. The present invention relates to an iridium complex compound represented by formula (1) having at least a naphthyridine skeleton as a ligand coordinated to an iridium atom.

Description

Iridium complex compound and composition, organic field luminescence containing above compound Element, display device and lighting device

Technical field

The present invention relates to a kind of iridium complex compounds, in particular to have as the emitting layer material of organic electroluminescent device Iridium complex compound, the composition containing the compound and organic electroluminescent device and have the organic field cause hair The display device and lighting device of optical element.In addition, further relate to it is a kind of can be to obtain the brand-new of iridium complex compound in high yield Make method.

Background technique

Organic EL illuminating, organic el display etc. utilize organic electroluminescent device (hereinafter referred to as " organic EL element ") Various electronic equipments it is constantly practical.Organic EL element is low and power consumption is small due to applying voltage, due also to being able to carry out three Primary colours shine, therefore are applied not only to large-scale display monitor, also start for using mobile phone, smart phone as in representative Miniscope.

In these organic el displays, the technology for making its display further increase the image of the sense of reality becomes future One of main development goal.It is therefore desirable to which also requirement can be in picture while the High precision of panels such as so-called 4K8K panel The range further expansion of the color of middle reproduction.Such as in order to meet one of standard as colorrendering quality and defined number Film advocates tissue (DCI) standard, it is necessary to further improve red and green coloration from the colour gamut of existing display.Especially About red, need to make coloration be x in cie color coordinate in the case where not making luminous efficiency, the deterioration of element driving service life =0.680 or more.It is therefore desirable to develop the red illuminating material that maximum luminous wavelength is present in longer wavelength side.

On the other hand, organic EL element is manufactured and organic material is deposited under vacuum mostly now.Separately Outside, organic EL element is manufactured and layer stackups that luminescent layer, electric charge injection layer, charge transport layer etc. is multiple.Therefore, in vacuum In vapour deposition method, evaporation process is cumbersome, producing rate variance, and in the organic EL element manufactured using vacuum vapour deposition, illumination Or the enlargement of the panel of display is extremely difficult.Therefore, in recent years, it can be used for giant display or photograph as efficiently manufacture The technique of bright organic EL element actively studies rubbing method.Rubbing method can hold compared with vacuum vapour deposition due to having It changes places the advantages of forming stable layer, it is therefore contemplated that being applied to the mass production or large-scale device of display or lighting device.

The luminiferous iridium of the phosphorescence of service efficiency and excellent in te pins of durability is matched in the luminescent material of such organic EL element Position compound.For the complex, constantly carry out target colorimetric or deliquescent adjusting in a solvent or Linguistic term as the raising of element durability, the selection of the basic framework of the main ligand using complex of these researchs, And the method for substituent group appropriate is imported to them to carry out.

The iridium complex compound used in organic EL element is the cyclometalated iridium complexes with bidentate ligand, this pair Tooth ligand is mainly coordinated by heteroatomic 2 atoms such as carbon atom and nitrogen-atoms or phosphorus atoms.It especially usually will be Complex with miscellaneous aromatic rings bidentate ligand as 2 such as 2- phenylpyridines, 2- phenylchinoline on iridium atom is as double Cyclometalated complex uses, or will have heteroaryl as 3 such as 2- phenylpyridines, 2- phenylchinoline on iridium atom The complex of fragrant ring bidentate ligand is used as three cyclometalated complex.It is known that three cyclometalated complex are for having Durability is higher when machine EL element, thus it is preferable to use.

In addition, can enumerate iridium complex compound as the high performance red illuminating material for being suitable for rubbing method, taste It pinged and ligand was furtherd investigate to improve luminous efficiency (for example, patent document 1).

So far, the synthetic method of many such iridium complex compounds is reported.In order to briefly describe, below In explanation, ligand uses 2- phenylpyridine.As one-step method for synthesizing, it is known to make iridium chloride (III) and 2- phenylpyridine this The method (non-patent literature 1, chemical formula 1) of the miscellaneous aromatic rings bidentate ligand reaction of sample.But in the method, reaction raw materials Chlorine component remain on cyclometalated iridium complexes, not only generate target facial isomer, but also generate it is many through formula isomery Isomeric by-products as body.

[chemical formula 1]

In addition, also often utilizing the one-step synthesis side for reacting tri acetylacetonato complex of iridium with miscellaneous aromatic rings bidentate ligand Method (non-patent literature 2, chemical formula 2).But this method generally requires hot conditions (180 DEG C or more), raw material complex can rise China, or due to the thermal stability of the raw material complex is insufficient and reaction of decomposing simultaneously, as a result, cyclometalated iridium complexes Yield be lower.

[chemical formula 2]

In order to avoid these situations, two steps via chlorine crosslinking iridium binuclear complex that non-patent literature 3 is widely used are closed At documented by method or non-patent literature 4 and patent document 2 by further made to be crosslinked by binuclear complex chlorine atom with Acetyl pyruvate is exchanged and is converted into after bis- (Cyclometalated) acetylacetone,2,4-pentanedione complex of iridium of monokaryon and then anti-with other ligands Answer the method for obtaining object.These methods miscellaneous distribution type three Cyclometalated iridium different suitable for the ligand of synthesis complex of iridium is matched Position compound.The reaction of especially the latter is able to suppress chlorine component and is mixed into product, requires high-purity preferably as synthesis The method of organic EL element material.

But in the former reaction, using in the unsaturated complex of iridium of coordination that silver salt removing is crosslinked chlorine and generates When mesosome is unstable, the decomposition of complex is only carried out sometimes and does not generate object completely.The reaction of the ligand especially reacted Property low situation, it is big such as volume, in order to improve dissolubility and the case where import many substituent groups or the alkalinity of ligand is low In the case where the trend it is obvious.In the reaction of the latter, in the case where the reactivity of ligand is low it is often required that at 180 DEG C or more At a high temperature of reacted, as a result, raw material compound decomposes, generates undesirable side reaction, thus becoming there are yield deterioration Gesture.

Therefore, the further improvement as two step synthetic method reports and matches in bis- (Cyclometalated) acetylacetone,2,4-pentanedione iridium Close in the reacting of object and other ligands that there are the method for silver salt (non-patent literatures 5).The mechanism of action of silver salt is still not clear, but pushes away It surveys since silver salt captures the acetyl acetone ligands dissociated in the reaction, thus inhibits back reaction, reaction yield improves.

Existing technical literature

Patent document

Patent document 1: International Publication No. 2015/087961

Patent document 2: Japanese Unexamined Patent Publication 2002-105055 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2016-64998 bulletin

Non-patent literature

Non-patent literature 1:J.Am.Chem.Soc., volume 107, page 1431~1432,1985

Non-patent literature 2:Inorg.Chem., volume 30, page 1685~1687,1991

Non-patent literature 3:Inorg.Chem., volume 33, page 545~550,1994

Non-patent literature 4:Inorg.Chem., volume 40, page 1704~1711,2001

Non-patent literature 5:J.Mater.Chem., volume 21, page 15494~15500,2011

Non-patent literature 6:S.Okada et al, Dalton Transactions, 2005,1583~1590.

Summary of the invention

It is well known, however, that relative to the trial of luminous efficiency, the luminous wave of maximum is improved by being furtherd investigate to ligand The long relationship that usually there is compromise with quantum yield, for example, according to Fig. 1 of Fig. 7 of non-patent literature 6 and patent document 3 Between the complex of similar skeleton, they are in linear relation.Therefore, actual conditions are still to cannot get to have both wishing The luminous efficiency of prestige and the material of maximum luminous wavelength.

The present invention is carried out in view of the above subject, project be to provide a kind of maximum luminous wavelength be more long wavelength and Show the emitting red light iridium complex compound of high quantum yield.In addition, the issue of the present invention is to provide a kind of driving service life Organic field luminescence comprising the emitting red light iridium complex compound long, luminous efficiency is high, good colorrendering quality is excellent Element.

In addition, the synthetic method about iridium complex compound, although being reported in the application non-patent literature 5 such as inventor anti- Condition is answered to attempt to synthesize, but the result is that is reacted almost without stopping reaction with small conversion ratio, only carrying out raw material cooperation The decomposition of object.

Therefore, the present invention is in view of the new reaction condition for thirsting for developing the range for expanding the reaction that can be applied, into one The project of step is to provide a kind of manufacturing method to be efficiently synthesized three Cyclometalated iridium complex compounds in high yield.

The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that having certain specific chemistry knot The iridium complex compound of structure has maximum luminous wavelength in longer wavelength side and shows high quantum yield.Be further discovered that include The driving service life of the organic electroluminescent device of the iridium complex compound is long, and luminous efficiency is high, and good colorrendering quality is excellent, So as to complete the present invention.

That is, purport of the invention is as follows.

[1] iridium complex compound that a kind of following formula (1) indicates.

[in formula (1), Ir indicates iridium atom.

Ring Cy¹It indicates to include carbon atom C¹And C²Aromatic rings or miscellaneous aromatic rings,

Ring Cy²It indicates to include carbon atom C³With nitrogen-atoms N¹The structure that indicates of any one of following formula (2)~formula (5),

Ring Cy³It indicates to include carbon atom C⁴And C⁵Aromatic rings or miscellaneous aromatic rings,

Ring Cy⁴It indicates to include carbon atom C⁶With nitrogen-atoms N²Miscellaneous aromatic rings.

Above-mentioned ring Cy¹~ring Cy⁴When being respectively present multiple, they be may be the same or different.

The integer that m is 1~3, the integer that n is 0~2,

M+n=3.

R¹~R⁴Each independently represent hydrogen atom or substituent group.

R¹~R⁴When being respectively present multiple, they be may be the same or different.

A, c and d is respectively in above-mentioned ring Cy¹, ring Cy³With ring Cy⁴On the maximum integer of group that can replace,

B is 5.]

[2] iridium complex compound according to above-mentioned [1], wherein the composition ring Cy in above-mentioned formula (1)¹, ring Cy³And ring Cy⁴The atomicity of ring be respectively 5~30.

[3] iridium complex compound according to above-mentioned [1] or [2], wherein the R in above-mentioned formula (1)¹~R⁴It is respectively independent Ground is the aromatic series of hydrogen atom, F, CN, the straight-chain of carbon atom number 1~30, branched or cyclic alkyl, carbon atom number 5~60 The heteroaromatic group of group or carbon atom number 5~60.

[4] iridium complex compound according to any one of above-mentioned [1]~[3], wherein the ring Cy in above-mentioned formula (1)¹ With ring Cy³It is each independently phenyl ring or naphthalene nucleus.

[5] iridium complex compound according to any one of above-mentioned [1]~[4], wherein the ring Cy in above-mentioned formula (1)⁴ For imidazole ring,Azoles ring, thiazole ring, benzimidazole ring, benzoAzoles ring, benzothiazole ring, pyridine ring, quinoline ring, isoquinoline Quinoline ring, pyridazine ring, pyrimidine ring, pyridine ring, triazine ring, cinnolines ring, phthalazines ring, quinazoline ring, quinoxaline ring or naphthyridines ring.

[6] iridium complex compound according to any one of above-mentioned [1]~[5], wherein make it with 1 × 10 under room temperature^{- 4}Mol/L concentration below is dissolved in the luminous wave of maximum of the shown phosphorescence spectrum out of solution obtained by 2- methyltetrahydrofuran A length of 620nm or more.

[7] a kind of composition contains iridium complex compound and organic solvent described in any one of above-mentioned [1]~[6].

[8] a kind of organic electroluminescent device contains iridium complex compound described in any one of above-mentioned [1]~[6].

[9] a kind of display device has organic electroluminescent device described in above-mentioned [8].

[10] a kind of lighting device has organic electroluminescent device described in above-mentioned [8].

In addition, the inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that by make it is bicyclic Metallized complex of iridium raw material and other ligand reactions and manufacture in the reacting of three Cyclometalated iridium complex compounds, in addition to silver (I) other than salt, also there is alkali together, to show extremely high reaction yield, so as to complete the present invention.

That is, another purport of the invention is as follows.

[11] a kind of manufacturing method of iridium complex compound, the iridium complex compound is by L^a ₂L^bIr or L^aL^b ₂Ir expression,

The manufacturing method makes L in the presence of being included in silver-colored (I) salt and organic base^a _pIrX_qThe compound and L of expression^bIt indicates Compound reaction process.

[in formula, Ir indicates iridium atom,

P and q each independently represents 0~3 integer, p+q=3,

L^aAnd L^bThe bidentate ligand for being coordinated in iridium atom comprising carbon atom and nitrogen-atoms is each independently represented, is existed more A L^aOr L^bIt may be the same or different,

X is the group that following formula (6) indicate.]

[in formula (6), * indicates the bonding position with above-mentioned iridium atom,

R¹¹And R¹³Indicate substituent group,

R¹²Indicate hydrogen atom or substituent group.]

[12] manufacturing method of the iridium complex compound according to above-mentioned [11], wherein above-mentioned L^a _pIrX_qIn p be 1 Or 2.

[13] manufacturing method of the iridium complex compound according to above-mentioned [11] or [12], wherein above-mentioned L^aAnd L^bIn At least either is indicated by following formula (7).

[in formula (7), * indicates the bonding position with above-mentioned iridium atom,

C¹¹、C¹²And C¹³Indicate carbon atom, N¹¹Indicate nitrogen-atoms,

Ring Cy⁵It indicates to include above-mentioned C¹¹With above-mentioned C¹²Aromatic rings or miscellaneous aromatic rings,

Ring Cy⁶It indicates to include above-mentioned N¹¹With above-mentioned C¹³Aromatic rings or miscellaneous aromatic rings,

R²¹And R²²Each independently represent hydrogen atom or substituent group, above-mentioned R²¹It is bonded to above-mentioned ring Cy⁵, above-mentioned R²²Bonding In above-mentioned ring Cy⁶。

X¹Expression may replace in above-mentioned ring Cy⁵Group maximum number, be integer.

X²Expression may replace in above-mentioned ring Cy⁶Group maximum number, be integer.]

The maximum luminous wavelength of iridium complex compound of the invention is long wavelength and shows high quantum yield.In addition, this The iridium complex compound of invention can use rubbing method production organic EL element due to dissolving in organic solvent.In addition, packet Organic EL element containing iridium complex compound of the invention is since it is possible to obtain high-luminous-efficiency, good colorrendering quality and pushes deep The dynamic service life, thus it is useful as display device and lighting device purposes.

It, can be to obtain the iridium complex compound of high-purity in high yield in addition, manufacturing method according to the invention.In addition, The iridium complex compound manufactured using the manufacturing method of the present invention is not only due to purity is high and is easy purification, and includes the iridium High-luminous-efficiency and long driving service life can be obtained in the organic EL element of complex, therefore as display device and lighting device Purposes and it is useful.

Detailed description of the invention

Fig. 1 is cutting for an example of the structure for showing schematically the organic electroluminescent device comprising iridium complex compound Face figure.

Fig. 2 is the maximum luminous wavelength for indicating the iridium complex compound of embodiment and comparative example and the relationship of quantum yield Figure.

Fig. 3 is the pass in the reaction time for indicating the synthesis example 2 in embodiment and the LC area percentage value (%) of compound 2 The figure of system.

Fig. 4 be the difference for indicating the manufacturing method because of embodiment and comparative example caused by reaction time and compound 20 LC The figure of the relationship of area percentage value.

LC of the expression of Fig. 5 because of reaction time and compound 21 caused by the difference of embodiment and the manufacturing method of comparative example The figure of the relationship of area percentage value.

Fig. 6 be the difference for indicating the manufacturing method because of embodiment and comparative example caused by reaction time and compound 22 LC The figure of the relationship of area percentage value.

Specific embodiment

It, can be with the present invention is not limited to the following embodiments and the accompanying drawings hereinafter, detailed description of embodiments of the present invention Various modifications are carried out in the range of purport and are implemented.In addition, in this specification " quality % " and " mass parts " respectively and " weight It is identical with " parts by weight " meaning to measure % ".

[iridium complex compound]

Iridium complex compound of the invention is the compound that following formula (1) indicates.Ir in formula (1) indicates iridium atom.

< ring Cy¹With ring Cy³>

In above-mentioned formula (1), ring Cy¹Indicate the carbon atom C comprising being coordinated in iridium atom¹And C²Aromatic rings or heteroaryl it is fragrant Ring, ring Cy³Indicate the carbon atom C comprising being coordinated in iridium atom⁴And C⁵Aromatic rings or miscellaneous aromatic rings.

As ring Cy¹With ring Cy³, can be fused rings obtained by monocycle or the bonding of multiple rings.When for fused rings, of ring Number is not particularly limited, and preferably 6 hereinafter, due to having the deliquescent trend for not damaging complex thus preferably 5 or less.

As ring Cy¹With ring Cy³, it is not particularly limited, but from the viewpoint of the chemical stability of complex, heteroaryl is fragrant The constitution element of ring in ring is other than carbon atom, preferably from nitrogen-atoms, oxygen atom, sulphur atom, silicon atom, phosphorus atoms and selenium It is selected in atom.

As ring Cy¹With ring Cy³Concrete example the phenyl ring of monocycle can be enumerated in aromatic rings each independently；Two rings Naphthalene nucleus；More than tricyclic fluorenes ring, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene ring, BaP ring,Ring, benzo phenanthrene ring, fluoranthene Ring etc..

In addition, the furan nucleus containing oxygen atom, benzofuran ring, dibenzofurans ring can be enumerated in miscellaneous aromatic rings；Sulfur-bearing The thiphene ring of atom, benzothiophene ring, dibenzothiophenes ring；Pyrrole ring, pyrazole ring, imidazole ring, the benzimidazole of nitrogen atom Ring, indole ring, indazole ring, carbazole ring, indolocarbazole ring, indeno carbazole ring, pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, Triazine ring, quinoline ring, isoquinolin ring, cinnolines ring, phthalazines ring, quinoxaline ring, quinazoline ring, quinazolinone ring, acridine ring, phenanthridines Ring, carboline ring or purine ring；Containing there are many heteroatomicAzoles ring,It is diazole ring, differentAzoles ring, benzisoxaAzoles ring, Thiazole ring, benzothiazole ring, isothiazole ring, benzisothiazole ring etc..

Wherein, organic EL element is used as in order to control emission wavelength or improve dissolubility in a solvent or improve Durability, usually import substituent group appropriate on these rings, the introduction method of preferably such substituent group is well-known Ring.

Therefore, among above-mentioned concrete example, preferably direct bonding is in the carbon atom C of iridium atom¹Or C⁴The ring constituted Aromatic rings, dibenzofurans ring, dibenzothiophenes ring, carbazole ring, indolocarbazole ring, indenes can be enumerated as its example for phenyl ring And carbazole ring etc..Wherein, further preferred phenyl ring, naphthalene nucleus, fluorenes ring, dibenzofurans ring, dibenzothiophenes ring and carbazole ring, more Further preferred phenyl ring or naphthalene nucleus.

Ring Cy¹With ring Cy³The atomicity of composition ring be not particularly limited, from maintaining the deliquescent of iridium complex compound Viewpoint considers that the constituting atom number of the ring is respectively preferably 5 or more, more preferably 6 or more.In addition, the constituting atom number of the ring 30 are respectively preferably hereinafter, more preferably 20 or less.

