CN1777663A

CN1777663A - Organic electroluminescent devices and metal complex compounds

Info

Publication number: CN1777663A
Application number: CN 200480010948
Authority: CN
Inventors: 新居一巳; 渡边康介; 五十岚达也; 市嶋靖司; 伊势俊大
Original assignee: Fujifilm Corp
Current assignee: UDC Ireland Ltd
Priority date: 2003-06-02
Filing date: 2004-06-01
Publication date: 2006-05-24
Anticipated expiration: 2024-06-01
Also published as: CN100551994C; CN101667626A; CN101667626B

Abstract

The present invention relates to an organic electroluminescent device having a pair of electrodes and at least one organic layer including a light-emitting layer between the pair of electrodes, wherein at least one layer between the pair of electrodes contains at least one metal complex having a tridentate-chain structure ligand or higher polydentate-chain structure ligand.

Description

Organnic electroluminescent device and metal complex compounds

Technical field

The present invention relates to electric energy is converted into the Organnic electroluminescent device (light-emitting device or EL device) of light.The invention still further relates to the metal complex that is suitable in the described Organnic electroluminescent device.

Background technology

Recently, various types of display unit are researched and developed actively.Wherein, more concerns concentrate on organic electroluminescent (EL) device.This is because organic El device is can be in the luminous display unit that has prospect of high radiance under the low voltage.

Recently, study energetically organic El device is applied to colour display device and incandescent source.Yet, develop high-grade colour display device and incandescent source and need strengthen turning blue, the characteristic (performance) of the device of green and ruddiness.

On the other hand, as the light-emitting device that uses rubescent look phosphor material, the platinum porphyrins complex compound that those uses contain the ring-type tridentate ligand is known in for example Nature395 as the device of luminescent material, and 151 (1998) and U.S. patent No.6,303, among the 231B1.Yet,, therefore need strengthen maximum is luminous because maximum luminous (brightness) of these devices is low.

In addition, report about the platinum porphyrins complex compound that contains dipyridyl series or phenanthroline series chain tetradentate ligand is existing (referring to Chem.Eur.J., 9, No.6,1264 (2003), U.S. patent No.6,653,654B1 and WO03/093283A1).Yet these complex compounds can not be realized the compatible of persistence and the characteristics of luminescence such as colour purity simultaneously.Therefore, need to improve these performances.For green luminescent material and blue light-emitting material, need develop advanced material all excellent aspect the characteristics of luminescence and persistence two in addition in the wavelength region may shorter than the emission wavelength zone of aforementioned luminescent material.

Summary of the invention

According to the present invention, as described below:

[1] Organnic electroluminescent device, it comprises pair of electrodes and at least one organic layer that comprises luminescent layer between described pair of electrodes, and wherein at least one layer between described pair of electrodes comprises at least a metal complex with three toothed chain structure parts or higher multiple tooth chain structure part.

[2] as [1] described Organnic electroluminescent device, the metal ion in the wherein said metal complex is selected from platinum, iridium, rhenium, palladium, rhodium, ruthenium and cupric ion.

[3] as [1] or [2] described Organnic electroluminescent device, wherein said metal complex does not have carbon-to-metal bond.

[4] as each described Organnic electroluminescent device of [1]-[3], wherein said metal complex is phosphorescent metal complex, and described metal complex is contained in the described luminescent layer.

[5] as each described Organnic electroluminescent device of [1]-[4], wherein said metal complex is the compound by formula (1) representative:

Formula (1)

Wherein, M ¹¹Representation metal ion; L ¹¹, L ¹², L ¹³, L ¹⁴And L ¹⁵Represent separately and M ¹¹The coordinate part; L ¹¹And L ¹⁴Be not joined together to form the ring-type part by atomic group; L ¹⁵Not with L ¹¹And L ¹⁴Bonding is to form the ring-type part; Y ¹¹, Y ¹²And Y ¹³Represent linking group, singly-bound or two key separately; L ¹¹And Y ¹²Between key, Y ¹²And L ¹²Between key, L ¹²And Y ¹¹Between key, Y ¹¹And L ¹³Between key, L ¹³And Y ¹³Between key and Y ¹³And L ¹⁴Between key represent singly-bound or two key separately; n ¹¹Represent 0 to 4.