< ring Cy²>

Ring Cy in above-mentioned formula (1)²To include carbon atom C³With the nitrogen-atoms N for being coordinated in iridium atom¹Following formula (2)~ Any one of (5) structure indicated.Carbon atom C³With above-mentioned ring Cy¹In carbon atom C²Bonding.

Ring Cy²For the structure that any one of formula (2)~(5) indicate, thus it enables that the maximum hair of iridium complex compound Optical wavelength easily long wavelengthization.

On the other hand, right using known structure, such as quinoline or quinazoline skeleton in the case where long wavelengthization In these ligands, need to extend the conjugation or substitution electron-withdrawing group in place or electron-donating group of pi-electron.But Since in this way, the reduction of luminescent quantum yield is made since the freedom degree of molecular motion increases instead, or make the HOMO/ of complex Lumo energy changes greatly, therefore the loads such as driving service life reduction can be generated when the luminescent material as organic EL element uses Sorrow.

Iridium complex compound of the invention, which has, is used as ring Cy²The nitrogen-atoms of the naphthyridines skeleton as shown in formula (2)~(5) is coordinated In the cyclometallated ligand of iridium.

Because naphthyridines skeleton it is biggish electron-withdrawing due to substantially reduce the LUMO of iridium complex compound, as a result can issue The red phosphorescent of more long wavelength.Meanwhile by being coordinated all ligands of the iridium complex compound by carbon atom and nitrogen-atoms In the cyclometallated ligand of the bidentate of iridium, thus it is more stable in chemistry, it can expect in the phosphorescence hair as organic EL element Luminescent material using when show high-durability.

The ligand of naphthyridines skeleton is minimum 1 in iridium complex compound, and other ligands are (that is, include ring Cy¹, ring Cy³With ring Cy⁴Structure assistant ligand) can be used and ring Cy²Structure is different to be coordinated in iridium by carbon atom and nitrogen-atoms The assistant ligand of bidentate can carry out the fine tuning of emission wavelength, deliquescent control according to the type of these assistant ligands.It is special It is not, the ligand of naphthyridines skeleton is greater than by using the band gap of HOMO-LUMO and the distribution more localization of HOMO and LUMO can be made Change the assistant ligand on the ligand of naphthyridines skeleton, can expect the raising of luminescent quantum yield and the increase of chemical stability.

As ring Cy², among above structure, from the ideal coloration of the emitting red light shown in organic el display From the viewpoint of, the preferably structure that indicates of formula (2), formula (3) or formula (4), the knot that further preferred formula (2) or formula (4) indicate Structure, the structure that particularly preferred formula (4) indicates.

< ring Cy⁴>

Ring Cy in above-mentioned formula (1)⁴It indicates to include carbon atom C⁶With the nitrogen-atoms N for being coordinated in iridium atom²Miscellaneous aromatic rings. In addition, carbon atom C⁶With above-mentioned ring Cy³In carbon atom C⁵Bonding.

Specifically, the pyridine ring of monocycle, pyridazine ring, pyrimidine ring, pyridine ring, triazine ring, pyrrole ring, pyrazoles can be enumerated It is ring, differentAzoles ring, thiazole ring,Azoles ring,Diazole ring, thiazole ring, purine ring；Bicyclic-fused quinoline ring, isoquinolin Ring, cinnolines ring, phthalazines ring, quinazoline ring, quinoxaline ring, naphthyridines ring, indole ring, indazole ring, benzisoxaAzoles ring, benzisoxa Thiazole ring, benzimidazole ring, benzoAzoles ring, benzothiazole ring；Tricyclic condensed acridine ring, phenanthroline ring, carbazole ring, click Quinoline ring；Benzophenanthrene phenazine ring, benzacridine ring or indoles and carboline ring for more than Fourth Ring condensing etc..

Wherein, due to it is more know to be easily guided into substituent group and be easily adjusted emission wavelength or dissolubility and with iridium When forming complex can yield synthetic method well, therefore preferably Fourth Ring fused rings below, below more preferable tricyclic Fused rings, most preferably monocycle or the fused rings of two rings.

Wherein, preferably imidazole ring,Azoles ring, thiazole ring, benzimidazole ring, benzoAzoles ring, benzothiazole ring, pyridine Ring, quinoline ring, isoquinolin ring, pyridazine ring, pyrimidine ring, pyridine ring, triazine ring, cinnolines ring, phthalazines ring, quinazoline ring, quinoxaline Ring or naphthyridines ring, more preferable benzimidazole ring, benzoAzoles ring, benzothiazole ring, pyridine ring, imidazole ring,Azoles ring, quinoline Ring, isoquinolin ring, pyridazine ring, pyrimidine ring or pyridine ring.Further preferred benzimidazole ring, benzoAzoles ring, benzothiazole Ring, pyridine ring, isoquinolin ring, pyridazine ring, pyrimidine ring or pyridine ring, particularly preferred benzimidazole ring, benzothiazole ring or pyridine Ring.Wherein, most preferably benzothiazole ring.

Ring Cy⁴In the atomicity of composition ring be not particularly limited, from the deliquescent viewpoint for maintaining iridium complex compound Considering, the constituting atom number of the ring is preferably 5 or more, and more preferably 6 or more.In addition, the constituting atom number of the ring is preferably 30 Hereinafter, more preferably 20 or less.

< R¹~R⁴>

R in above-mentioned formula (1)¹~R⁴It respectively indicates and is bonded to ring Cy¹~ring Cy⁴Hydrogen atom or substituent group.In addition, R¹~ R⁴Be it is independent, may be the same or different.R¹~R⁴When being respectively present multiple, they can be identical, can also not Together.

A, c and d is respectively in ring Cy¹, ring Cy³With ring Cy⁴The maximum integer of upper substitutive group, b 5.

In addition, the R of 2 or more adjoinings¹Each other, R²Each other, R³Each other or R⁴It can be mutually bonded each other and form fat Race, aromatic series or heteroaromatic (heteroaromatic) monocycle or fused rings.

R¹~R⁴Kind be not particularly limited, it is contemplated that the accurate control of the emission wavelength of target or with it is used molten The compatibility of agent, with the compatibility of host compound etc. when organic EL element is made and select optimal substituent group.Carry out When these optimizing research, preferred substituent group is each independently the substitution of hydrogen atom or the substituent group selected from following description Base.

(substituent group)

As substituent group ,-D ,-F ,-Cl ,-Br ,-I ,-N (R ') can be enumerated₂,-CN ,-NO₂,-OH ,- COOR ' ,-C (=O) R ' ,-C (=O) NR ' ,-P (=O) (R ')₂,-S (=O) R ' ,-S (=O)₂R ' ,-OSO₂R ', carbon Straight-chain, branched or the cyclic alkyl of atomicity 1~30, the straight-chain of carbon atom number 1~30, branched or cyclic annular alcoxyl Base, the straight-chain of carbon atom number 1~30, branched or cyclic alkylthio, the straight-chain of carbon atom number 2~30, branched or ring Shape alkenyl, the straight-chain of carbon atom number 2~30, branched or cyclic alkyne, the aromatic group of carbon atom number 5~60, carbon are former The heteroaromatic group of subnumber 5~60, the aryloxy group of carbon atom number 5~40, the arylthio of carbon atom number 5~40, carbon atom number 5 ~60 aralkyl, the heteroarylalkyl of carbon atom number 5~60, the ammonia diaryl base of carbon atom number 10~40, carbon atom number 10~ 40 aryl heteroaryl amino or two heteroaryl aminos of carbon atom number 10~40.

The alkyl, the alkoxy, the alkylthio group, the alkenyl, the alkynyl, the aralkyl and the heteroarylalkyl can be further It is replaced by 1 or more R ', 1-CH in these group₂Not adjacent-the CH of base or 2 or more₂Base can be taken On behalf of-CR '=CR ' ,-C ≡ C- ,-Si (R ') 2- ,-C (=O)-,-NR '-,-O- ,-S- ,-C (=O) NR '-or divalent fragrance Race's group.In addition, 1 or more hydrogen atom in these groups can be replaced by D, F, Cl, Br, I or CN.

The aromatic group, the heteroaromatic group, the aryloxy group, the arylthio, the ammonia diaryl base, the aryl heteroaryl Base amino and two heteroaryl amino can be further replaced by 1 or more R ' each independently.It is carried out about R ' aftermentioned.

As the example of the straight-chain of carbon atom number 1~30, branched or cyclic alkyl, methyl, ethyl, positive third can be enumerated Base, isopropyl, normal-butyl, n-pentyl, n-hexyl, n-octyl, 2- ethylhexyl, isopropyl, isobutyl group, cyclopenta, cyclohexyl, N-octyl, norborny, adamantyl etc..From the viewpoint of durability, carbon atom number preferably 1 or more, additionally, it is preferred that 30 with Under, more preferable 20 hereinafter, most preferably 12 or less.

As the example of the straight-chain of carbon atom number 1~30, branched or cyclic alkoxy, methoxyl group, ethoxy can be enumerated Base, positive propoxy, n-butoxy, positive hexyloxy, isopropoxy, cyclohexyloxy, 2- ethoxy ethoxy, 2- ethoxy ethoxy Ethyoxyl etc..From the viewpoint of durability, carbon atom number preferably 1 or more, additionally, it is preferred that 30 hereinafter, more preferable 20 hereinafter, most It is preferred that 12 or less.

As the example of the straight-chain of carbon atom number 1~30, branched or cyclic alkylthio, methyl mercapto, second sulphur can be enumerated Base, positive rosickyite base, positive butylthio, just own sulfenyl, isopropyisulfanyl, cyclohexylthio, 2- methylbutylthio, just own sulfenyl etc..From resistance to From the viewpoint of long property, carbon atom number preferably 1 or more, additionally, it is preferred that 30 hereinafter, more preferable 20 hereinafter, most preferably 12 or less.

As the example of the straight-chain of carbon atom number 2~30, branched or cyclic alkenyl radical, can enumerate vinyl, allyl, Acrylic, heptenyl, cyclopentenyl, cyclohexenyl group, cyclo-octene base etc..From the viewpoint of durability, carbon atom number preferably 2 with On, additionally, it is preferred that 30 hereinafter, more preferable 20 hereinafter, most preferably 12 or less.

As the example of the straight-chain of carbon atom number 2~30, branched or cyclic alkyne, can enumerate acetenyl, propinyl, Butynyl, pentynyl, hexin base, heptynyl, octynyl etc..From the viewpoint of durability, carbon atom number preferably 2 or more, separately Outside, preferably 30 hereinafter, more preferable 20 hereinafter, most preferably 12 or less.

The aromatic group of carbon atom number 5~60 and the heteroaromatic group of carbon atom number 5~60 can be with single rings Or the form of fused rings exists, or be further bonded on a ring or the condensed aromatic group for having other types or Group made of heteroaromatic group.

As their example, can enumerate phenyl, naphthalene, anthryl, benzo anthryl, phenanthryl, benzo phenanthryl, pyrenyl,Base, Fluoranthene base, base, benzo pyrenyl, benzofluoranthrene base, tetrad phenyl, 5-linked phenyl, xenyl, terphenyl, fluorenyl, two fluorenes of spiral shell Base, dihydrophenanthrenyl, dihydro pyrenyl, tetrahydro pyrenyl, indeno fluorenyl, furyl, benzofuranyl, isobenzofuran-base, dibenzo Furyl, thienyl, benzothienyl, dibenzothiophene, pyrrole radicals, indyl, isoindolyl, carbazyl, benzo carbazole Base, indolocarbazole base, indeno carbazyl, pyridyl group, cinnoline base, different cinnoline base, acridinyl, phenanthridinyl, phenothiazinyl, phenoPiperazine base, pyrazolyl, indazolyl, imidazole radicals, benzimidazolyl, naphtho- imidazole radicals, phenanthro- imidazole radicals, pyridine imidazole radicals, Oxazolyl, benzoOxazolyl, naphtho-Oxazolyl, thiazolyl, benzothiazolyl, pyrimidine radicals, benzo pyrimidine radicals, pyridazinyl, quinoline Quinoline base, diaza anthryl, diaza pyrenyl, pyrazinyl, phenoPiperazine base, phenothiazinyl, naphthyridines base, azepine carbazyl, benzo click Quinoline base, Phen, triazolyl, benzotriazole base,Di azoly, thiadiazolyl group, triazine radical, 2,6- diphenyl -1,3,5- three Piperazine -4- base, tetrazole radical, purine radicals, diazosulfide base etc..

From the viewpoint of dissolubility and the balance of durability, the carbon atom number of these groups is preferably 5 or more, in addition, Preferably 50 hereinafter, more preferably 40 hereinafter, most preferably 30 or less.

The example of aryloxy group as carbon atom number 5~40 can enumerate phenoxy group, methylphenoxy, naphthoxy, methoxyl group Phenoxy group etc..From the viewpoint of dissolubility and the balance of durability, carbon atom number preferably 5 or more, additionally, it is preferred that 30 hereinafter, More preferable 25 hereinafter, most preferably 20 or less.

The example of arylthio as carbon atom number 5~40 can enumerate thiophenyl, methylphenyl-sulfanyl, naphthalene sulfenyl, methoxyl group Thiophenyl etc..From the viewpoint of dissolubility and the balance of durability, carbon atom number preferably 5 or more, additionally, it is preferred that 30 hereinafter, More preferable 25 hereinafter, most preferably 20 or less.

The example of aralkyl as carbon atom number 5~60 can enumerate 1,1- dimethyl -1- phenyl methyl, 1,1- bis- just Butyl -1- phenyl methyl, 1,1- di-n-hexyl -1- phenyl methyl, 1,1- di-n-octyl -1- phenyl methyl, phenyl methyl, phenyl Ethyl, 3- phenyl-1- propyl, 4- phenyl-1- normal-butyl, 1- methyl-1-phenylethyl, 5- phenyl-1- n-propyl, 6- phenyl- 1- n-hexyl, 6- naphthalene -1- n-hexyl, 7- phenyl -1- n-heptyl, 8- phenyl -1- n-octyl, 4- phenylcyclohexyl etc..From molten From the viewpoint of the balance of Xie Xingyu durability, carbon atom number preferably 5 or more, in addition, more preferably 40 or less.

The example of heteroarylalkyl as carbon atom number 5~60, can enumerate 1,1- dimethyl -1- (2- pyridyl group) methyl, 1,1- di-n-hexyl -1- (2- pyridyl group) methyl, (2- pyridyl group) methyl, (2- pyridyl group) ethyl, 3- (2- pyridyl group) -1- third Base, 4- (2- pyridyl group)-1- normal-butyl, 1- methyl-1-(2- pyridyl group) ethyl, 5- (2- pyridyl group)-1- n-propyl, 6- (2- Pyridyl group) -1- n-hexyl, 6- (2- pyrimidine radicals) -1- n-hexyl, 6- (2,6- diphenyl -1,3,5- triazine -4- base) -1- just oneself Base, 7- (2- pyridyl group) -1- n-heptyl, 8- (2- pyridyl group) -1- n-octyl, 4- (2- pyridyl group) cyclohexyl etc..From dissolubility From the viewpoint of the balance of durability, the carbon atom number of these groups is preferably 5 or more, additionally, it is preferred that for 50 hereinafter, more excellent 40 are selected as hereinafter, most preferably 30 or less.

The example of ammonia diaryl base as carbon atom number 10~40, can enumerate diphenyl amino, phenyl (naphthalene) amino, Two (xenyl) amino, two (para-terpheny base) amino etc..From the viewpoint of dissolubility and the balance of durability, these groups Carbon atom number be preferably 10 or more, additionally, it is preferred that being 36 hereinafter, more preferably 30 hereinafter, most preferably 25 or less.

The example of aryl heteroaryl amino as carbon atom number 10~40 can enumerate phenyl (2- pyridyl group) amino, benzene Base (2,6- diphenyl -1,3,5- triazine -4- base) amino etc..From the viewpoint of dissolubility and the balance of durability, these bases The carbon atom number of group is preferably 10 or more, additionally, it is preferred that for 36 hereinafter, more preferably 30 hereinafter, most preferably 25 or less.

As two heteroaryl aminos of carbon atom number 10~40, two (2- pyridyl group) amino, two (2,6- hexichol can be enumerated Base -1,3,5- triazine -4- base) amino etc..From the viewpoint of dissolubility and the balance of durability, the carbon atom number of these groups Preferably 10 or more, additionally, it is preferred that for 36 hereinafter, more preferably 30 hereinafter, most preferably 25 or less.

Above-mentioned R¹~R⁴Can be mutually the same when they are multiple, it can also be different from each other.

In above-mentioned R¹~R⁴Among, from the sight for not damaging the durability as the luminescent material in organic EL element especially Point considers, be more preferably each independently hydrogen atom, F ,-CN, the straight-chain of carbon atom number 1~30, branched or cyclic alkyl, The aryloxy group of carbon atom number 5~40, the arylthio of carbon atom number 5~40, the ammonia diaryl base of carbon atom number 10~40, carbon atom The heteroaromatic group of the aralkyl of number 5~60, the aromatic group of carbon atom number 5~60 or carbon atom number 5~60, into one Step is preferably each independently hydrogen atom, F ,-CN, the straight-chain of carbon atom number 1~30, branched or cyclic alkyl, carbon atom The heteroaromatic group of the aralkyl of number 5~60, the aromatic group of carbon atom number 5~60 or carbon atom number 5~60, it is optimal Choosing be each independently hydrogen atom, F, CN, the straight-chain of carbon atom number 1~30, branched or cyclic alkyl, carbon atom number 5~ 60 aromatic group or the heteroaromatic group of carbon atom number 5~60.

Above-mentioned R¹~R⁴The position of substitution be not particularly limited.Wherein, R¹Or R³In ring Cy¹Or ring Cy³Respectively phenyl ring when, In the case where paying attention to the durability of complex, preferably R¹Or R³At least 4 or 5 of the phenyl ring are replaced in, further preferably extremely It is replaced in 4 less.The R¹Or R³Preferably above-mentioned aromatic group or heteroaromatic group.

R²Sometimes preferably in ring Cy²In be unworthy of that there are at least one positioned at the ortho position of nitrogen-atoms of iridium atom.Reason is: Due to blocking the nitrogen-atoms using sterically hindered, solvation etc. can be mitigated from externalities, inhibit to emission wavelength and The influence of other physical property.

< R ' >

The R of above-mentioned formula (1)¹~R⁴In R ' be each independently selected from-H ,-D ,-F ,-Cl ,-Br ,-I ,-N (R ")₂、-CN、- NO₂、-Si(R”)₃、-B(OR”)₂,-C (=O) R " ,-P (=O) (R ")₂,-S (=O)₂R”、-OSO₂R ", carbon atom number 1~30 Straight-chain, branched or cyclic alkyl, the straight-chain of carbon atom number 1~30, branched or cyclic alkoxy, carbon atom number 1~ 30 straight-chain, branched or cyclic alkylthio, straight-chain, branched or the cyclic alkenyl radical of carbon atom number 2~30, carbon atom number 2~30 straight-chain, branched or cyclic alkyne, the aromatic group of carbon atom number 5~60, carbon atom number 5~60 heteroaryl Fragrant race's group, the aryloxy group of carbon atom number 5~40, the arylthio of carbon atom number 5~40, the aralkyl of carbon atom number 5~60, carbon The heteroarylalkyl of atomicity 5~60, the ammonia diaryl base of carbon atom number 10~40, carbon atom number 10~40 aryl heteroaryl ammonia Two heteroaryl aminos of base or carbon atom number 10~40.

The alkyl, the alkoxy, the alkylthio group, the alkenyl, the alkynyl, the aralkyl and the heteroarylalkyl can be further It is replaced by 1 or more R ', 1-CH in these groups₂Not adjacent-the CH of base or 2 or more₂Base can be substituted For-CR "=CR "-,-C ≡ C- ,-Si (R ")₂,-C (=O)-,-NR "-,-O- ,-S- ,-C (=O) NR "-or divalent aromatic series base Group.In addition, the more than one hydrogen atom in these groups can be replaced by D, F, Cl, Br, I or-CN.

In addition, the aromatic group, the heteroaromatic group, the aryloxy group, the arylthio, the ammonia diaryl base, the virtue Base heteroaryl amino and two heteroaryl amino can be further replaced by 1 or more R ".It is carried out about R " aftermentioned.

The example of above-mentioned group in R ' respectively with above-mentioned < R¹~R⁴The record meaning of group in > is identical.

In addition, the R ' of 2 or more adjoinings can be mutually bonded and be formed the monocycle of aliphatic, aromatic series or heteroaromatic Or fused rings.

< R " >

R " in above-mentioned R ' is each independently selected from H, D, F, CN, the aliphatic alkyl of carbon atom number 1~20, carbon atom number 1~20 aromatic group or the heteroaromatic group of carbon atom number 1~20.

The R " of 2 or more adjoinings can be mutually bonded and be formed the monocycle or thick of aliphatic, aromatic series or heteroaromatic Cyclization.

< concrete example >

The preferred concrete example of iridium complex compound of the invention described below, but the present invention is not limited to this.

< maximum luminous wavelength >

Iridium complex compound of the invention can make emission wavelength more long wavelength.As the length for indicating emission wavelength Index is preferably 620nm or more according to the maximum luminous wavelength that step described below is measured, more preferably 625nm or more, Further preferably 630nm or more.Additionally, it is preferred that 700nm is hereinafter, more preferably 680nm or less.By in these ranges, thus In the presence of can embody as organic el display preferred red illuminating material preferred color.

(measuring method)

Utilize spectrophotometer (the organic EL quantum yield measurement device C9920- of Hamamatsu Photonics corporation 02), to make at normal temperature the iridium complex compound with 1 × 10^{- 4}Mol/L concentration below be dissolved in 2- methyltetrahydrofuran and The solution obtained measures phosphorescence spectrum.The wavelength for showing the maximum value of obtained phosphorescence spectrum intensity is considered as in the present invention most Big emission wavelength.

[synthetic method of iridium complex compound]

The synthetic method > of < ligand

The ring Cy with naphthyridines skeleton of the ligand of iridium complex compound of the invention²Synthesis can by combination known to Organic synthesis and carry out.Naphthyridines skeleton is the key that the skeleton as pharmaceuticals compound, therefore its synthetic method crowd institute It is known.Especially based on Suzuki-palace Pu coupling reaction and pyridine ring synthetic reaction, substituent group further is combined to them and is imported instead It answers, thus, it is possible to synthesize various derivatives.

Hereinafter, being illustrated with illustrating.It should be noted that R indicates hydrogen atom or appoints in scheme (A) below~scheme (D) The substituent group of meaning, there are multiple R may be the same or different.In addition, Me indicates that methyl, Et indicate ethyl.

The inverse synthesis side of 1 example of the synthesis of 1,7- naphthyridines skeleton of the invention is shown as in above scheme (A) Case.1,7- naphthyridines skeleton can pass through the cyclization of 3- amino -4- acyl pyridine intermediate and aromatic methyl ketone intermediate And it synthesizes.The former can be derived by 3- aminoisonicotinic acid.The 3- aminoisonicotinic acid can be further by using note in scheme (A) The method recorded in the literature carried is synthesized in the form of having halogen atom or trifluoromethanesulfonic acid ester group at an arbitrary position.

It can further utilize Suzuki-palace Pu coupling reaction that they are imported with the substituent group of various forms.The substituent group Import can ligand synthesis phase midway or be finally introducing, or can also be by being temporarily forming in the midway that ligand synthesizes It is further set to react and import after iridium complex compound.

The inverse synthesis side of 1 example of the synthesis of 1,5- naphthyridines skeleton of the invention is shown as in above scheme (B) Case.1,5- naphthyridines skeleton can pass through the cyclization of 3- amino -2- acyl pyridine intermediate and aromatic methyl ketone intermediate And it synthesizes.The former can be derived by 3- aminopicolinate.The 3- aminopicolinate can be further by using scheme (B) The method recorded in the literature of middle record is synthesized in the form of having halogen atom at an arbitrary position.

In addition, 1,6- naphthyridines ring, 1,8- naphthyridines ring can also by being used using corresponding amino carboxyl pyridine as raw material, Target ligand is synthesized using with above-mentioned almost same chemical conversion.

The naphthyridines cyclization carried out using the cyclization of above-mentioned amino carboxyl pyridine intermediate and methyl ketone At reaction be referred to as Friedlaender reaction, can with bibliography (Chem.Rev.2009,109,2652, or, Organic Reactions, 28 (2), 37-201) and implement.Alternatively, for example also can use document (Chem.Pharm.Bull.24 (8) 1813-1821 (1976)) in record other methods and synthesize.

The synthetic method > for the iridium complex compound that < formula (1) indicates

The iridium complex compound of the invention that formula (1) indicates can use combination of known method etc. and synthesize.Below It is described in detail.

For the synthetic method of iridium complex compound, following method may be exemplified: using phenyl pyrazoline in order to facilitate understanding Shown in the following proposal (C) of pyridine ligand as an example via chlorine crosslinking iridium binuclear complex method (M.G.Colombo, T.C.Brunold, T.Riedener, H.U.Gudel, Inorg.Chem., 1994,33,545-550), shown in following proposal (D) So that chlorine crosslinking is exchanged with acetyl pyruvate and is obtained object after being converted into mononuclear complex by binuclear complex Method (S.Lamansky, P.Djurovich, D.Murphy, F.Abdel-Razzaq, R.Kwong, I.Tsyba, M.Borz, B.Mui, R.Bau, M.Thompson, Inorg.Chem., 2001,40,1704-1711) etc., but not limited to this.

For example, the typical reaction condition that following proposal (C) indicates is as follows.As the first step, pass through 2 equivalent of the first ligand With 1 reacting for equivalent of iridium chloride n hydrate and synthesize chlorine crosslinking iridium binuclear complex.Solvent usually using cellosolvo and The mixed solvent of water, can also the solvent-free or other solvents of use.By using excessive ligand or alkali can also be used Additives are waited to promote to react.Also other bridging property anion ligands such as bromine can be used to replace chlorine.

Reaction temperature is not particularly limited, it is usually preferred to 0 DEG C or more, more preferable 50 DEG C or more.Additionally, it is preferred that 250 DEG C with Under, more preferable 150 DEG C or less.By in these ranges, to have in the case where being not accompanied by by-product or decomposition reaction only It carries out goal response and obtains highly selective trend.

Second step contacts it with Ligands by halide ion agent for capturing as addition silver trifluoromethanesulfonate To title complex.Solvent, can be solvent-free according to the type of ligand usually using ethoxy ethanol or diethylene glycol dimethyl ether Or other solvents are used, multi-solvents can also be mixed and used.

Even if halide ion agent for capturing is not added sometimes to be reacted yet, therefore be not necessarily required to, but the capture The addition of agent is advantageous raising reaction yield, the higher facial isomer of selectivity synthesis quantum yield.Reaction temperature does not have It is particularly limited to, usually the range at 0 DEG C~250 DEG C carries out.

In addition, being illustrated to following proposal (D) typical reaction condition indicated.

The binuclear complex of the first step can synthesize in the same manner as scheme (C).Second step is by making as acetylacetone,2,4-pentanedione The alkalization of the reactive hydrogen of the 1,3- dione compounds can be captured more than 1 equivalent of 1,3- dione compounds and as sodium carbonate 1 equivalent of object or more is closed to react with the binuclear complex, so that it is converted to 1, the mononuclear complex that 3- diketonate ligand is coordinated.It is logical It is often used ethoxy ethanol, the methylene chloride equal solvent of dissolvable raw material binuclear complex, ligand can also be with nothing when being liquid The mode of solvent is implemented.Reaction temperature is not particularly limited, and usually carries out in the range of 0 DEG C~200 DEG C.

Phase III reacts the Ligands of 1 equivalent or more.The type and amount of solvent are not particularly limited, Ligands At the reaction temperatures for can be solvent-free in the case where liquid.Reaction temperature it is not also specifically limited, due to slightly lacking reactivity, Therefore it is usually reacted under 100 DEG C~300 DEG C of higher temperatures.It is therefore preferable that using the high boiling solvent such as glycerol.

It is refined after end reaction in order to remove unreacting material, byproduct of reaction and solvent.It can be using usual Synthetic Organic Chemistry in purification operations, as recorded in above-mentioned non-patent literature, mainly utilize normal phase silica gel column chromatography method And it is refined.Hexane, heptane, methylene chloride, chloroform, ethyl acetate, toluene, methyl ethyl ketone or methanol can be used in developping solution Single solvent or mixed liquor.Purification can change condition and carry out repeatedly.It can according to need and implement other chromatographic technique (reverse phases Silica gel chromatography, Size Exclusion Chromatography, paper chromatography), liquid separation cleaning, reprecipitation, recrystallization, powder suspension cleaning, subtract Press dry the purification operations such as dry.

The purposes > of < iridium complex compound

Iridium complex compound of the invention can be preferably used as material used in organic electroluminescent device, i.e. organic field The red illuminating material of electroluminescent element can also be preferably used as shining for organic electroluminescent device or other light-emitting components etc. Material.

[composition containing iridium complex compound]

Iridium complex compound of the invention is preferably used together with solvent since dissolubility is excellent.Hereinafter, to containing The composition (composition containing iridium complex compound) of iridium complex compound and solvent of the invention is illustrated.

Composition containing iridium complex compound of the invention contains above-mentioned iridium complex compound of the invention and organic molten Agent.Composition containing iridium complex compound of the invention is usually more for utilizing wet type membrane formation forming layer or film, especially It is preferably used to form the organic layer of organic electroluminescent device.The organic layer is particularly preferably luminescent layer.

That is, the composition containing iridium complex compound is preferably composition for organic electroluminescent element, and then particularly preferably As luminescent layer formation composition.

The content of iridium complex compound of the invention in the composition containing iridium complex compound is usually 0.001 matter % or more, preferably 0.01 mass % or more are measured, in addition, usually 99.9 mass % are hereinafter, preferably 99 mass % or less.It is logical Crossing makes the content of the iridium complex compound in the composition in the range, can be from adjacent layer (for example, hole transmission layer 4, sky Cave barrier layer 6) injection in hole, electronics is efficiently carried out to luminescent layer, reduce driving voltage.It should be noted that iridium of the invention Complex can only contain a kind in the composition containing iridium complex compound, can also combine and contain two or more.

In the case that composition of the invention containing iridium complex compound is used for such as organic electroluminescent device purposes, It, can be containing used in organic electroluminescent device, particularly luminescent layer other than above-mentioned iridium complex compound, solvent Charge-transporting compound.

The feelings for the luminescent layer for forming organic electroluminescent device using the composition of the invention containing iridium complex compound Under condition, iridium complex compound of the invention is preferably comprised as luminescent material, contains other charge-transporting compounds as electricity Lotus transmits material of main part.

The solvent contained in composition containing iridium complex compound of the invention is formed and is contained for being formed a film using wet type There is the layer of iridium complex compound and there is volatile liquid component.

The solvent has highly dissoluble to the iridium complex compound of the invention as solute, as long as therefore aftermentioned electricity The solvent of lotus transporting compound excellent dissolution, is just not particularly limited.As preferred solvent, for example, can enumerate n-decane, The alkanes such as hexamethylene, ethyl cyclohexane, decahydronaphthalenes, bis cyclohexane；Toluene, dimethylbenzene, mesitylene, cyclohexylbenzene, Naphthane etc. is aromatic hydrocarbon；The halogenated aromatics hydro carbons such as chlorobenzene, dichloro-benzenes, trichloro-benzenes；1,2- dimethoxy benzene, 1,3- diformazan Oxygroup benzene, methyl phenyl ethers anisole, phenetole, 2- methoxy toluene, 3- methoxy toluene, 4- methoxy toluene, 2,3- dimethylanisole, The aromatic series ethers such as 2,4- dimethylanisole, diphenyl ether；Phenylacetate, phenyl propionate, methyl benzoate, ethyl benzoate, The aromatic series esters such as propyl benzoate, n-butylbenzoate；The alicyclic ketones such as cyclohexanone, cyclooctanone, fenchone；Cyclohexanol, ring The alicyclic alcohols such as octanol；The aliphatic ketones such as methyl ethyl ketone, two butanone；The aliphatic alcohols such as butanol, hexanol；Glycol dinitrate Aliphatic ethers such as ether, ethylene glycol diethyl ether, propylene glycol -1- methyl ether acetate (PGMEA) etc..

It is wherein preferably alkanes, aromatic hydrocarbon, especially cyclohexylbenzene has ideal in wet type film-forming process Viscosity and boiling point.

These solvents can be used alone, and in addition can also use two or more with ratio in any combination.

The boiling point of solvent is usually 80 DEG C or more, preferably 100 DEG C or more, more preferably 120 DEG C or more, in addition, usually For 270 DEG C hereinafter, preferably 250 DEG C hereinafter, more preferably boiling point is 230 DEG C or less.If being lower than the range, wet type film forming When, it is possible to cause film forming stability to reduce because solvent is evaporated from composition.

The content of solvent is preferably 1 mass % or more, more preferably 10 matter in the composition containing iridium complex compound % or more, particularly preferably 50 mass % or more are measured, additionally, it is preferred that being 99.99 mass % hereinafter, more preferably 99.9 mass % Hereinafter, particularly preferably 99 mass % or less.If the content of solvent is lower than the lower limit, it is likely that the viscosity of composition is excessively high And Film forming operations reduce.On the other hand, if being higher than the upper limit, the thickness mistake of film obtained from solvent is removed after film forming It is thin, therefore have the tendency that being difficult to form a film.It should be noted that usually luminescent layer with a thickness of 3~200nm or so.

As other charge-transporting compounds that the composition of the invention containing iridium complex compound contains, can make With the previous charge-transporting compound for being used as organic electroluminescent device material.Such as can enumerate pyridine, carbazole, naphthalene, Pyrene, anthracene,Quaterphenyl, phenanthrene, coronene, fluoranthene, benzophenanthrene, fluorenes, acetyl naphtho- fluoranthene, cumarin, to bis- (2- phenylethylenes Base) benzene and they derivative, quinacridone derivative, 4- (dicyano methylene) -2- methyl -6- (p- dimethylamino benzene Vinyl) -4H- pyrans (DCM, (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) - 4H-pyran)) based compound, 1-benzopyran derivatives, Rhodamine Derivatives, benzo thia anthracene derivant, azepine benzo thia Anthracene, substitution have the condensation aromatic ring compound of arylamino, substitution to have styryl derivative of arylamino etc..

They can be used alone, and in addition can also use two or more with ratio in any combination.

In addition, the content of other charge-transporting compounds in the composition containing iridium complex compound is matched relative to containing iridium 1 mass parts of iridium complex compound of the invention in the composition of position compound are usually 1000 below the mass preferably 100 Below the mass, further preferably 50 below the mass, usually more than 0.01 mass parts, it is more than preferably 0.1 mass parts, It is more than further preferably 1 mass parts.

It, as needed, can be in addition to above-mentioned compound etc. in composition containing iridium complex compound of the invention Further contain other compounds.For example, other solvents can also be contained in addition to above-mentioned solvent.As such solvent, example N,N-Dimethylformamide, n,N-dimethylacetamide amides, dimethyl sulfoxide etc. can such as be enumerated.They can individually make With a kind, in addition two or more can also be used with ratio in any combination.

[organic electroluminescent device]

Organic electroluminescent device of the invention at least has anode, cathode and above-mentioned anode and above-mentioned cathode on substrate Between at least 1 layer of organic layer, which is characterized in that at least 1 layer in above-mentioned organic layer contains complex of the invention.On Stating organic layer includes luminescent layer.

Organic layer containing complex of the invention is more preferably the layer formed using the composition in the present invention, into The layer that one step is formed preferably by wet type membrane formation.It is preferably the luminescent layer by the layer that above-mentioned wet type membrane formation is formed.

Fig. 1 is the schematic diagram for indicating the section of the preferred structural example of organic electroluminescent device 10 of the invention, in Fig. 1, Symbol 1 indicates that substrate, symbol 2 indicate that anode, symbol 3 indicate that hole injection layer, symbol 4 indicate that hole transmission layer, symbol 5 indicate Luminescent layer, symbol 6 indicate that hole blocking layer, symbol 7 indicate that electron transfer layer, symbol 8 indicate that electron injecting layer, symbol 9 indicate Cathode.

Material suitable for these structures can apply well known material, be not particularly limited, but below as an example Son records representative materials, the preparation method about each layer.In addition, when reference bulletin, paper, it can be in those skilled in the art The common knowledge of member suitably uses, using the content.

(substrate 1)

Substrate 1 is the supporting mass of organic electroluminescent device, usually using quartz or glass plate, metal plate, metal foil, modeling Expect film or piece etc..Wherein, the preferred transparent synthetic resin such as glass plate or polyester, polymethacrylates, polycarbonate, polysulfones Plate.From being not easy from the aspect of the deterioration of organic electroluminescent device occurs because of outside air, substrate 1 is preferably gas barrier The high material of property.Therefore, especially when using the barrier properties for gases in this way such as plastic substrate low material, preferably in base Fine and close silicon oxide layer etc. is arranged to improve barrier properties for gases in at least single side of plate 1.

(anode 2)

Anode 2 undertakes the function to the layer of luminescent layer side injection hole.Anode 2 is usually by aluminium, gold, silver, nickel, palladium, platinum etc. Metal；The metal oxides such as the oxide of indium and/or tin；The metal halides such as cupric iodide；It is carbon black and poly- (3 methyl thiophene), poly- Electroconductive polymers such as pyrroles, polyaniline etc. are constituted.It is dry that the formation of usual anode 2 passes through sputtering method, vacuum vapour deposition etc. mostly Formula method carries out.In addition, using the particles such as the metal particles such as silver, cupric iodide, carbon black, the metal oxide microparticle of electric conductivity, conduction Property macromolecule micropowder etc. and when forming anode 2, can also be by being scattered in binder resin solution appropriate and being coated on base It is formed on plate.In addition, film can also be directly formed on substrate by being electrolysed to be overlapped when being electroconductive polymer, or The applying conductive macromolecule on substrate and form anode 2 (Appl.Phys.Lett., volume 60, page 2711,1992 years).

Anode 2 is usually single layer structure, and stepped construction can also suitably be made.It, can be the when anode 2 is stepped construction Different conductive materials is laminated on 1 layer of anode.

The thickness of anode 2 can be determined according to the required transparency and material etc..Especially when requiring high transparency, It is preferred that the transmissivity of visible light reaches 60% or more thickness, further preferably reach 80% or more thickness.The thickness of anode 2 Usually 5nm or more, preferably 10nm or more, in addition, usually 1000nm is hereinafter, preferably 500nm or less.On the other hand, When not needing the transparency, any thickness can be made according to required intensity etc. in the thickness of anode 2, in this case, anode 2 can Think thickness identical with substrate 1.