[6] as each described Organnic electroluminescent device of [1]-[5], wherein said metal complex is the compound by formula (2) representative:

Formula (2)

Wherein, M ²¹Representation metal ion; Y ²¹Represent linking group, singly-bound or two key; Y ²²And Y ²³Represent singly-bound or linking group separately; Q ²¹And Q ²²Representative forms the atomic group of nitrogen heterocyclic ring necessity separately; Y ²¹With by Q ²¹Key and Y between the ring that forms ²¹With by Q ²²Key between the ring that forms is represented singly-bound or two key separately; X ²¹And X ²²Represention oxygen atom, sulphur atom or replacement or unsubstituted nitrogen-atoms separately; R ²¹, R ²², R ²³And R ²⁴Represent hydrogen atom or substituting group separately, R ²¹And R ²², and R ²³And R ²⁴Can be separately each other bonding to form ring; L ²⁵Representative and M ²¹The coordinate part; n ²¹Represent 0 to 4 integer.

[7] as [6] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (2) representative, wherein by Q ²¹The ring that forms and by Q ²²Each pyridine ring naturally of the ring that forms, and Y ²¹The linking group that representative is made up of at least one atom.

[8] as [6] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (2) representative, wherein by Q ²¹The ring that forms and by Q ²²Each pyridine ring naturally of the ring that forms, and Y ²¹Represent singly-bound or two key, and X ²¹And X ²²Represent sulphur atom or replacement or unsubstituted nitrogen-atoms separately.

[9] as [6] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (2) representative, wherein by Q ²¹The ring that forms and by Q ²²Each 5 member heterocyclic ring containing nitrogen naturally of the ring that forms.

[10] as [6] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (2) representative, wherein by Q ²¹The ring that forms and by Q ²²Each contains 6 yuan of heterocycles of at least two nitrogen-atoms naturally the ring that forms.

[11] as [1] or [2] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (9) representative:

Formula (9)

Wherein, M ^A1Representation metal ion; Q ^A1And Q ^A2Representative forms the atomic group of nitrogen heterocyclic ring necessity separately; R ^A1, R ^A2, R ^A3And R ^A4Represent hydrogen atom or substituting group separately; R ^A1And R ^A2, and R ^A3And R ^A4Can be respectively each other bonding to form ring; Y ^A2And Y ^A3Represent linking group or singly-bound separately; Y ^A1Represent linking group, singly-bound or two key so that two two parts in bracket are linked together; L ^A5Representative and M ^A1The coordinate part; n ^A1Represent 0 to 4 integer.

[12] as [1] or [2] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (10) representative,

Formula (10)

Wherein, M ^B1Representation metal ion; Y ^B1Represent linking group; Y ^B2And Y ^B3Represent linking group or singly-bound separately; X ^B1And X ^B2Represention oxygen atom, sulphur atom or replacement or unsubstituted nitrogen-atoms separately; n ^B1And n ^B2Represent 0 to 1 integer separately; R ^B1, R ^B2, R ^B3, R ^B4, R ^B5And R ^B6Represent hydrogen atom or substituting group separately; R ^B1And R ^B2, and R ^B3And R ^B4Can be respectively each other bonding to form ring; L ^B5Representative and M ^B1The coordinate part; n ^B3Represent 0 to 4 integer; Y ^B1Not with R ^B5Or R ^B6Connect.

[13] as each described Organnic electroluminescent device of [1]-[4], wherein said metal complex is the compound by formula (8) representative,

Formula (8)

Wherein, M ⁸¹Representation metal ion; L ^B1, L ⁸², L ⁸³And L ⁸⁵Represent separately and M ⁸¹The coordinate part; L ^B1And L ⁸³Be not joined together to form ring-type part or tetradentate ligands or higher polydentate ligand by atomic group; L ⁸⁵Not directly and L ⁸¹Or L ⁸³Bonding, but pass through metal link; Y ⁸¹And Y ⁸²Represent linking group, singly-bound or two key separately; n ⁸¹Represent 0 to 3 integer.