When the surface of anode 2 is formed a film, preferably by implementing ultraviolet light+ozone, oxygen plasma, argon before film forming The processing of plasma etc. and remove the impurity on anode, and pre-adjust its ionization potential and improve hole injection.

(hole injection layer 3)

It undertakes from the layer of the function of anode side luminescent layer side transporting holes and is commonly known as hole injection/transport layer or sky Cave transport layer.Moreover, undertake from the layer of the function of anode side luminescent layer side transporting holes be 2 layers or more when, will be closer to sun The layer of pole side is known as hole injection layer 3.Strengthening from anode in terms of the function of luminescent layer side transporting holes, it is preferable to use Hole injection layer 3.When using hole injection layer 3, in general, hole injection layer 3 is formed on anode.

The film thickness of hole injection layer 3 is usually 1nm or more, preferably 5nm or more, in addition, usually 1000nm is hereinafter, excellent It is selected as 500nm or less.

The forming method of hole injection layer 3 can be vacuum vapour deposition, or wet type membrane formation.It is excellent in film forming Aspect on, preferably formed by wet type membrane formation.

Hole injection layer 3 preferably comprises hole transport ability compound, further preferably hole transport ability compound and electronics Acceptance compound.Radical cation compound is further preferably comprised in hole injection layer, particularly preferably containing freely Base cation compound and hole transport ability compound.

(hole transport ability compound)

Hole injection layer formation usually contains the hole transport ability compound as hole injection layer 3 with composition.In addition, When for wet type membrane formation, usually also further contain solvent.The preferred hole transport ability of hole injection layer formation composition it is high and It can efficiently transmit by injected holes.It is therefore preferable that hole mobility is big, it is not likely to produce into during fabrication or using whens waiting For the impurity of trap.Additionally, it is preferred that excellent in stability, ionization potential is small, high to the transparency of visible light.In particular, being infused in hole When entering layer 3 and connecting with luminescent layer 5, preferably will not future light emitting layer 5 luminous delustring, do not form that swash base compound with luminescent layer 5 Object and reduce luminous efficiency.

As hole transport ability compound, from anode 2 to the charge injection barrier of hole injection layer 3 from the viewpoint of, it is excellent Select the compound of the ionization potential with 4.5eV~6.0eV.As the example of hole transport ability compound, aromatic amine can be enumerated Based compound, phthalocyanine based compound, porphyrin based compound, oligo-thiophenes based compound, polythiophene based compound, benzyl phenyl system Compound connects compound, hydrazone based compound, silazane based compound based compound, quinacridone obtained by tertiary amine with fluorenyl Based compound etc..

In above-mentioned exemplary compounds, from the aspect of amorphism and visible light permeability, optimization aromatic amination Close object, particularly preferred aromatic uncle amine compound.Here, aromatic uncle amine compound refers to the change with aromatic nitrile base structure Object is closed, also comprising the compound with the group from aromatic nitrile base.

The type of aromatic uncle amine compound is not particularly limited, and obtains uniformly from surface smoothing effect easy to use Shine from the aspect of, it is preferable to use weight average molecular weight be 1000~1000000 high-molecular compound (repetitive unit connection Polymeric compounds).As the preferred example of aromatic nitrile base high-molecular compound, can enumerate with following formula (I) tables The high-molecular compound etc. of the repetitive unit shown.

(in formula (I), Ar¹And Ar²It each independently represents the aromatic group that can have substituent group or can have substituent group Heteroaromatic group.Ar³~Ar⁵It each independently represents the aromatic group that can have substituent group or can have substituent group Heteroaromatic group.Y indicates the linking group in following linking group groups.In addition, Ar¹~Ar⁵In be bonded to it is identical Two groups of N atom can be mutually bonded and form ring.)

It is following that linking group is shown.

(in the above formulas, Ar⁶~Ar¹⁶It each independently represents the aromatic group that can have substituent group or can have and take The heteroaromatic group of Dai Ji.R⁵~R⁶Each independently represent hydrogen atom or arbitrary substituent group.)

As Ar¹~Ar¹⁶Aromatic group and heteroaromatic group, from the dissolubility of high-molecular compound, heat resistance, Hole is injected from the aspect of transporting, and the group of phenyl ring, naphthalene nucleus, phenanthrene ring, thiphene ring, pyridine ring is preferred from, further excellent Select the group from phenyl ring, naphthalene nucleus.

The concrete example of aromatic nitrile base high-molecular compound as the repetitive unit indicated with formula (I), can enumerate state Border discloses the aromatic nitrile base high-molecular compound recorded in No. 2005/089024.

(electronic acceptance compound)

In order to improve the conductivity of hole injection layer 3 by the oxidation of hole transport ability compound, preferably in sky Contain electronic acceptance compound in cave implanted layer 3.

As electronic acceptance compound, preferably with oxidability, have from above-mentioned hole transport ability compound receive The compound of the ability of one electronics, specifically, it is preferable that electron affinity is the compound of 4eV or more, it is further preferably electric Sub- affinity is the compound of 5eV or more.

As such electronic acceptance compound, such as can enumerate selected from triarylboron, metal halide, road Lewis acid, organic acid,1 kind or 2 in salt, the salt of arylamine and metal halide and arylamine and lewis acidic salt Kind or more compound etc..Specifically, 4- isopropyl -4 '-methyldiphenyl base iodine can be enumeratedFour (pentafluorophenyl group) borates, What the organic groups such as triphenylsulfonium tetrafluoroborate replacedSalt (International Publication No. 2005/089024)；Iron chloride (III) (Japanese Unexamined Patent Publication 11-251067 bulletin), the inorganic compound of the high valence such as ammonium peroxydisulfate；The cyano such as tetracyanoethylene Compound；The aromatic series boron compounds such as three (pentafluorophenyl group) borines (Japanese Unexamined Patent Publication 2003-31365 bulletin)；Fullerene is derivative Object and iodine etc..

(radical cation compound)

As radical cation compound, preferably by as the change for removing an electronics from hole transport ability compound The ionic compound learned the radical cation of kind and anion is constituted.Wherein, radical cation comes from hole transport ability High-molecular compound when, radical cation be from the repetitive unit of high-molecular compound remove an electronics obtained by tie Structure.

As radical cation, an electricity is removed preferably from as compound described in hole transport ability compound Chemical seed obtained by son.Consider from amorphism, the transmissivity of visible light, heat resistance and dissolubility etc., preferably from conduct Chemical seed obtained by an electronics is removed in the preferred compound of hole transport ability compound institute.

Here, radical cation compound can be by by hole transport ability compound above-mentioned and electronics acceptance It closes object mixing and generates.That is, by mixing hole transport ability compound above-mentioned and electronic acceptance compound, thus Electronics occurs and is transferred to electronic acceptance compound from hole transport ability compound, generates the freedom by hole transport ability compound Base cation and the radical cation compound that anion is constituted.

PEDOT/PSS (Adv.Mater., 2000, volume 12, page 481), emeraldine hydrochloride (J.Phys.Chem., Nineteen ninety, volume 94, page 7716) etc. the radical cation compound from high-molecular compound also by carrying out oxidation polymerization (dehydrogenation polymerization) and generate.

Oxidation polymerization mentioned here refers to using peracetic dithionite etc. that monomer is chemical or electrochemical in an acidic solution Learn oxidation.When oxidation polymerization (dehydrogenation polymerization), producing high-molecular is oxidized by monomer, while generating to come from acid solution Anion be to anion, from high molecular repetitive unit remove an electronics obtained by radical cation.

< forms 3 > of hole injection layer using wet type membrane formation

It when forming hole injection layer 3 using wet type membrane formation, is generally as follows to be formed: the material of hole injection layer 3 will be become It is mixed with the solvent (hole injection layer solvent) that can dissolve the material and prepares the composition of film forming (hole injection layer is formed With composition), which is coated on composition and is equivalent to the layer of the lower layer of hole injection layer 3 (usually Anode 2) on form a film, and make it dry.

As long as hole injection layer forms the unobvious damage present invention of concentration with the hole transport ability compound in composition Effect, just be it is arbitrary, in terms of the uniformity of film thickness on, it is preferably lower, in addition, another aspect, in hole injection layer 3 It is not likely to produce in the aspect of defect, it is preferably higher.Specifically, it is preferable that being 0.01 mass % or more, further preferably 0.1 matter % or more, particularly preferably 0.5 mass % or more are measured, in addition, on the other hand, preferably 70 mass % are hereinafter, further preferably For 60 mass % hereinafter, particularly preferably 50 mass % or less.

As solvent, such as ether series solvent, ester series solvent, aromatic hydrocarbon series solvent, acid amides series solvent can be enumerated etc..

As ether series solvent, such as glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol -1- monomethyl ether acetic acid can be enumerated The fatty ethers such as ester (PGMEA) and 1,2- dimethoxy benzene, 1,3- dimethoxy benzene, methyl phenyl ethers anisole, phenetole, 2- methoxy methyl Aromatic ethers such as benzene, 3- methoxy toluene, 4- methoxy toluene, 2,3- dimethylanisole, 2,4- dimethylanisole etc..

As ester series solvent, such as phenylacetate, phenyl propionate, methyl benzoate, ethyl benzoate, benzoic acid can be enumerated Aromatic esters such as propyl ester, n-butylbenzoate etc..

As aromatic hydrocarbon series solvent, such as toluene, dimethylbenzene, cyclohexyl benzene, 3- isopropyl biphenyl, 1 can be enumerated, 2,3, 4- durol, 1,4- diisopropyl benzene, methyl naphthalene etc..As acid amides series solvent, for example, can enumerate n,N-Dimethylformamide, DMAC N,N' dimethyl acetamide etc..

In addition to this, dimethyl sulfoxide etc. also can be used.

The formation based on wet type membrane formation of hole injection layer 3 is usually carried out: preparing hole injection layer formation group After closing object, being coated on the layer (usually anode 2) for be equivalent to the lower layer of hole injection layer 3 makes its film forming, and is done It is dry.For hole injection layer 3, keep coated film dry by heating, being dried under reduced pressure etc. usually after film forming.

< forms 3 > of hole injection layer using vacuum vapour deposition

In the case where forming hole injection layer 3 using vacuum vapour deposition, in general, by the constituent material of hole injection layer 3 One kind or two or more be put into of (above-mentioned hole transport ability compound, electronic acceptance compound etc.) is set in vacuum tank Crucible in when two or more material (use, will usually be each placed in different crucibles), will be arranged in vacuum tank using vacuum pump Gas is to 10^{- 4}After Pa or so, heating crucible (when using two or more material, is usually heated respective crucible), controls earthenware The evaporation capacity of material in crucible, which is evaporated, (when using two or more material, usually separately to be controlled evaporation capacity and is steamed Hair), hole injection layer 3 is formed on the anode on the substrate staggered relatively with crucible.It should be noted that using material of more than two kinds When material, their mixture can also be put into crucible and be heated, it is made to evaporate and form hole injection layer 3.

As long as the unobvious damage of vacuum degree when vapor deposition effect of the invention, there is no limit, usually 0.1 × 10^{? 6}Torr(0.13×10^{- 4}Pa)~9.0 × 10^{- 6}Torr(12.0×10^{- 4}Pa).As long as the unobvious damage present invention of evaporation rate Effect, there is no limit, usuallyAs long as the unobvious damage of film-forming temperature when vapor deposition is originally The effect of invention, there is no limit, is preferably carried out with 10 DEG C~50 DEG C.

(hole transmission layer 4)

Hole transmission layer 4 is the layer for undertaking the function from anode side luminescent layer side transporting holes.Hole transmission layer 4 is at this Not required layer in the organic electroluminescent device of invention, but strengthening from anode 2 to the function of 5 transporting holes of luminescent layer Aspect is, it is preferable to use the layer.When using hole transmission layer 4, in general, hole transmission layer 4 is formed between anode 2 and luminescent layer 5. Additionally, there are when above-mentioned hole injection layer 3, it is formed between hole injection layer 3 and luminescent layer 5.

The film thickness of hole transmission layer 4 is usually 5nm or more, preferably 10nm or more, in addition, on the other hand, usually 300nm is hereinafter, preferably 100nm or less.

The forming method of hole transmission layer 4 can be vacuum vapour deposition, or wet type membrane formation.It is excellent in film forming Aspect on, preferably formed by wet type membrane formation.

Hole transmission layer 4 usually contains the hole transport ability compound as hole transmission layer 4.As hole transmission layer 4 In the hole transport ability compound that contains, can especially enumerate with 4,4 '-bis- [N- (1- naphthalene)-N- phenyl amino] biphenyl as representative Containing 2 or more tertiary amine and replace the aromatic diamine that has 2 or more fused aromatic rings on nitrogen-atoms (Japan be special Open flat 5-234681 bulletin), the aromatic series with star burst structure such as 4,4 ', 4 "-three (1- naphthylphenyl amino) triphenylamines They they amine compounds (J.Lumin., 72-74 volume, page 985,1997), the aromatic amine chemical combination that is made of the tetramer of triphenylamine Object (Chem.Commun., page 2175,1996), 2,2 ', 7,7 '-four (diphenyl amino) -9, the spiro compounds such as 9 '-spiral shell, two fluorenes Object (Synth.Metals, volume 91, page 209,1997), 4, carbazole derivates such as 4 '-N, N carbazole biphenyl of '-two etc..In addition, example As can also it is preferable to use polyvinyl carbazole, polyvinyl triphenylamine (Japanese Unexamined Patent Publication 7-53953 bulletin), contain four Poly (arylene ether) ether sulfone (Polym.Adv.Tech., volume 7, page 33,1996) of phenyl benzidine etc..

< forms 4 > of hole transmission layer using wet type membrane formation

When forming hole transmission layer 4 using wet type membrane formation, usually with form above-mentioned hole using wet type membrane formation and infuse The case where entering layer 3 is used in the same manner hole transmission layer formation and replaces hole injection layer formation composition with composition and shape At.

When forming hole transmission layer 4 using wet type membrane formation, in general, hole transmission layer formation composition further contains Solvent.It can be used in hole transmission layer formation solvent used in composition and in above-mentioned hole injection layer formation group Close the identical solvent of solvent used in object.

The concentration of hole transport ability compound in hole transmission layer formation composition can with hole injection layer shape At the identical range of concentration with the hole transport ability compound in composition.

The formation based on wet type membrane formation of hole transmission layer 4 can be same as the membrane formation process of hole injection layer 3 above-mentioned Ground carries out.

< forms 4 > of hole transmission layer using vacuum vapour deposition

Using vacuum vapour deposition formed hole transmission layer 4 when, also usually can with formed using vacuum vapour deposition it is above-mentioned The case where hole injection layer 3, is used in the same manner hole transmission layer formation and replaces hole injection layer formation composition with composition And it is formed.Membrance casting conditions such as vacuum degree, evaporation rate and temperature when vapor deposition etc. can be with the vacuum with above-mentioned hole injection layer 3 Identical condition forms a film when vapor deposition.

(luminescent layer 5)

Luminescent layer 5 be undertake when to electric field is provided between a pair of electrodes by from 2 injected holes of anode with from 9 note of cathode The electronics entered in conjunction with and be excited and carry out the layer of luminous function.Luminescent layer 5 is formed between anode 2 and cathode 9 Layer, for luminescent layer 5, there are when hole injection layer 3, being formed between hole injection layer 3 and cathode 9 on anode 2, There are when hole transmission layer 4, be formed between hole transmission layer 4 and cathode 9 on anode 2.

As long as the unobvious damage of the film thickness of luminescent layer 5 effect of the invention, is arbitrary, is not likely to produce defect in film It is preferably thicker in aspect, in addition, on the other hand, in terms of be easy as low driving voltage on, it is preferably relatively thin.Therefore, excellent It is selected as 3nm or more, further preferably 5nm or more, in addition, on the other hand, it is often preferred that 200nm is hereinafter, further preferably For 100nm or less.

Luminescent layer 5 is preferably comprised and is transmitted with charge at least containing the material (luminescent material) with luminosity The material (charge-transporting material) of property.As luminescent material, as long as containing iridium coordinationization of the invention in any luminescent layer Object is closed, other luminescent materials can also be suitably used.Hereinafter, to other hairs other than iridium complex compound of the invention Luminescent material is described in detail.

(luminescent material)

As long as luminescent material carries out luminous and do not damage effect of the invention with desired emission wavelength, without special Limitation, can use well known luminescent material.Luminescent material can be fluorescence luminescent material, or phosphorescent light-emitting materials, It is preferred that the good material of luminous efficiency, from the viewpoint of internal quantum, preferred phosphorescent light-emitting materials.

As fluorescence luminescent material, such as material below can be enumerated.

As provide blue-light-emitting fluorescence luminescent material (blue-fluorescence luminescent material), such as can enumerate naphthalene, pyrene, Anthracene, cumarin,To the derivative etc. of bis- (2- phenyl vinyl) benzene and they.

As the fluorescence luminescent material (green fluorescence luminescent material) of offer green emitting, such as quinacridone can be enumerated and spread out Biology, coumarin derivative, Al (C₉H₆NO)₃Equal aluminum complexes etc..

As providing Yellow luminous fluorescence luminescent material (yellow fluorescence luminescent material), such as rubrene, phonetic can be enumerated Pyridine ketone (ペ リ ミ De Application) derivative etc..

As the fluorescence luminescent material (red fluorescence luminescent material) of offer emitting red light, such as 4- (dicyano can be enumerated Methylene) -2- methyl -6- (p- dimethylaminostyryl) -4H- pyrans (DCM, (4- (dicyanomethylene) -2- Methyl-6- (p-dimethylaminostyryl) -4H-pyran)) based compound, 1-benzopyran derivatives, rhodamine derivative Object, benzo thia anthracene derivant, azepine benzo thioxanthene etc..

In addition, as phosphorescent light-emitting materials, for example, can enumerate containing selected from long period type periodic table (hereinafter, as long as no Illustrate, refer to long period type periodic table when mentioning " periodic table ") the 7th~11 race in metal organometallic complex Deng.As the metal of the 7th~11 race selected from periodic table, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, gold etc. are preferably enumerated.

As the ligand of organometallic complex, preferably (miscellaneous) arylpyridine ligand, (miscellaneous) arylpyrazole ligand etc. (miscellaneous) Ligand obtained by aryl and pyridine, pyrazoles, phenanthroline etc. are connect, particularly preferred phenyl pyridine ligand, phenylpyrazole ligand.This In, (miscellaneous) aryl indicates aryl or heteroaryl.

As preferred phosphorescent light-emitting materials, specifically, can for example enumerate three (2- phenylpyridines) closes iridium, three (2- benzene Yl pyridines) close ruthenium, three (2- phenylpyridines) conjunction palladium, bis- (2- phenylpyridines) conjunction platinum, three (2- phenylpyridines) conjunction osmium, three (2- benzene Yl pyridines) close phenylpyridinato complex and octaethyl platinum porphyrins, octaphenyl platinum porphyrins, the octaethyl palladium porphyrins, octaphenyl such as rhenium Metalloporphyrin complexes such as palladium porphyrin etc..