[14] as [13] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (8) representative, wherein L ⁸¹, L ⁸²And L ⁸³Represent separately by carbon atom and M ⁸¹Coordinate aromatic carbocyclic or heterocycle, or by nitrogen-atoms and M ⁸¹The coordinate nitrogen heterocyclic ring; And L ⁸¹, L ⁸²And L ⁸³In be described nitrogen heterocyclic ring one of at least.

[15] as [1] or [2] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (X1) representative:

Formula (X1)

Wherein, M ^X1Representation metal ion; Q ^X11, Q ^X12, Q ^X13, Q ^X14, Q ^X15And Q ^X16Represent separately and M ^X1Coordinate atom or have and M ^X1The atomic group of coordinate atom; L ^X11, L ^X12, L ^X13And L ^X14Represent singly-bound, two key or linking group separately; By Q ^X11-L ^X11-Q ^X12-L ^X12-Q ^X13The atomic group of forming and by Q ^X14-L ^X13-Q ^X15-L ^X14-Q ^X16The atomic group of forming is represented tridentate ligand separately; M ^X1And Q ^X11Between key, M ^X1And Q ^X12Between key, M ^X1And Q ^X13Between key, M ^X1And Q ^X14Between key, M ^X1And Q ^X15Between key and M ^X1And Q ^X16Between key each coordinate bond or covalent linkage naturally.

[16] as [15] described Organnic electroluminescent device, wherein said metal complex by formula (X1) representative is the compound by formula (X2) representative:

Formula (X2)

Wherein, M ^X2Representation metal ion; Y ^X21, Y ^X22, Y ^X23, Y ^X24, Y ^X25And Y ^X26Represent separately and M ^X2The coordinate atom; Each Q ^X21, Q ^X22, Q ^X23, Q ^X24, Q ^X25And Q ^X26Representative and each Y ^X21, Y ^X22, Y ^X23, Y ^X24, Y ^X25And Y ^X26Form the atomic group of aromatic ring or heterocycle necessity; L ^X21, L ^X22, L ^X23And L ^X24Represent singly-bound, two key or linking group separately; M ^X2And Y ^X21Between key, M ^X2And Y ^X22Between key, M ^X2And Y ^X23Between key, M ^X2And Y ^X24Between key, M ^X2And Y ^X25Between key and M ^X2And Y ^X26Between key each coordinate bond or covalent linkage naturally.

[17] as [15] described Organnic electroluminescent device, wherein said metal complex by formula (X1) representative is the compound by formula (X3) representative:

Formula (X3)

Wherein, M ^X3Representation metal ion; Y ^X31, Y ^X32, Y ^X33, Y ^X34, Y ^X35And Y ^X36Represent carbon atom, nitrogen-atoms or phosphorus atom separately; L ^X31, L ^X32, L ^X33And L ^X34Represent singly-bound, two key or linking group separately; M ^X3And Y ^X31Between key, M ^X3And Y ^X32Between key, M ^X3And Y ^X33Between key, M ^X3And Y ^X34Between key, M ^X3And Y ^X35Between key and M ^X3And Y ^X36Between key each coordinate bond or covalent linkage naturally.

[18] as each described Organnic electroluminescent device of [1]-[17], wherein said organic layer comprises at least one luminescent layer and hole transmission layer, and described organic layer also comprises the layer that at least one is selected from exciton barrier-layer, hole injection layer, hole blocking layer and electron transfer layer.

[19] as each described Organnic electroluminescent device of [1]-[18], wherein said organic layer comprises at least one luminescent layer, and the material of main part of described luminescent layer is selected from amine compound, the accurate oxide compound of metal-chelating (compound that promptly has metal-oxygen key), and wherein said metal is aluminium, zinc or transition metal, polyarylene compound, fused aromatic isocyclic compound and non-complexing aromatic heterocycle compounds.

[20] as each described Organnic electroluminescent device of [1]-[19], wherein said organic layer comprises at least one electron transfer layer, and wherein electron transport material is selected from the accurate oxide compound of metal-chelating, polyarylene compound, fused aromatic isocyclic compound and non-complexing aromatic heterocycle compounds.

[21] as each described Organnic electroluminescent device of [1]-[20], wherein said organic layer comprises at least one luminescent layer, and the material of main part of described luminescent layer is made up of at least two kinds of compounds.

[22] compound of representing by formula (11):

Formula (11)

Wherein, R ^C1And R ^C2Represent hydrogen atom or substituting group separately; R ^C3, R ^C4, R ^C5And R ^C6Represent substituting group separately; n ^C3And n ^C6Represent 0 to 3 integer separately; n ^C4And n ^C5Represent 0 to 4 integer separately; When there being a plurality of R ^C3, R ^C4, R ^C5Or R ^C6The time, each R ^C3, R ^C4, R ^C5Or R ^C6Can be same to each other or different to each other, and a plurality of R ^C3, R ^C4, R ^C5Or R ^C6Separately each other bonding to form condensed ring.

[23] compound of representing by formula (12):

Formula (12)

Wherein, R ^D3And R ^D4Represent hydrogen atom or substituting group separately; R ^D1And R ^D2Represent substituting group separately; n ^D1And n ^D2Represent 0 to 4 integer separately; When there being a plurality of R ^D1Or R ^D2The time, each R ^D1Or R ^D2Can be same to each other or different to each other, and a plurality of R ^D1Or R ^D2Bonding is to form ring each other; Y ^D1Representative has vinyl, phenylene, pyridine ring, pyrazine ring, the pyrimidine ring of replacement in 1-and 2-position or has the alkylidene group of 1 to 8 carbon atom.

[24] compound of representing by formula (X1):

Formula (X1)

[25] compound of representing by formula (X2):

Formula (X2)

Wherein, M ^X2Representation metal ion; Y ^X21, Y ^X22, Y ^X23, Y ^X24, Y ^X25And Y ^X26Represent separately and M ^X2The coordinate atom; Each Q ^X21, Q ^X22, Q ^X23, Q ^X24, Q ^X25And Q ^X26Representative and each Y ^X21, Y ^X22, Y ^X23, Y ^X24, Y ^X25And Y ^X26The atomic group of each self-forming aromatic ring or heterocycle necessity; L ^X21, L ^X22, L ^X23And L ^X24Represent singly-bound, two key or linking group separately; M ^X2And Y ^X21Between key, M ^X2And Y ^X22Between key, M ^X2And Y ^X23Between key, M ^X2And Y ^X24Between key, M ^X2And Y ^X25Between key and M ^X2And Y ^X26Between key each coordinate bond or covalent linkage naturally.

[26] compound of representing by formula (X3):

Formula (X3)

Used in this manual term " chain part " is meant and removes for example part of porphyrin and phthalocyanine of decyclization part.With formula (8) is example, and described term is not meant and directly links to each other, but passes through Y ⁸¹, L ⁸², Y ⁸²And M ⁸¹And the ligand L that links to each other ⁸¹And L ⁸³Even working as L ⁸¹, Y ⁸¹, L ⁸², Y ⁸²Or L ⁸³Contain in the situation of ring structure such as benzene, pyridine and quinoline, described part is meant the chain part, as long as L ⁸¹And L ⁸³Directly do not link to each other, but pass through Y ⁸¹, L ⁸², Y ⁸²And M ⁸¹And link to each other.Can be at L ⁸¹And Y ⁸¹, or Y ⁸¹And L ⁸², or L ⁸²And Y ⁸², or Y ⁸²And L ⁸³Between exist other aromatic group to form ring.

Below will be more comprehensively and describe other and other characteristic and advantage of the present invention in detail.

Embodiment

Organnic electroluminescent device of the present invention (this and after be sometimes referred to as device of the present invention) be characterised in that and it comprise pair of electrodes and at least one organic layer that comprises luminescent layer between described pair of electrodes (described organic layer can include organic compounds, or comprise mineral compound in addition), wherein the arbitrary layer between described pair of electrodes comprises the phosphorescent metal complex with three toothed chain parts or higher multiple tooth chain part.