As the luminescent material of macromolecular, poly- (9,9- dioctyl fluorene -2,7- diyl), poly- [(9,9- dioctyls can be enumerated Fluorenes -2,7- diyl)-copolymerization-(4,4 '-(N- (4- secondary butyl phenenyl)) diphenylamine)], poly- [(9,9- dioctyl fluorene -2,7- two Base)-copolymerization-(Isosorbide-5-Nitrae-benzo -2 { 2,1 ' -3 }-triazole)] etc. polyfluorenes based material, poly- [2- methoxyl group -5- (2- ethylhexyl oxygen Base) -1,4- phenylene vinylidene] etc. polyphenylene vinylenes based material.

(charge-transporting material)

Charge-transporting material is the material with positive charge (hole) or negative electrical charge (electronics) transporting, as long as not damaging Effect of the invention, is just not particularly limited, and can use well known luminescent material.

The compound used in the luminescent layer of organic electroluminescent device 5 in the past can be used in charge-transporting material Deng the compound used particularly preferable as the material of main part of luminescent layer 5.

As charge-transporting material, specifically, aromatic amine based compound, phthalocyanine based compound, porphyrin can be enumerated Based compound, oligo-thiophenes based compound, polythiophene based compound, benzyl phenyl based compound, with fluorenyl connection tertiary amine change Close object, hydrazone based compound, silazane based compound, silane amine compound, phosphinylidyne amine compound, quinacridone based compound Deng compound illustrated by the hole transport ability compound as hole injection layer 3 etc., in addition to this, anthracene system chemical combination can be also enumerated Object, pyrene based compound, carbazole based compound, pyridine based compound, phenanthroline based compound,Two azole compounds, thiophene, which are coughed up, is Electron-transportings compound such as compound etc..

In addition, for example can also it is preferable to use be that representative containing with 4,4 '-bis- [N- (1- naphthalene)-N- phenyl amino] biphenyl There are 2 or more tertiary amines and replaces the aromatic diamine (Japanese Unexamined Patent Publication for there are 2 or more fused aromatic rings on nitrogen-atoms 5-234681 bulletin), the aromatic series amine system with star burst structure such as 4,4 ', 4 "-three (1- naphthylphenyl amino) triphenylamines Compound (J.Lumin., 72-74 volume, page 985,1997), the aromatic series amine system chemical combination that is made of the tetramer of triphenylamine Object (Chem.Commun., page 2175,1996), 2,2 ', 7,7 '-four (diphenyl amino) -9, the fluorenes system such as 9 '-spiral shell, two fluorenes chemical combination Object (Synth.Metals, volume 91, page 209,1997), 4, carbazoles based compound such as 4 '-N, N carbazole biphenyl of '-two etc. is as empty Compound illustrated by the hole transport ability compound of cave transport layer 4 etc..In addition, in addition to this, can also enumerate 2- (4- biphenyl Base) -5- (to tert-butyl-phenyl) -1,3,4-Bis- (1- the naphthalene) -1,3,4- of diazole (tBu-PBD), 2,5-Diazole (BND) DengTwo azole compounds, 2,5- bis- (6 '-(2 ', 2 "-bipyridyl)) -1,1- dimethyl -3,4- diphenyl thiophenes are coughed up (PyPySPyPy) etc. thiophenes cough up based compound, bathophenanthroline (BPhen), 2,9- dimethyl -4,7- diphenyl -1,10- phenanthroline Phenanthroline based compounds such as (BCP, bathocuproines) etc..

< forms 5 > of luminescent layer using wet type membrane formation

The forming method of luminescent layer 5 can be vacuum vapour deposition, or wet type membrane formation, but since film forming is excellent It is different, therefore preferred wet type membrane formation.Wet type membrane formation refers to following method in the present invention: being employed as film build method, is coated with Such as spin-coating method of method, dip coating, die coating method, stick coating method, scraper for coating method, rolling method, spray coating method, capillary rubbing method, The method that ink-jet method, silk screen print method, gravure printing method, flexographic plate print process etc. are formed a film with wet type, by coated film drying Film is carried out to be formed.

Using wet type membrane formation formed luminescent layer 5 when, usually with above-mentioned hole injection layer 3 is formed using wet type membrane formation The case where be used in the same manner will become luminescent layer 5 material and can dissolve the material solvent (luminescent layer solvent) mix it is made Standby luminescent layer formation replaces hole injection layer formation composition with composition and is formed.

As solvent, such as in addition to formation ether series solvent, the ester series solvent, fragrance enumerated for hole injection layer 3 Other than race's hydrocarbon system solvent, acid amides series solvent, it is molten can also to enumerate alkane series solvent, halogenated aromatic hydrocarbon system solvent, aliphatic alcohol system Agent, alicyclic alcohol series solvent, aliphatic ketone series solvent and alicyclic ketone series solvent etc..The concrete example of solvent is enumerated below, but only Otherwise effect of the invention is damaged, then it's not limited to that.

For example, the rouge such as glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol -1- methyl ether acetate (PGMEA) can be enumerated Fat race ether series solvent；1,2- dimethoxy benzene, 1,3- dimethoxy benzene, methyl phenyl ethers anisole, phenetole, 2- methoxy toluene, 3- methoxy The aromatic ethers systems such as base toluene, 4- methoxy toluene, 2,3- dimethylanisole, 2,4- dimethylanisole, diphenyl ether are molten Agent；The aromatic esters such as phenylacetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butylbenzoate Series solvent；Toluene, dimethylbenzene, mesitylene, cyclohexyl benzene, naphthane, 3- isopropyl biphenyl, 1,2,3,4- durol, 1, The aromatic hydrocarbon series solvents such as 4- diisopropyl benzene, methyl naphthalene；The amides such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide system Solvent；The alkane series solvent such as n-decane, hexamethylene, ethyl cyclohexane, decahydronaphthalenes, bis cyclohexane；Chlorobenzene, dichloro-benzenes, trichlorine The halogenated aromatics hydrocarbon system solvent such as benzene；The aliphatic alcohols series solvent such as butanol, hexanol；The alicyclic alcohols such as cyclohexanol, Lotka-Volterra circle system system is molten Agent；The aliphatic ketones series solvents such as methyl ethyl ketone, two butanone；Alicyclic ketone series solvent such as cyclohexanone, cyclooctanone, fenchone etc..Wherein, special Not preferred alkane series solvent and aromatic hydrocarbon series solvent.

In addition, film more evenly in order to obtain, preferably makes solvent from the liquid film after rigid film forming with speed appropriate evaporation. Therefore, the boiling point of solvent is usually 80 DEG C or more, preferably 100 DEG C or more, more preferably 120 DEG C or more, in addition, being usually 270 DEG C hereinafter, preferably 250 DEG C hereinafter, more preferably boiling point be 230 DEG C or less.

As long as the unobvious damage of the usage amount of solvent effect of the invention, be it is any, be easy due to sticky low into In the aspect of row film forming operation, luminescent layer, which is formed, uses total content in composition preferably more, in addition, on the other hand, It is easy in the aspect to be formed a film with thick film, it is preferably lower.

In the composition containing iridium complex compound, the content of solvent is preferably 1 mass % or more, more preferably 10 matter % or more, particularly preferably 50 mass % or more are measured, additionally, it is preferred that being 99.99 mass % hereinafter, more preferably 99.9 mass % Hereinafter, particularly preferably 99 mass % or less.

As solvent removal process, heating or decompression can use.As the heating mechanism used in heating means, it is It is whole to film that heat is balancedly provided, preferred cleaning baking oven, heating plate.

As long as the heating temperature in heating process does not damage effect of the invention, be it is arbitrary, shorten drying time Aspect on, preferable temperature is higher, to material damage it is few in terms of on, preferable temperature is lower.The upper limit be usually 250 DEG C with Under, preferably 200 DEG C hereinafter, further preferably 150 DEG C or less.Lower limit is usually 30 DEG C or more, and preferably 50 DEG C or more, into One step is preferably 80 DEG C or more.It may be above the luminous material of usually used charge transport materials or phosphorescence higher than the temperature of the upper limit The heat resistance of material causes to decompose, crystallize.When for temperature lower than lower limit, removes solvent and need the long period.In heating process Heating time according to the boiling point of the solvent in luminescent layer formation composition, vapour pressure, the heat resistance of material and heating condition And it suitably determines.

< forms 5 > of luminescent layer using vacuum vapour deposition

When forming luminescent layer 5 using vacuum vapour deposition, usually by the constituent material of luminescent layer 5 (luminescent material above-mentioned, electricity Lotus transporting compound etc.) in it is one kind or two or more be put into the crucible being set in vacuum tank (use material of more than two kinds When material, will usually be each placed in different crucibles), using vacuum pump 10 will be vented in vacuum tank^{- 4}After Pa or so, add Hot crucible (when using material of more than two kinds, usually heating respective crucible), the evaporation capacity for controlling the material in crucible is steamed It sends out (being evaporated using evaporation capacity is controlled when material of more than two kinds each independently), is infused with crucible hole staggered relatively Enter formation luminescent layer 5 in transport layer.It should be noted that their mixture can also be put into earthenware when using material of more than two kinds Crucible is heated, it is made to evaporate and form luminescent layer 5.

As long as the unobvious damage of vacuum degree when vapor deposition effect of the invention, there is no limit, usually 0.1 × 10^{? 6}Torr(0.13×10^{- 4}Pa)~9.0 × 10^{- 6}Torr(12.0×10^{- 4}Pa).As long as the unobvious damage present invention of evaporation rate Effect, there is no limit, usuallyAs long as the unobvious damage of film-forming temperature when vapor deposition Effect of the invention, there is no limit, is preferably carried out with 10 DEG C~50 DEG C.

(hole blocking layer 6)

Hole blocking layer 6 can be set between luminescent layer 5 and aftermentioned electron injecting layer 8.Hole blocking layer 6 be with The mode that the interface of the cathode side of luminescent layer 5 connects is layered in the layer on luminescent layer 5.

The hole blocking layer 6 has the function of the hole arrival cathode 9 for preventing to shift to come from anode 2 and will be from yin The effect that 9 injected electrons of pole is efficiently transmitted to the direction of luminescent layer 5.As required by the material for constituting hole blocking layer 6 Physical property, can enumerate that electron mobility is high and hole mobility is low, energy gap (difference of HOMO-LUMO) is big, excited triplet state energy level (T1) high.

As the material for the hole blocking layer 6 for meeting such condition, such as bis- (2- methyl -8-hydroxyquinoline) can be enumerated The mixed ligand coordination compounds such as phenol aluminium, bis- (2- methyl -8-hydroxyquinoline) triphenyl silanol aluminium, bis- (2- methyl -8- hydroxyl quinolines Quinoline) aluminium-mu-oxo-is bis--metal complexs such as (2- methyl -8-hydroxyquinoline) aluminium dual-nuclei structure model, diphenylethyllene connection The compound of styryl such as benzene derivative (Japanese Unexamined Patent Publication 11-242996 bulletin), -5 (4- of 3- (4- xenyl) -4- phenyl Tert-butyl-phenyl) -1, the triazole derivatives such as 2,4- triazoles (Japanese Unexamined Patent Publication 7-41759 bulletin), the phenanthroline such as bathocuproine spread out Biological (Japanese Unexamined Patent Publication 10-79297 bulletin) etc..In addition, that records in International Publication No. 2005/022962 has at least The compound of 1 2,4,6 substituted pyridine ring is it is also preferred that material as hole blocking layer 6.

There is no limit can landform same as the forming method of luminescent layer 5 above-mentioned for the forming method of hole blocking layer 6 At.

As long as the unobvious damage of the film thickness of hole blocking layer 6 effect of the invention, be it is arbitrary, usually 0.3nm with On, preferably 0.5nm or more, in addition, usually 100nm is hereinafter, preferably 50nm or less.

(electron transfer layer 7)

Electron transfer layer 7 is set to luminescent layer 5 and electronics for the purpose for further increasing the current efficiency of element Between implanted layer 8.

Electron transfer layer 7 from can provide electric field electrode between will be from 9 injected electrons of cathode efficiently to luminescent layer 5 Direction transmission compound formed.As the electron-transporting compound used in electron transfer layer 7, need for from cathode 9 or electron injecting layer 8 electron injection efficiency it is high and there is high electron mobility, can efficiently transmit institute's injected electrons Compound.

The electron-transporting compound used in electron transfer layer 7 is generally preferably from cathode 9 or the electricity of electron injecting layer 8 Sub- injection efficiency is high, can efficiently transmit the compound of institute's injected electrons.As electron-transporting compound, it is specific and It says, such as the metal complexs (Japanese Unexamined Patent Application 59-194393 bulletin), 10- such as aluminum complex that can enumerate 8-hydroxyquinoline The metal complex of hydroxy benzo [h] quinoline,Oxadiazole derivative, distyrylbiphenyl derivatives, thiophene cough up derivative, 3- Flavonol metal complex, 5- flavonol metal complex, benzoAzoles metal complex, benzothiazole metal combination Object, three benzimidazolyl benzene (No. 5645948 specifications of U.S. Patent No.), quinoxaline compounds (Japanese Unexamined Patent Publication 6-207169 Number bulletin), phenanthroline derivative (Japanese Unexamined Patent Publication 5-331459 bulletin), 2- tert-butyl -9,10-N, N '-dicyan anthraquinone Diimine, N-shaped hydrogenated amorphous silicon carbide, N-shaped zinc sulphide, N-shaped zinc selenide etc..

The film thickness of electron transfer layer 7 is usually 1nm or more, preferably 5nm or more, in addition, on the other hand, usually 300nm is hereinafter, preferably 100nm or less.

Electron transfer layer 7 is by being layered in hole blocking layer using wet type membrane formation or vacuum vapour deposition as described above Above formed.Usually using vacuum vapour deposition.

(electron injecting layer 8)

Electron injecting layer 8, which plays, efficiently to be injected to electron transfer layer 7 or luminescent layer 5 from 9 injected electrons of cathode Effect.

In order to efficiently carry out electron injection, the low metal of the preferred work function of material of electron injecting layer 8 is formed.As example The alkali metal such as sodium, caesium, the alkaline-earth metal such as barium, calcium etc. can be used in son.Generally preferable 0.1nm~the 5nm of its film thickness.

In addition, in metal complexs institute's generation such as aluminum complex of the nitrogen-containing heterocycle compounds such as bathophenanthroline, 8-hydroxyquinoline The alkali metal such as sodium contaminated, potassium, caesium, lithium, rubidium (Japanese Unexamined Patent Publication 10-270171 bulletin, day in the Organic Electron Transport Material of table Recorded in this special open 2002-100478 bulletin, Japanese Unexamined Patent Publication 2002-100482 bulletin etc.) it also can be improved electronics note Enter transporting and has both excellent film quality, thus preferably.

Film thickness is usually 5nm or more, preferably 10nm or more, in addition, usually 200nm is hereinafter, it is preferred that in 100nm or less Range.

Electron injecting layer 8 is by being layered in luminescent layer 5 using wet type membrane formation or vacuum vapour deposition or hole thereon hinders It is formed in barrier.

The case where detailed content of the case where wet type membrane formation is with luminescent layer 5 above-mentioned are identical.

(cathode 9)

Cathode 9 plays the role of injecting electronics to the layer (electron injecting layer 8 or luminescent layer 5 etc.) of luminescent layer side.As yin The material of pole 9, can be used the material used in above-mentioned anode 2, but in terms of efficiently carry out electron injection on, preferably Using the low metal of work function, such as the metals or their alloy etc. such as tin, magnesium, indium, calcium, aluminium, silver can be used.As specific Example, such as the alloy electrodes of low work functions such as magnesium-silver alloy, magnesium-indium alloy, aluminum-copper-lithium alloys can be enumerated etc..

In terms of the stability of element, it is high and protect to the metal layer of atmospheric stability that work function is laminated preferably on cathode 9 Protect the cathode 9 being made of the metal of low work function.As the metal of stacking, such as aluminium, silver, copper, nickel, chromium, gold, platinum can be enumerated etc. Metal.

The film thickness of cathode is usually identical as anode 2.

(other layers)

As long as the unobvious damage of organic electroluminescent device of the invention effect of the invention, so that it may further have it Its layer.I.e., it is possible to have other arbitrary layers than that described above between anode 2 and cathode 9.

< others element constitutes >

It should be explained that, or structure in contrast with the above description, that is, cathode, electronics note are stacked gradually on substrate Enter layer, luminescent layer, hole injection layer, anode.

The other > of <

It, can be with single organic field when organic electroluminescent device of the invention is applied to organic electroluminescence device The form of electroluminescent element uses, and can also make in the form of multiple organic electroluminescent devices are configured to the composition of array-like With can also be used in the form of anode 2 and cathode 9 are configured to the rectangular composition of X-Y.

[display device and lighting device]

Display device and lighting device of the invention has organic electroluminescent device present invention as described above.This hair Form, the structure of bright display device and lighting device are not particularly limited, and organic field luminescence member of the invention can be used Part assembles according to conventional methods.

For example, " organic el display " can be used, (OHM company issues a magazine for Heisei on August 20th, 16, former quiet scholar, Anda thousand Wave vector, village Tian Yingxing write) in record method form display device and lighting device of the invention.

[manufacture L^a ₂L^bIr or L^aL^b ₂The method for the iridium complex compound that Ir is indicated]

Make bis-cyclometallated complex of iridium raw material and other ligand reactions the invention further relates to one kind and manufactures tricyclic metal Change the method for iridium complex compound.

That is, the manufacturing method of the present invention is a kind of manufacture L^a ₂L^bIr or L^aL^b ₂The method for the iridium complex compound that Ir is indicated, Being included in the presence of silver-colored (I) salt and organic base makes L^a _pIrX_qThe compound and L of expression^bThe process of the compound reaction of expression.

The manufacturing method that the manufacturing method of the present invention can also be used as the iridium complex compound of formula above-mentioned (1) expression makes With.

In L^a _pIrX_q、L^b、L^a ₂L^bIr and L^aL^b ₂In Ir, Ir indicates iridium atom, p and q each independently represent 0~3 it is whole Number, p+q=3, L^aAnd L^bThe multidentate ligand for being coordinated in iridium atom containing carbon atom and nitrogen-atoms is each independently represented, is existed Multiple L^aOr L^bIt may be the same or different, X is the group that following formula (6) indicate.

[in formula (6), * indicates the bonding position with above-mentioned iridium atom,

R¹¹And R¹³Indicate substituent group,

R¹²Indicate hydrogen atom or substituent group.]

< L^aAnd L^b>

Above-mentioned L^aAnd L^bIt is at least with double coordination in the ligand of iridium atom, as long as being covalent with one of the bonding scheme of iridium Key, another one be coordinate bond or carbene ligands key, then the type of its chemical structure is just not particularly limited, or 3 teeth with On multidentate ligand, but preferred bidentate ligand.

From the viewpoint of iridium complex compound from manufacture as organic EL element materials'use, ligand L^aAnd L^bRespectively with The type that iridium atom carries out the atom of covalent bonding is carbon atom, carries out the preferred carbon of atom of coordination bonding or carbene ligands bonding Atom, nitrogen-atoms, phosphorus atoms, oxygen atom or sulphur atom, more preferably carbon atom or nitrogen-atoms, further preferably nitrogen-atoms.

When atom with iridium atom progress covalent bonding is carbon atom, from reactive height and as organic EL element material From the viewpoint of use, the carbon atom of sp2 hybridized orbit has been preferably formed.In turn, double bond, aromatic rings are more preferably formd Or the carbon atom of miscellaneous aromatic rings, further preferably form the carbon atom of aromatic rings or miscellaneous aromatic rings.

When progress coordination bonding or the atom of carbene ligands bonding are carbon atom or nitrogen-atoms, from reactive high and conduct From the viewpoint of organic EL element materials'use, the carbon atom or nitrogen-atoms of sp2 hybridized orbit are preferably formed, more preferably The carbon atom or nitrogen-atoms for foring double bond, aromatic rings or miscellaneous aromatic rings, the carbon for further preferably foring miscellaneous aromatic rings are former Son or nitrogen-atoms, most preferably form the nitrogen-atoms of miscellaneous aromatic rings.

L^aAnd L^bCan be mutually the same, can also be different from each other, it is replaced in the type and its molecular weight of respective substituent group There is no limit.Additionally, there are multiple L^aOr L^bIt can also be identical or different.

L^aAnd L^bFurther preferred form by following formula (7) indicate.

[in formula (7), * indicates the bonding position with iridium atom,

C¹¹、C¹²And C¹³Indicate carbon atom, N¹¹Indicate nitrogen-atoms,

Ring Cy⁵It indicates to include above-mentioned C¹¹With above-mentioned C¹²Aromatic rings or miscellaneous aromatic rings,

Ring Cy⁶It indicates to include above-mentioned N¹¹With above-mentioned C¹³Aromatic rings or miscellaneous aromatic rings.

R²¹And R²²Each independently represent hydrogen atom or substituent group, above-mentioned R²¹It is bonded to above-mentioned ring Cy⁵, above-mentioned R²²Bonding In above-mentioned ring Cy⁶。

X¹Expression may replace in above-mentioned ring Cy⁵Group maximum number, be integer.

X²Expression may replace in above-mentioned ring Cy⁶Group maximum number, be integer.]

< ring Cy⁵>

Ring Cy⁵Indicate the carbon atom C comprising being coordinated in iridium atom¹¹And C¹²Aromatic rings or miscellaneous aromatic rings.

Ring Cy⁵It can be fused rings obtained by monocycle or the bonding of multiple rings.When for fused rings, the number of ring is not limited especially It is fixed, preferably 6 hereinafter, preferably 5 hereinafter, by the number presence for these sections do not damage complex it is deliquescent become Gesture, thus preferably.

Ring Cy⁵It is not particularly limited, from the viewpoint of the chemical stability of complex, the composition member of preferably miscellaneous aromatic rings Element is further selected from nitrogen-atoms, oxygen atom, sulphur atom, silicon atom, phosphorus atoms and selenium atom other than carbon atom.

As ring Cy⁵Concrete example, the phenyl ring of monocycle can be enumerated in aromatic rings；The naphthalene nucleus of two rings；Fluorenes more than tricyclic Ring, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene ring, BaP ring,Ring, benzo phenanthrene ring, fluoranthene ring etc..

In addition, the furan nucleus containing oxygen atom, benzofuran ring, dibenzofurans ring can be enumerated in miscellaneous aromatic rings；Sulfur-bearing The thiphene ring of atom, benzothiophene ring, dibenzothiophenes ring；Pyrrole ring, pyrazole ring, imidazole ring, the benzimidazole of nitrogen atom Ring, indole ring, indazole ring, carbazole ring, indolocarbazole ring, indeno carbazole ring, pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, Triazine ring, quinoline ring, isoquinolin ring, cinnolines ring, phthalazines ring, quinoxaline ring, quinazoline ring, quinazolinone ring, acridine ring, phenanthridines Ring, carboline ring or purine ring；Containing there are many heteroatomicAzoles ring,It is diazole ring, differentAzoles ring, benzisoxaAzoles ring, Thiazole ring, benzothiazole ring, isothiazole ring, benzisothiazole ring etc..

In order to control emission wavelength or improve dissolubility in a solvent or improve as the resistance to of organic EL element Long property, imports substituent group appropriate on these rings mostly.In above-mentioned ring, the introduction method of preferably such substituent group is many Well known ring.

Therefore, in above-mentioned concrete example, the carbon atom C that is preferably directly connected to iridium atom¹¹The ring constituted is benzene Ring.As the example of phenyl ring, can enumerate aromatic rings, dibenzofurans ring, dibenzothiophenes ring, carbazole ring, indolocarbazole ring, Indeno carbazole ring etc..Wherein, further preferred phenyl ring, naphthalene nucleus, fluorenes ring, dibenzofurans ring, dibenzothiophenes ring or carbazole ring, Particularly preferred phenyl ring and/or naphthalene nucleus.

Constitute ring Cy¹¹Atomicity be not particularly limited, from maintain iridium complex compound dissolubility from the viewpoint of, should The constituting atom number of ring is respectively preferably 5 or more, more preferably 6 or more.In addition, the constituting atom number of the ring be preferably 30 with Under, more preferably 20 or less.

< ring Cy⁶>

Ring Cy⁶It indicates to include carbon atom C¹²With the nitrogen-atoms N for being coordinated in iridium atom¹¹Miscellaneous aromatic rings.Specifically, can lift The pyridine ring of monocycle, pyridazine ring, pyrimidine ring, pyridine ring, triazine ring, pyrrole ring, pyrazole ring, different outAzoles ring, thiazole ring, Azoles ring,Diazole ring, thiazole ring, purine ring；Bicyclic-fused quinoline ring, isoquinolin ring, cinnolines ring, phthalazines ring, quinazoline Ring, quinoxaline ring, naphthyridines ring, indole ring, indazole ring, benzisoxaAzoles ring, benzisothiazole ring, benzimidazole ring, benzoAzoles ring, benzothiazole ring；Tricyclic condensed acridine ring, phenanthroline ring, carbazole ring, carboline ring；The benzo more than Fourth Ring condensed Phenanthridines ring, benzacridine ring or indoles and carboline ring etc..

Wherein, due to being easily guided into substituent group, emission wavelength, dissolubility height and being easy reaction, preferably Fourth Ring is below Fused rings, more preferable tricyclic fused rings below, most preferably monocycle or the fused rings of two rings.

Specifically, it is preferable that imidazole ring,Azoles ring, thiazole ring, benzimidazole ring, benzoAzoles ring, benzothiazole ring, Pyridine ring, quinoline ring, isoquinolin ring, pyridazine ring, pyrimidine ring, pyridine ring, triazine ring, cinnolines ring, phthalazines ring, quinazoline ring, quinoline Quinoline ring or naphthyridines ring.In turn, more preferable imidazole ring, benzimidazole ring, benzothiazole ring, pyridine ring, quinoline ring, isoquinolin Ring, pyridazine ring, pyrimidine ring, pyridine ring, triazine ring, cinnolines ring, phthalazines ring, quinazoline ring, quinoxaline ring or naphthyridines ring, further It is preferred that benzimidazole ring, benzothiazole ring, pyridine ring, quinoline ring, isoquinolin ring, pyridazine ring, pyrimidine ring, pyridine ring, cinnolines ring, Phthalazines ring, quinazoline ring, quinoxaline ring or naphthyridines ring.

In particular, ligand L^aAnd L^bIn at least either ring Cy⁶Preferably benzimidazole ring, benzothiazole ring, pyridine Ring, quinoline ring, isoquinolin ring, pyridazine ring, pyrimidine ring, pyridine ring, cinnolines ring, phthalazines ring, quinazoline ring, quinoxaline ring or naphthyridines Ring, further preferably benzimidazole ring, benzothiazole ring, pyridine ring, quinoline ring, isoquinolin ring, quinazoline ring, quinoxaline ring Or naphthyridines ring.In addition, as ring Cy⁶, it preferably is contained in ring Cy²In the knot that indicates of cited any one of formula (2)~(5) Structure.

< R²¹、R²²、X¹And X²>

R in formula (7)²¹And R²²It respectively indicates and is bonded to ring Cy⁵With ring Cy⁶Hydrogen atom or substituent group.R²¹And R²²It is each From independence, may be the same or different.

X¹Expression may replace in ring Cy⁵Substituent group maximum number, be integer.R²¹, can be mutually the same when being multiple, It can be different from each other.Equally, X²Expression may replace in ring Cy⁶Substituent group maximum number, be integer.R²²It, can be with when being multiple It is mutually the same, it can also be different from each other.

In addition, R²¹And/or R²²There are it is multiple when, the R of 2 or more adjoinings²¹Each other and/or R²²It each other can mutual key Close and formed the monocycle or fused rings of aliphatic aromatic or heteroaromatic.

R²¹And R²²Type be not particularly limited, it may be considered that the luminous wave that the iridium complex compound of manufacture is expected Long accurate control, with the compatibility of used solvent, be made organic EL element when with the compatibility of host compound etc. And select optimal substituent group.Range of the particularly preferred substituent group in following description.

R²¹And R²²It is preferred that being each independently selected from hydrogen atom ,-D ,-F ,-Cl ,-Br ,-I ,-N (R ')₂、-CN、-NO₂、- OH ,-COOR ' ,-C (=O) R ' ,-C (=O) NR ' ,-P (=O) (R ')₂,-S (=O) R ' ,-S (=O)₂R’、-OSO₂R ', carbon are former Straight-chain, branched or the cyclic alkyl of subnumber 1~30, the straight-chain of carbon atom number 1~30, branched or cyclic alkoxy, Straight-chain, branched or the cyclic alkylthio of carbon atom number 1~30, the straight-chain of carbon atom number 2~30, branched or cyclic annular alkene Base, the straight-chain of carbon atom number 2~30, branched or cyclic alkyne, the aromatic group of carbon atom number 5~60, carbon atom number 5 ~60 heteroaromatic group, the aryloxy group of carbon atom number 5~40, the arylthio of carbon atom number 5~40, carbon atom number 5~60 Aralkyl, the heteroarylalkyl of carbon atom number 5~60, the ammonia diaryl base of carbon atom number 10~40, carbon atom number 10~40 Two heteroaryl aminos of aryl heteroaryl amino or carbon atom number 10~40.

The alkyl, the alkoxy, the alkylthio group, the alkenyl and the alkynyl can be further replaced by 1 or more R ', 1-CH in these groups₂Not adjacent-the CH of base or 2 or more₂Base can be substituted into-R '-C=CR '-,-C ≡ C- ,- Si(R’)₂,-C (=O)-,-NR '-,-O- ,-S- ,-C (=O) NR '-or divalent aromatic group.

In addition, 1 or more hydrogen atom in these groups can be replaced D, F, Cl, Br, I or-CN.

The aromatic group, the aryloxy group, the arylthio, the aralkyl, the heteroarylalkyl, is somebody's turn to do at the heteroaromatic group Ammonia diaryl base, the aryl heteroaryl amino and two heteroaryl amino can be each independently further by 1 or more R ' It is replaced.The group recorded in R ' and the < R ' > of [iridium complex compound] above-mentioned is identical, and preferred form is also identical.

R²¹And R²²In alkyl, alkoxy, alkylthio group, alkenyl and alkynyl, aromatic group, heteroaromatic group, fragrant oxygen Base, arylthio, aralkyl, heteroarylalkyl, ammonia diaryl base, aryl heteroaryl amino and two heteroaryl aminos and [iridium above-mentioned Complex] < R¹~R⁴The group recorded in > is identical, and preferred form is also identical.In addition, R ' also with [iridium above-mentioned Complex] < R ' > in the group recorded it is identical, preferred form is also identical.

< p and q >

P and q each independently represents 0~3 integer, p+q=3.As long as meeting these, there is no particular limitation, p is preferred It is 1 or 2.

< R¹¹~R¹³>

X is the group that formula (6) indicate, the R in formula (6)¹¹And R¹³Indicate substituent group, R¹²Indicate hydrogen atom or substituent group.

R¹¹~R¹³The type of substituent group be not particularly limited, there is stability, Yi Jiti preferably as intermediate raw material The high property being easy in the reaction with iridium atom dissociation.

R¹¹And R¹³It is preferred that being each independently selected from-N (R ')₂, the straight-chain of carbon atom number 1~30, branched or cyclic annular alkane Base, the straight-chain of carbon atom number 1~30, branched or cyclic alkoxy, the straight-chain of carbon atom number 2~30, branched or ring Shape alkenyl, the aromatic group of carbon atom number 5~60, the heteroaromatic group of carbon atom number 5~60, carbon atom number 5~40 Aryloxy group, the aralkyl of carbon atom number 5~60, the heteroarylalkyl of carbon atom number 5~60, carbon atom number 10~40 ammonia diaryl Two heteroaryl aminos of base, the aryl heteroaryl amino of carbon atom number 10~40 or carbon atom number 10~40.

Be preferably selected from straight-chain, branched or the cyclic alkyl of carbon atom number 1~30, the straight-chain of carbon atom number 1~30, Branched or cyclic alkoxy, the straight-chain of carbon atom number 2~30, branched or cyclic alkenyl radical, carbon atom number 5~60 fragrance The heteroaromatic group of race's group, carbon atom number 5~60.These groups can be further replaced by above-mentioned R '.

More preferably the straight-chain of carbon atom number 1~30, branched or cyclic alkyl, carbon atom number 1~30 straight-chain, Branched or cyclic alkoxy, the straight-chain of carbon atom number 2~30, branched or cyclic alkenyl radical, carbon atom number 5~60 fragrance The heteroaromatic group of race's group, carbon atom number 5~60, the further preferably straight-chain of carbon atom number 1~30, branched or Cyclic alkyl, the most preferably straight-chain or branched-chain alkyl of carbon atom number 1~6.

R¹²Preferably hydrogen atom ,-D ,-N (R ')₂, straight-chain, branched or the cyclic alkyl of carbon atom number 1~30, carbon it is former The aromatic group of subnumber 5~60, the heteroaromatic group of carbon atom number 5~60, the aralkyl of carbon atom number 5~60 or carbon are former The heteroarylalkyl of subnumber 5~60.

It is preferably selected from hydrogen atom, the straight-chain of carbon atom number 1~30, branched or cyclic alkyl, carbon atom number 1~30 Straight-chain, branched or cyclic alkoxy, the straight-chain of carbon atom number 2~30, branched or cyclic alkenyl radical, carbon atom number 5~ The heteroaromatic group of 60 aromatic group, carbon atom number 5~60.These groups can further be taken by above-mentioned R ' Generation.Most preferably hydrogen atom.

< L^a _pIrX_q>

L as raw material^a _pIrX_qThe complex of expression can use what patent document 2 or non-patent literature 4 were recorded Method is synthesized.In addition, for example can also be with reference book IRIDIUM (III) IN OPTOELECTRONIC AND PHOTONICS APPLICATIONS ed.by.Eli Zysman-Colman Wiley, 2017 it is equal in the document quoted.

Relative to raw material L^a _pIrX_qThe ligand L of the complex of expression^bEquivalent be not particularly limited, normally due to matching Body L^bMolecular weight it is big, viscosity is also high, therefore usually more than 0.1 equivalent, it is more than preferably 0.2 equivalent, more preferably 1 equivalent More than.In addition, ligand L^bEquivalent be usually 50 equivalents hereinafter, preferably 30 equivalents are hereinafter, below more preferably 10 equivalents.

Also there is no limit for the adding method of ligand, total amount can be made to be present in reaction system when reacting and starting, in addition, Total amount can also be put on way together or in batches, or continuously be supplied into reaction system in the reaction.

< silver (I) salt >

Silver used in the manufacturing method of the present invention (I) salt is not particularly limited, and can preferably make in the reaction system Ag (I)⁺ Free silver (I) salt of ion, therefore do not include the silver halides such as silver chlorate, silver bromide and silver oxide and silver sulfide.

The example of silver (I) salt used in the present invention can enumerate silver acetate, trifluoro second as the silver salt of organic acid Sour silver, silver formate, sad silver, 2 ethyl hexanoic acid silver, silver benzoate, pyridine carboxylic acid silver, actol, silver citrate, hexamethylene fourth Sour silver, p-methyl benzenesulfonic acid silver, methanesulfonic acid silver, silver trifluoromethanesulfonate, N, N- dimethyl dithiocarbamic acid silver, bis- (fluoroforms Sulfonyl) the sour silver of acid imide, fluoroform mercaptan silver etc..In addition, the silver salt as inorganic acid, can enumerate silver carbonate, silver nitrate, Silver sulfate, silver nitrite, silver chlorate, silver perchlorate, silver orthophosphate, silver cyanide, siliver chromate, wolframic acid silver, hexafluoroarsenate silver, boric acid Silver, hexafluoro antimony silver, Silver hexafluorophosphate etc..

Relative to L^a _pIrX_qThe equivalent of silver (I) salt of the complex of expression is not particularly limited, and silver-colored (I) salt is generally Solid can increase viscosity when making an addition to reaction system, therefore usually more than 0.1 equivalent, more than preferably 0.2 equivalent, more excellent It is selected as 1 equivalent or more.In addition, the equivalent of silver-colored (I) salt is for 50 equivalents hereinafter, preferably 30 equivalents are hereinafter, more preferably 10 equivalents Below.

Also there is no limit for the adding method of silver-colored (I) salt, total amount can be made to be present in reaction system when reacting and starting, Total amount can be put on way together or in batches, or continuously be supplied into reaction system in the reaction.

< organic base >

For organic base used in the manufacturing method of the present invention, the organic amine, at least of carbon atom number 3~60 can be enumerated In the pyridines etc. of 2 and 6 carbon atom numbers 3~60 with aliphatic substitution.

The example of organic amine as carbon atom number 3~60 can enumerate trimethylamine, triethylamine, diisopropylethylamine, three N-butylamine, tri-n-octyl amine, N-methylmorpholine, the 11 carbon -7- alkene of 1,8- diazabicyclo [5,4,0], N, accelerine etc..

As at least fat used in the pyridines of 2 and 6 carbon atom numbers 3~60 with aliphatic substitution The type of race's substituent group, can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl, just oneself Base, n-octyl, 2- ethylhexyl, isopropyl, isobutyl group, cyclopenta, cyclohexyl, n-octyl, norborny, adamantyl etc.. In order to obtain the balance of alkalinity with nucleophilicity, preferred 10 or less carbon atom number, the substitution below of more preferable carbon atom number 6 can be used Base.As their example, 2,6- lutidines, 2,4,6- trimethylpyridines, 2,6- di-tert-butyl pyridine etc. can be enumerated.

In order not to cause adverse effect to reaction, preferably it is not easy to be coordinated in iridium atom and bulky alkali, therefore preferably three Ethamine, diisopropylethylamine, 2,6- lutidines or 2,6- di-tert-butyl pyridine, further preferably alkalinity are flat with nucleophilicity The high diisopropylethylamine of weighing apparatus property.

Relative to L^a _pIrX_qThe equivalent of the organic base of the complex of expression is not particularly limited, usually 0.1 equivalent More than, more than preferably 0.2 equivalent, more than more preferably 0.5 equivalent.In addition, the equivalent of organic base be usually 50 equivalents hereinafter, Preferably 30 equivalents are hereinafter, below more preferably 10 equivalents.By in these range, to be played in the presence of not hindering to react The trend of effect.

Also there is no limit for the adding method of organic base, total amount can be made to be present in reaction system when reacting and starting, Total amount can be put into together or in batches or continuously be supplied into reaction system on way in the reaction.

< solvent >

L^a _pIrX_qComplex (the raw material L of expression^a _pIrX_q) and ligand L^bReaction can be in the absence of solvent Implement, solvent also can be used and implement.As long as the type of solvent does not cause adverse effect to reaction, there is no limit for type. It is preferable to use make used raw material L^a _pIrX_q, ligand L^bThe solvent of the type sufficiently dissolved.Solvent can be used alone, can also To mix a variety of uses.

The type of solvent is not particularly limited, and well known solvent can be used.Such as cyclohexyl benzene, diethylene glycol (DEG) two can be enumerated Methyl ether, toluene etc..

Also there is no limit for the adding method of solvent.Initially it can begin to use total amount from reaction, it can also in the reaction on the way Total amount is put into together or in batches or is continuously supplied into reaction system.In addition it is also possible to make solvent gas on the way in the reaction Change, removes solvent out of reaction system and reacted.

< raw material L^a _pIrX_qAnd ligand L^bReaction condition >

(temperature)

Reaction temperature different, usually 25 DEG C or more, preferably 50 DEG C according to the combination of used reaction raw materials etc. More than, more preferably 100 DEG C or more.In addition, usually 300 DEG C hereinafter, preferably 270 DEG C hereinafter, more preferably 250 DEG C with Under.By in these temperature ranges, thus in the presence of can while inhibiting the undesirable side reactions such as the decomposition of complex into The trend of row reaction.

(pressure)

Reaction pressure is not particularly limited.Usually implement under atmospheric pressure, but improves way continuous removal of solvent in the reaction When removal efficiency when can carry out under reduced pressure, on the contrary, inhibiting the volatilization of solvent etc. and efficiently being carried out under stable viscosity It can also be reacted under elevated pressure when stirring.

Embodiment

More specific description is carried out to the present invention hereinafter, showing embodiment.But the present invention is not limited to implementations below Example, the present invention is without departing from its purport, so that it may arbitrarily change and implement.In formula, Me indicates that methyl, Et indicate ethyl, Ph Table phenyl, Ac indicate that acetyl group, Tf indicate that trifyl, iPr indicate that isopropyl, S-Phos indicate 2- dicyclohexylphosphontetrafluoroborate- 2 ', 6 '-dimethoxy -1,1 '-biphenyl, DMSO indicate that dimethyl sulfoxide, THF indicate that tetrahydrofuran, NBS indicate N- bromo amber Acid imide, DME indicate that dimethyl ether, PPA indicate that polyphosphoric acid, CHB indicate cyclohexyl benzene.

It should be noted that reaction all carries out under nitrogen flowing in embodiment below and comparative example.In addition, liquid color The determination condition for composing (LC) is as follows.

Device: Shimadzu Scisakusho Ltd's LC-20A system

Chromatographic column: GL Sciences Co. Ltd. system Inertsil ODS-3 (3 μm, 4.6 × 25cm),

Eluent composition: acetonitrile/tetrahydrofuran

Eluent flow rate: 0.8ml/min

Oven temperature: 40 DEG C

Detection: UV254nm

[synthesis example 1]

The synthesis > of < compound 1

Chloro- 4- isonicotinic acid (10.1g, the COMBI-BLOCKS corporation of 5- amino -2- is packed into the eggplant type flask of 300mL OR-6918) and it is dehydrated dimethylformamide (50mL), is impregnated in ice-water bath (1 DEG C), further puts into carbonyl dimidazoles (11.2g) is stirred.After 15 minutes, it is added dimethylformamide (20mL), is rinsed with dimethylformamide (20mL) Afterwards, it is further stirred at room temperature 3 hours.Add this mixture to N, O- dimethyl hydroxylamine hydrochloride (8.4g) and diisopropyl In the dimethyl formamide solution (20mL) of base ethylamine (15mL), stirred 3 hours at 80 DEG C.Thereafter, it is concentrated under reduced pressure, Essence is carried out to residue using silica gel column chromatography (neutral silica gel 550mL, methylene chloride, then, methylene chloride/methanol=95/5) System obtains the intermediate 1 that the above-mentioned formula of 9.7g indicates.

It is packed into intermediate 1 (9.7g) and toluene (100mL) into the eggplant type flask of 500mL, is azeotroped off moisture under decompression Afterwards, dehydration tetrahydrofuran (100mL) is added, is impregnated in ice-water bath (1 DEG C).Grignard Reagent liquid was added thereto with 5 minutes, into one Step is stirred at room temperature 90 minutes, and the grignard reagent liquid is by being packed into bits shape magnesium in the four-hole boiling flask of 300mL in advance (2.4g), and use dehydration tetrahydrofuran (50mL) solution for containing 2- bromonaphthalene (16.7g) is added dropwise within 30 minutes while stirring, so Afterwards stir 90 minutes and prepare.After saturated aqueous ammonium chloride (40mL) is added thereto, addition methylene chloride (500mL), Water (300mL) and sodium carbonate (1g) carry out liquid separation cleaning, utilize silicagel column color further after concentration with the dry oily phase of magnesium sulfate Spectrometry (silica gel 400mL, methylene chloride, then, and methylene chloride/methanol=95/5) it is refined, obtain the above-mentioned formula table of 10.8g The intermediate 2 shown.

3- (n-octyl) phenylboric acid (33.5g) and 3- bromoacetophenone (26.3g) are packed into the eggplant type flask of 1L, into one Toluene (500mL), ethyl alcohol (60mL) and the 2M tripotassium phosphate aqueous solution (190mL) being bubbled through nitrogen is added in step, at oil bath (100 DEG C) Middle stirring flows back for 6 hours.After being cooled to room temperature, water phase is removed, is concentrated under reduced pressure and obtains residue, utilize silicagel column color Spectrometry (silica gel 600mL, dichloromethane/hexane=2/8) refines the residue, obtains in the above-mentioned formula expression of 35.0g Mesosome 3.

It is packed into intermediate 2 (10.8g) and intermediate 3 (13.3g) into 1L eggplant type flask, potassium hydroxide is further added Ethyl alcohol (120mL) solution of (9.8g) stirs 2.5 hours in oil bath (90 DEG C) when carrying out reflux.Then, saturation chlorine is added Change aqueous ammonium (40mL), carries out liquid separation with methylene chloride (500mL) and water (500mL) and clean.After the dry oily phase of magnesium sulfate, Solvent is removed under reduced pressure and obtains residue, using silica gel column chromatography (silica gel 600mL, dichloromethane/hexane=9/1, then, two Chloromethanes/hexane=1/0) residue is refined, obtain the intermediate 4 that the above-mentioned formula of 5.9g indicates.

Intermediate 4 (5.9g), 2,6- dimethylphenylboronic acid (5.1g), tripotassium phosphate are packed into 1L eggplant type flask (4.6g), acid chloride (0.13g), 2- dicyclohexylphosphontetrafluoroborate -2 ', (0.46g, Johnson Matthey are public for 6 '-dimethoxy-biphenyls Take charge of S-Phos processed) and toluene (250mL), it stirs in 90 DEG C of oil baths 1 hour, after then being stirred 2.5 hours at 105 DEG C, adds Enter barium hydroxide octahydrate (2.6g) to futher stir 3.5 hours.After being cooled to room temperature, liquid separation is carried out with water (500mL) and is cleaned, After the dry oily phase of magnesium sulfate, it is concentrated under reduced pressure and obtains residue, utilize silica gel column chromatography (silica gel 300mL, dichloromethane Alkane/ethyl acetate=1/0, then, dichloromethane/ethyl acetate=95/5) residue is refined, obtain the above-mentioned formula of 5.5g The intermediate 5 of expression.

2- (3- bromophenyl) benzothiazole (31.7g), B- [1,1 ': 3 ', 1 "-terphenyl]-are packed into 1L eggplant type flask 3- ylboronic acid (33.7g), tetrakis triphenylphosphine palladium (0) (2.2g), are further added toluene (350mL), the ethyl alcohol being bubbled through nitrogen (100mL) and 2M tripotassium phosphate aqueous solution (200mL) stirs 4 hours at 100 DEG C.After being cooled to room temperature, removes water phase and remove Remove solvent and obtain residue, using silica gel column chromatography (silica gel 600mL, dichloromethane/hexane=3/7, then, methylene chloride/ Hexane=5/5) residue is refined, obtain the intermediate 6 that the above-mentioned formula of 45.9g indicates.

Intermediate 5 (4.3g), iridium chloride n hydrate (1.3g, iridium content 52%), 2- are added into 100mL eggplant type flask Ethoxy ethanol (30mL) and water (10mL), are stirred in 160 DEG C of oil bath.Halfway, the solvent of evaporation is without reflux And it evaporates.The quantity of solvent evaporated is 45mL at the end of reaction.Cellosolvo (30mL) is added after 3 hours.It is total anti- It answers 9.5 hours.After reaction, reaction solution is put into water (200mL), solid is precipitated in leaching, utilizes silica gel column chromatography (silica gel 150mL, dichloromethane/ethyl acetate=95/5, then, dichloromethane/ethyl acetate=3/7) to the precipitation solid into Row purification obtains the intermediate 7 that the above-mentioned formula of 3.8g indicates.

Into 100mL four-hole boiling flask be packed into intermediate 7 (4.8g), intermediate 6 (7.0g), silver trifluoromethanesulfonate (2.5g) and Diethylene glycol dimethyl ether (40mL), is impregnated in 135 DEG C of oil bath and is stirred.1,2.5,3,6,6.5,7.5 from reaction Diisopropyl ethyl amine (the μ L of respectively 60,140,140,70,70,70 and 70) is packed into after with 8.5 hours.Keep reaction small 9.5 When stop, after cooling, solvent is removed under reduced pressure and obtains residue, using silica gel column chromatography (dichloromethane/hexane=6/4, after And dichloromethane/hexane=5/5, then, dichloromethane/hexane=6/4) residue is refined, thus obtain 0.58g Above-mentioned formula indicate compound 1.

[synthesis example 2 (embodiment B1)]

The synthesis > of < compound 2

It is packed into the eggplant type flask of 300mL 3- amino -2-Pyridinecarboxylic Acid (12.6g, Fluorochem corporation) and de- Water dimethyl sulfoxide (100mL) is impregnated in ice-water bath (1 DEG C), further puts into carbonyl dimidazoles (16.7g) and is stirred.15 After minute, it is rinsed, is then further stirred at room temperature 5 hours with dimethyl sulfoxide (2mL).It is added into the mixture The mixture of N, O- dimethyl hydroxylamine hydrochloride (13.4g) and diisopropyl ethyl amine (24mL) is stirred at room temperature 6 hours, Then it stands at room temperature whole night.Then, it is concentrated under reduced pressure, liquid separation is carried out to residue with water and methylene chloride and is cleaned.To oil Mutually remove solvent after, using silica gel column chromatography (neutral silica gel 600mL, methylene chloride, then, methylene chloride/methanol= 1000/10) it is refined, obtains the intermediate 8 that the above-mentioned formula of 11.8g indicates.

Intermediate 8 (11.8g) and dehydration tetrahydrofuran (140mL) are added into the eggplant type flask of 500mL, is impregnated in ice water It bathes (1 DEG C).Grignard reagent liquid was added thereto with 5 minutes, the dehydration tetrahydrofuran of 60mL is further added, is stirred at room temperature 2.5 hours, the grignard reagent liquid was to stir one on one side by being packed into bits shape magnesium (4.8g) to the four-hole boiling flask of 300mL in advance Dehydration tetrahydrofuran (70mL) solution for containing 2- bromonaphthalene (40.4g) was added dropwise with 50 minutes for side, then stirs 90 minutes and prepares 's.After saturated aqueous ammonium chloride (400mL) is added thereto, methylene chloride (200mL), water (300mL) and sodium carbonate is added (10g) carries out liquid separation cleaning, with the dry oily phase of magnesium sulfate, further after concentration, using silica gel column chromatography (silica gel 1500mL, Methylene chloride/methanol=100/1, then, methylene chloride/methanol=100/2) it is refined, the above-mentioned formula for obtaining 13.1g indicates Intermediate 9.

It is packed into intermediate 9 (13.1g) and methylene chloride (200mL) into 1L eggplant type flask, puts into N- bromo at room temperature Succinimide (10.4g), is stirred in room temperature.Additional methylene chloride 200mL, futher stirs 40 minutes after 50 minutes. Liquid separation is carried out with water 500mL and methylene chloride 500mL to clean, is dried with magnesium sulfate, and lower removing solvent is depressurized.Utilize silica gel Column chromatography (silica gel 600mL is only unfolded with methylene chloride with the accumulation silica gel of methylene chloride/methanol=100/1) is to obtaining Residue refined, obtain 14.7g above-mentioned formula indicate intermediate 10.

Intermediate 10 (5.5g), 2,6- dimethylphenylboronic acid (3.8g), 2M tripotassium phosphate are packed into 1L eggplant type flask Aqueous solution (50mL), tetrakis triphenylphosphine palladium (0) (0.86g), twoAlkane (70mL) and toluene (70mL), in 105 DEG C of oil baths Stirring 2.5 hours.After being cooled to room temperature, solvent is removed under reduced pressure, it is residual to what is obtained with methylene chloride (300mL) and water (300mL) Slag carries out liquid separation cleaning, after the dry oily phase of magnesium sulfate, is concentrated under reduced pressure and obtains residue, utilize silica gel column chromatography (silicon Glue 500mL is only unfolded with methylene chloride with methylene chloride/methanol=100/1 accumulation silica gel) residue is refined, Obtain the intermediate 11 that the above-mentioned formula of 5.7g indicates.

It is packed into intermediate 11 (6.8g) and intermediate 3 (7.7g) into 1L eggplant type flask, potassium hydroxide is further added Ethyl alcohol (73mL) solution of (6.1g) stirs 3 hours when carrying out reflux in oil bath (90 DEG C), further makes the temperature of oil bath It is stirred 7 hours for 100 DEG C.Then, solvent is removed under reduced pressure, it is clear to carry out liquid separation to residue with methylene chloride (1L) and water (1L) It washes.After the dry oily phase of magnesium sulfate, solvent is removed under reduced pressure and obtains residue, (silica gel 500mL, is only used using silica gel column chromatography After methylene chloride expansion, silica gel 600mL, only toluene 4L, then, and only methylene chloride 1L) residue is refined 2 times, obtain 6.6g Above-mentioned formula indicate intermediate 12.

Into 1L eggplant type flask be added intermediate 6 (28.9g), iridium chloride n hydrate (10.7g, Furuya Metal system, Iridium content 52%), cellosolvo (0.7L) and water (60mL), return stirring 9 hours.It filters out precipitate and obtains filter cake, The half amount of the filter cake is encased in the eggplant type flask of 500mL, 3,5- heptane diketone (7.4g), potassium carbonate (10.2g) is added With cellosolvo (250mL), return stirring 8 hours.After being cooled to room temperature, the solvent of filtered out liquid is removed under reduced pressure, Residue is obtained, the residue is refined using silica gel column chromatography (silica gel 500mL, be unfolded with methylene chloride), as a result Obtain the intermediate 13 that the above-mentioned formula of 14.9g indicates.

It is packed into the 100mL eggplant type flask for having the serpentine condenser with side pipe for removing distilled out solvent Intermediate 12 (3.78g), intermediate 13 (4.49g), silver trifluoromethanesulfonate (I) (2.17g) and toluene (4mL), in 225 DEG C of oil It is reacted 1 hour in bath.Reaction evaporates whole solvents in 10 minutes after starting.Since reaction starts to see object in latter 1.5 hours LC area percentage value is only 2%, therefore stops reaction, carries out essence using column chromatography (silica gel 600mL, be only unfolded with toluene) System recycling 4.46g.

Intermediate 13 (3.57g), silver trifluoromethanesulfonate (I) (1.40g) and diethylene glycol dimethyl ether are added thereto (2mL) makes 220 DEG C of oil bath and is stirred.Halfway, diisopropyl ethyl amine is added to 300 μ L after 105 minutes, 125 200 μ L are added after minute, 150 μ L are added after 165 minutes, as a result utilize high performance liquid chromatography (HPLC) analysis and observation to mesh The yield of mark object greatly improves.It is stirred in stopping in 3 hours, is cooled to room temperature, passes through 2 column chromatographys (silica gel 850mL, dichloromethanes Alkane/hexane=1/1, silica gel 600mL, is unfolded thereafter with toluene/hexane=1/1) and obtain what the above-mentioned formula of 0.70g indicated Compound 2.

The relationship in above-mentioned reaction time and the LC area percentage value (%) of object is shown in following table 1 and Fig. 3.

[table 1]

[synthesis example 3]

The synthesis > of < compound 3 and 4

It is packed into intermediate 2 (6.6g) and 2- acetyl thiophene (3.3g) into 1L eggplant type flask, hydroxide is further added Ethyl alcohol (95mL) solution of sodium (28g) stirs 5.5 hours in oil bath (80 DEG C) when carrying out reflux.Then, water is added 250mL filters out precipitate, is cleaned 3 times, is dried with water 200mL and ethyl alcohol 20mL, and the above-mentioned formula for as a result obtaining 5.4g indicates Intermediate 14.

Bis- bromo-m-xylene of 2,5- (14.1g), n-octyl ylboronic acid (12.8g), 2M are packed into 1L eggplant type flask Tripotassium phosphate aqueous solution (80mL), tetrakis triphenylphosphine palladium (0) (0.98g), ethyl alcohol (30mL) and toluene (90mL), at 105 DEG C It is stirred 1.5 hours in oil bath.After being cooled to room temperature, water phase is removed, solvent is removed under reduced pressure, obtains residue, utilizes silica gel column chromatography Method (silica gel 600mL, be only unfolded with hexane) refines the residue, obtains the intermediate 15 that the above-mentioned formula of 18.5g indicates.

Bits shape magnesium (1.4g) and dry tetrahydrofuran (10mL) are packed into 300mL four-hole boiling flask and iodine (14mg) is stirred It mixes.Then, dry tetrahydrofuran (30mL) solution of intermediate 15 (18.5g) was added dropwise with 50 minutes at room temperature.Then it stirs 90 minutes.It is packed into trimethyl borate (22mL) and dry tetrahydrofuran (180mL) into another 1L eggplant type flask and makes interior temperature It is -30 DEG C, above-mentioned reaction solution was added dropwise with 35 minutes thereto.Then after being warming up to room temperature with 50 minutes, in 57 DEG C of oil bath Stirring 2 hours.Then, liquid obtained by diluting 35% hydrochloric acid 22mL with water 130mL is added, with ethyl acetate (1 150mL It is extracted with 2 100mL), is cleaned with salt water.Ethyl acetate is removed under reduced pressure and obtains residue, utilizes silica gel column chromatography Method (400mL, ethyl acetate/hexane=1/9, then, and ethyl acetate/hexane=1/1, then only methanol) essence is carried out to the residue System obtains the intermediate 16 that the above-mentioned formula of 12.6g indicates.

Intermediate 14 (11.8g), intermediate 16 (12.6g), barium hydroxide octahydrate are packed into 1L eggplant type flask (17.5g), tetrakis triphenylphosphine palladium (0) (1.6g), dimethoxy-ethane (270mL) and water (100mL), are stirred in 90 DEG C of oil baths It mixes 2 hours.Then, acid chloride (0.24g), 2- dicyclohexylphosphontetrafluoroborate -2 ', the tetrahydro furan of 6 '-dimethoxy-biphenyls (1.2g) is added It mutters (100mL) solution, futher stirs 2 hours.After being cooled to room temperature, solvent is removed under reduced pressure, the residue dichloromethane that will be obtained Alkane (500mL) and water (200mL) carry out liquid separation cleaning, after the dry oily phase of magnesium sulfate, are concentrated under reduced pressure and obtain residue, benefit With silica gel column chromatography (silica gel 300mL, dichloromethane/ethyl acetate=1/0, then, dichloromethane/ethyl acetate=9/1) The residue is refined, the intermediate 17 that the above-mentioned formula of 7.3g indicates is obtained.

It is packed into 2-Thiophene Carboxylic Acid (21.9g), 2- aminothiophenol (20.5g) into the detachable flask of 500mL and gathers Phosphoric acid (41.0g), is transferred in 150 DEG C of oil bath, is stirred 8 hours with mechanical agitator.Then, with water (500mL) and dichloro Methane (500mL) carries out liquid separation cleaning, with magnesium sulfate (50mL) dry oily phase, solvent is removed under reduced pressure and obtains residue, utilizes silicon Rubber column gel column chromatography (silica gel 600mL, dichloromethane/hexane=4/6) refines the residue, obtains the above-mentioned formula table of 31.5g The intermediate 18 shown.

Intermediate 17 (6.2g), iridium chloride n hydrate (1.7g, iridium content 52%), 2- are added into 100mL eggplant type flask Ethoxy ethanol (30mL) and water (5mL), are stirred in 145 DEG C of oil bath.Halfway, the solvent of evaporation without reflux and It evaporates.The quantity of solvent evaporated is 10mL at the end of reaction.Cellosolvo (2mL) He Eryi is added after 4.5 hours Ethylamine (0.86mL).Total reaction 8.5 hours.Reaction solution is put into water (150mL) after reaction, leaching analysis Solid out, using silica gel column chromatography (silica gel 600mL, dichloromethane/ethyl acetate=1/0, then, methylene chloride/acetic acid second Ester=1/1) the precipitation solid is refined, obtain the intermediate 19 that the above-mentioned formula of 4.7g indicates.

Intermediate 19 (4.7g), intermediate 18 (3.3g), silver trifluoromethanesulfonate (2.3g) are packed into 100mL four-hole boiling flask With diethylene glycol dimethyl ether (30mL), it is impregnated in 135 DEG C of oil bath and is stirred.After reaction starts 1.5,2.5 and 3.5 hours It is packed into diisopropyl ethyl amine (respectively 550 μ L).Stop reaction at 5.5 hours, solvent is removed under reduced pressure and obtains after cooling Residue refines residue using silica gel column chromatography (silica gel 500mL, dichloromethane/hexane=1/1), obtains above-mentioned formula The compound 3 of expression and the mixture of compound 4.Separation essence further is carried out to them using reverse phase ODS silica gel column chromatography System, thus obtains the compound 3 of 0.5g, the compound 4 of 1.5g.

[embodiment A1]

Luminescent quantum yield and most is carried out according to following methods to the compound 1 as iridium complex compound of the invention The measurement of big emission wavelength.

The evaluation > of < luminescent quantum yield

Compound 1 is dissolved in 2- methyltetrahydrofuran (2MeTHF) at room temperature, and (Aldrich system, dehydration, does not add Add stabilizer), preparation 1 × 10^{- 5}The solution of mol/l.The solution is packed into the quartz cell with Teflon (registered trademark) cock In, progress 20 minutes or more nitrogen is bubbled, and measures absolute quantum yield at room temperature.Result is shown in table 2.

It should be noted that using following instrument in the measurement of luminescent quantum yield (PL quantum yield).

Device: the organic EL quantum yield measurement device C9920-02 of Hamamatsu Photonics corporation

Light source: monochromatic source L9799-01

Detector: multichannel detector PMA-11

Exciting light: 380nm

The measurement > of < maximum luminous wavelength

Utilize spectrophotometer (the organic EL quantum yield measurement device C9920- of Hamamatsu Photonics corporation 02) to make compound 1 at normal temperature with 1 × 10^{- 4}Mol/L concentration below is dissolved in solution obtained by 2- methyltetrahydrofuran Measure phosphorescence spectrum.Using the wavelength of the display maximum value of obtained phosphorescence spectrum intensity as maximum luminous wavelength.

[embodiment A2~A4,1~A3 of Comparative examples A]

In embodiment A1, compound 2~4 or compound D-3 described below, compound D-5, compound D-9 are used Or compound D-10 replaces compound 1, in addition to this, is prepared as solution, measures luminescent quantum yield and maximum shines Wavelength.Show the result in table 2.It should be noted that luminescent quantum yield relative value table obtained by the value of Comparative examples A 1 is set as 1 Show.

[table 2]

Fig. 2 is illustrated in obtained by table 2 is mapped.The maximum luminous wavelength of the iridium complex compound of the invention of embodiment A1 For 650nm, compared with 1~A3 of Comparative examples A, hence it is evident that be long wavelength.In addition, embodiment A1 is shown in Fig. 2 than by comparative example The quantum efficiency of (the very big wavelength of embodiment A1) is high when 650nm shown by the extended line of A1 and the data bus connection of Comparative examples A 2 Quantum yield.It may be said that the compound of the present invention shows the maximum luminous wavelength and amount that are detached from Comparative examples A 1 and Comparative examples A 2 The higher quantum yield of the linear relation of sub- yield.

The production > of < organic electroluminescent device

Manufacture has the organic electroluminescent device of structure shown in Fig. 1 in accordance with the following methods.But not formed Fig. 1 In hole blocking layer 6 and electron injecting layer 8.

[embodiment A5]

By indium tin oxide (ITO) transparent conductive film with the thickness of 70nm is deposited on glass substrate 1 and is sputtered Film forming product (GEOMATEC corporation, spatter film forming product), using common photoetching technique and hydrochloric acid to the spatter film forming product It is patterned with the striped of 2mm width and forms anode 2.Surfactant is successively carried out to figuratum ito substrate is formed The ultrasonic cleaning of aqueous solution, the washing of ultrapure water, the ultrasonic cleaning of ultrapure water, ultrapure water washing after, utilize compression empty Gas makes it dry, and finally carries out ultraviolet and ozone cleaning.The ITO is functioned as transparent electrode 2.

Next, aryl amine polymers, structural formula (A-1) that preparation is indicated containing structural formula below (P-1) indicate 4- isopropyl -4 '-methyldiphenyl base iodineThe hole injection layer of four (pentafluorophenyl group) borates and butyl benzoate is formed with painting Cloth liquid.The coating fluid is formed a film on anode with following conditions using spin-coating method, obtains the hole injection layer 3 of film thickness 40nm.

< hole injection layer, which is formed, uses coating fluid >

Solvent: butyl benzoate

Coating fluid concentration: 2.0 mass % of P-1

: 0.4 mass % of A-1

The membrance casting condition > of < hole injection layer 3

Spin-coating method atmosphere: in atmosphere

Heating condition: in atmosphere, 240 DEG C, 1 hour

Next, hole transmission layer of the preparation containing the compound (P-2) with following structures shown is formed with coating Liquid is formed a film with following conditions using spin-coating method, makes its polymerization using heating, the hole transmission layer 4 of film thickness 25nm is consequently formed.

< hole transmission layer, which is formed, uses coating fluid >

Solvent: cyclohexylbenzene

Coating fluid concentration: 2.0 mass %

< membrance casting condition >

Spin-coating method atmosphere: in dry nitrogen

Heating condition: 230 DEG C, 30 minutes (under dry nitrogen)

Next, as charge transport materials, being used organic compound described below (H-1) when forming luminescent layer With organic compound (H-2), come using iridium complex compound (compound 1) according to following compositions shown as luminescent material The composition containing iridium complex compound is prepared, is spun on hole transmission layer according to condition described below, thus obtains film thickness The luminescent layer of 84nm.

< luminescent layer, which is formed, uses coating fluid >

Solvent: 1547 parts by weight of cyclohexylbenzene

Luminescent layer composition: 30 parts by weight of H-1

70 parts by weight of H-2

1 20 parts by weight of compound

< membrance casting condition >

Spin-coating method atmosphere: in dry nitrogen

Heating condition: 120 DEG C × 20 minutes (under dry nitrogen)

Here, substrate of the film forming until luminescent layer is transferred in vacuum deposition apparatus, will be steamed using vacuum vapour deposition Plating speed control existsRange and make the organic compound (ET-1) with following structures shown and The 2:3 mixture layer of Liq is stacked on luminescent layer 5, forms the electron transfer layer 7 of film thickness 30nm.Hole blocking layer 6 is not formed.

Here, it proceeds to the element until electron transfer layer 7 is deposited to be set in another evaporation coating device, make as cathode The striated shadow mask of the 2mm wide of the mask of vapor deposition is closely sealed with the mode orthogonal with the ITO striped of anode 2 and element.It is not formed Electron injecting layer 8.

Next, the aluminium as cathode 9 is heated also with molybdenum boat, the aluminium layer of film thickness 80nm is formed.Above 2 layers Vapor deposition when substrate temperature be maintained at room temperature.

Then, element deteriorates in preservation because of the moisture etc. in atmosphere in order to prevent, according to following record method into Row encapsulation process.

In nitrogen glove box, photocuring is coated with the width of about 1mm in the peripheral part of the glass plate of 23mm × 23mm size Property resin 30Y-437 (ThreeBond corporation), central portion be arranged moisture absorption sheet material (Dynic corporation).It will finish The substrate that cathode is formed is bonded thereon in the face the being deposited mode opposed with desiccant sheet material.Then, only to being coated with light The area illumination ultraviolet light of curable resin, makes resin solidification.

Thus the organic electroluminescent device of the light-emitting area part with the size of 2mm × 2mm is obtained.

[embodiment A6]

In embodiment A5, the compound 1 used when forming luminescent layer is changed to compound 2, in addition to this, with implementation Example A3 similarly makes organic electroluminescent device.

[Comparative examples A 5]

In embodiment A5, the compound 1 used when forming luminescent layer is changed to the compound D-21 of following formula expression, In addition to this, organic electroluminescent device is made in the same manner as embodiment A3.

[Comparative examples A 6]

In embodiment A5, the compound 1 used when forming luminescent layer is changed to the compound D-22 of following formula expression, In addition to this, organic electroluminescent device is made in the same manner as embodiment A3.

The result of element function is shown in table 3.The driving service life under the constant current driven of the compound of comparative example is all short In corresponding embodiment.Which imply the durability of the complex of comparative example is low.

[table 3]

[embodiment B2-1]

Be packed into 25mL eggplant type flask intermediate 20 (72mg) that above-mentioned formula indicates and intermediate 21 (192mg, 1eq), Silver trifluoromethanesulfonate 31mg (1eq) and cyclohexyl benzene 0.3mL carries out nitrogen displacement.About 5 points of heating stirring in 200 DEG C of oil baths Zhong Hou, is added 2,6- di-tert-butyl pyridine 42mg (1eq), thus the further heating stirring in 200 DEG C of oil baths obtains above-mentioned formula The compound 20 of expression.

[comparative example B1 and embodiment B2-2]

Intermediate 20 (72mg), intermediate 21 (192mg, 1eq), silver trifluoromethanesulfonate are packed into 25mL eggplant type flask 31mg (1eq) and cyclohexyl benzene 0.3mL carries out nitrogen displacement.Heating stirring about 105 minutes in 200 DEG C of oil baths.Up to the present As comparative example B1.

Followed by, 2,6- di-tert-butyl pyridine 42mg (1eq) is further added, is further heated in 200 DEG C of oil baths Stirring 30 minutes.LC analysis is carried out after 135 minutes total.As embodiment B2-2.

[comparative example B2 and embodiment B2-3]

Intermediate 20 (72mg), intermediate 21 (192mg, 1eq), 2,6- di-t-butyl pyrrole are packed into 25mL eggplant type flask Pyridine 42mg (1eq) and cyclohexyl benzene 0.3mL carries out nitrogen displacement.Heating stirring about 105 minutes in 200 DEG C of oil baths.To being at present Only it is used as comparative example B2.

Followed by, silver trifluoromethanesulfonate 31mg (1eq) is added, the further heating stirring in 200 DEG C of oil baths.It is total LC analysis is carried out after 135 minutes.As embodiment B2-3.

For embodiment B2-1~B2-3, comparative example B1 and comparative example B2, the reaction for generating compound 20 is tracked using LC. Result is summarized in table 4 and Fig. 4.These are the result shows that exist simultaneously silver-colored (I) salt and organic base to yield It improves extremely effective.

[table 4]

[embodiment B3-1]

Be packed into 25mL eggplant type flask intermediate 22 (84.5mg) that above-mentioned formula indicates and intermediate 23 (184mg, 1eq), silver trifluoromethanesulfonate 32mg (1eq) and cyclohexyl benzene 0.3mL carries out nitrogen displacement.The heating stirring in 220 DEG C of oil baths About after five minutes, 2,6- di-tert-butyl pyridine 43mg (1eq) is added, the further heating stirring in 220 DEG C of oil baths obtains above-mentioned The compound 21 that formula indicates.

[comparative example B3 and embodiment B3-2]

Intermediate 22 (84.5mg), intermediate 23 (184mg, 1eq), 2,6- di-t-butyl are packed into 25mL eggplant type flask Pyridine 43mg (1eq) and cyclohexyl benzene 0.3mL carries out nitrogen displacement.Heating stirring about 65 minutes in 220 DEG C of oil baths.To current Until be used as comparative example B3.

Followed by, silver trifluoromethanesulfonate 32mg (1eq) is added, the further heating stirring in 220 DEG C of oil baths.Total 95 LC analysis is carried out after minute and after 125 minutes.As embodiment B3-2.

For embodiment B3-1, embodiment B3-2 and comparative example B3, the reaction for generating compound 21 is tracked using LC.It will knot Fruit is summarized in table 5 and Fig. 5.These the result shows that make silver-colored (I) salt and organic base exist simultaneously the raising to yield in the reaction It is extremely effective.

[table 5]

[embodiment B4-1]

Intermediate 20 (72mg), the intermediate 24 (172mg, 1eq) that above-mentioned formula indicates, three are packed into 25mL eggplant type flask Fluorine methanesulfonic acid silver 32mg (1.5eq) and cyclohexyl benzene 0.5mL carries out nitrogen displacement.Heating stirring about 5 minutes in 200 DEG C of oil baths Afterwards, diisopropyl ethyl amine 42mg (1eq) is added, the further heating stirring in 220 DEG C of oil baths obtains the change that above-mentioned formula indicates Close object 22.

[comparative example B4 and embodiment B4-2]

Intermediate 20 (72mg), intermediate 24 (172mg, 1eq), silver trifluoromethanesulfonate are packed into 25mL eggplant type flask 32mg (1.5eq) and cyclohexyl benzene 0.5mL carries out nitrogen displacement.Heating stirring about 60 minutes in 200 DEG C of oil baths.To being at present Only it is used as comparative example B4.

Followed by, diisopropyl ethyl amine 42mg (1eq) further is added, further heating is stirred in 220 DEG C of oil baths It mixes 30 minutes.LC analysis is carried out after 90 minutes total.As embodiment B4-2.

For embodiment B4-1, embodiment B4-2 and comparative example B4, the reaction for generating compound 22 is tracked using LC.It will knot Fruit is summarized in table 6 and Fig. 6.These the result shows that make silver-colored (I) salt and organic base exist simultaneously the raising to yield in the reaction It is extremely effective.

[table 6]

It is described the invention in detail referring to specific implementation form, but is not departing from the spirit and scope of the present invention In the case where various changes, amendment can be added, this is clear to those skilled in the art.The application is based on 2016 Japanese patent application (Japanese Patent Application 2016-197202) filed in October 5 is simultaneously incorporated in this for its content as reference.

Industrial availability

The present invention can not only be preferred for using organic electroluminescent device as the material of the organic assembly of representative, moreover it is possible to Enough it is preferably used for the various fields of organic electroluminescent device, such as flat-panel monitor (such as OA computer is used or wall Hanging type television), utilize light source (such as the back of the light source of duplicator, liquid crystal display, instrument class as the feature of planar luminous body Light source), display board, identification light, the fields such as lighting device.

Symbol description

1 substrate

2 anodes

3 hole injection layers

4 hole transmission layers

5 luminescent layers

6 hole blocking layers

7 electron transfer layers

8 electron injecting layers

9 cathodes

10 organic electroluminescent devices

Claims (10)

1. An iridium complex represented by the following formula (1), In formula (1), Ir represents an iridium atom, Ring Cy ¹ represents an aromatic or heteroaromatic ring containing carbon atoms C ¹ and C ² , The ring Cy ² represents a structure represented by any one of the following formulae (2) to (5) containing a carbon atom C ³ and a nitrogen atom N ¹ , Ring Cy ³ represents an aromatic or heteroaromatic ring containing carbon atoms C ⁴ and C ⁵ , Ring Cy ⁴ represents a heteroaromatic ring containing carbon atom C ⁶ and nitrogen atom N ² , When there are multiple rings Cy ¹ to Cy ⁴ , they may be the same or different, m is an integer from 1 to 3, n is an integer from 0 to 2, m+n=3, R ¹ to R ⁴ each independently represent a hydrogen atom or a substituent, When a plurality of R ¹ to R ⁴ are present, they may be the same or different, a, c and d are integers of the maximum number of groups that can be substituted on said ring Cy ¹ , ring Cy ³ and ring Cy ⁴ , respectively, b is 5, 2 . The iridium complex according to claim 1 , wherein the number of atoms in the rings constituting the ring Cy ¹ , the ring Cy ³ and the ring Cy ⁴ in the formula (1) is 5 to 30, respectively. 3 . 3 . The iridium complex according to claim 1 or 2 , wherein R ¹ to R ⁴ in the formula (1) are each independently a hydrogen atom, F, CN, a direct carbon atom having 1 to 30 carbon atoms. 4 . A chain, branched or cyclic alkyl group, an aromatic group with 5 to 60 carbon atoms, or a heteroaromatic group with 5 to 60 carbon atoms. 4 . The iridium complex according to claim 1 , wherein the ring Cy ¹ and the ring Cy ³ in the formula (1) are each independently a benzene ring or a naphthalene ring. 5 . The iridium complex according to any one of claims 1 to 4, wherein the ring Cy ⁴ in the formula (1) is an imidazole ring, azole ring, thiazole ring, benzimidazole ring, benzo azole ring, benzothiazole ring, pyridine ring, quinoline ring, isoquinoline ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, cinnoline ring, phthalazine ring, quinazoline ring, quinoxa oxoline or naphthyridine ring. 6 . The iridium complex according to claim 1 , wherein the iridium complex according to claim 1 , obtained by dissolving the iridium complex at a concentration of 1×10 ⁻⁴ mol/L or less in 2-methyltetrahydrofuran at room temperature. 7 . The displayed phosphorescence spectrum has a maximum emission wavelength of 620 nm or more. 7. A composition comprising the iridium complex according to any one of claims 1 to 6 and an organic solvent. 8 . An organic electroluminescence element comprising the iridium complex according to claim 1 . 9. A display device comprising the organic electroluminescent element according to claim 8. 10. A lighting device comprising the organic electroluminescent element according to claim 8.