As the metal complex that uses among the present invention with three toothed chain parts or higher multiple tooth chain part (this and after be sometimes referred to as metal complex of the present invention), preferably has metal complex from three teeth to octadentate chain part, more preferably has metal complex from four teeth to octadentate chain part, be more preferably the metal complex that has from four tooth to six toothed chain parts, most preferably have the metal complex of four toothed chain parts.

The chain part that uses among the present invention preferably contains at least one nitrogen heterocyclic ring (for example pyridine, quinoline, pyrrole ring) so that (as if being example with formula (1), then described metal is M with major metal through nitrogen-atoms ¹¹) coordination.

Preferred metal complex of the present invention is carbon containing-metallic bond not.Also be between atoms metal and carbon atom, not become key in the preferable alloy complex compound.Especially about term " not carbon containing-metallic bond ", the preferable alloy complex compound has following arbitrary key.Also be preferred containing metal-nitrogen key, metal-oxygen key, metal-sulfur key, metal-phosphorus key and metal-selenium key.More preferably metal-nitrogen key, metal-oxygen key, metal-sulfur key and metal-phosphorus key.Be more preferably metal-nitrogen key, metal-oxygen key and metal-sulfur key.

Compound used among the present invention is not particularly limited, as long as this compound is phosphorescent compound.Preferably be not less than-30 ℃ of phosphorescent compounds, more preferably be not less than-10 ℃, be more preferably at and be not less than 0 ℃, and particularly preferably in being not less than 10 ℃.This compound can fluoresce simultaneously.In this case, preferably this compound is not less than 2 times of its fluorescence intensity at 20 ℃ phosphorescence intensity, more preferably is not less than 10 times, is more preferably and is not less than 100 times.

Used phosphor material has and is not less than 10% phosphorescence quantum yield (20 ℃) and phosphorescence λ among preferred the present invention _Max(emission maximum phosphorescence) in the scope of 400nm to 700nm, more preferably phosphorescence quantum yield (20 ℃) is not less than 15% and phosphorescence λ _MaxIn the scope of 400nm to 575nm, be more preferably phosphorescence quantum yield (20 ℃) and be not less than 20% and phosphorescence λ _MaxIn the scope of 400nm to 560nm.

Metal complex of the present invention is incorporated in the arbitrary layer between the pair of electrodes, preferably it is incorporated in hole injection/hole transmission layer and/or luminescent layer, more preferably it is incorporated in luminescent layer.Metal complex of the present invention is being incorporated in the situation of luminescent layer, the phosphorescent compound concentrations in the luminescent layer is 1-30 weight % based on the weight of luminescent layer separately, and more preferably 2-20 weight % is more preferably 3-15 weight %.

A preferred implementation of metal complex of the present invention has by the tetradentate ligand of formula (1) representative or higher polydentate ligand.Preferred implementation by the metal complex of formula (1) representative is by formula (2), (5), (9) or (10) representative.

Formula (5)

By the preferred implementation of the metal complex of formula (2) representative by formula (3) representative.

Formula (3)

By the preferred implementation of the metal complex of formula (9) representative by formula (6) or formula (7) representative, and by the preferred implementation of the metal complex of formula (7) representative by formula (11) representative.

By the preferred implementation of the metal complex of formula (10) representative by formula (12) representative.

Formula (6)

Formula (7)

Compound by formula (1) representative below will be described.

M ¹¹Representation metal ion.This metal ion is not particularly limited, but preferably divalence or trivalent metal ion.As divalence or trivalent metal ion, preferred platinum, iridium, rhenium, palladium, rhodium, ruthenium, copper, europium, gadolinium and terbium ion.More preferably platinum, iridium and europium ion in these ions are more preferably platinum and iridium ion, especially preferred platinum ion.

L ¹¹, L ¹², L ¹³And L ¹⁴Represent separately and M ¹¹The coordinate part.As being contained in L ¹¹, L ¹², L ¹³Or L ¹⁴In and and M ¹¹The coordinate atom, preferred nitrogen, oxygen, sulphur and carbon atom are more preferably nitrogen, oxygen and carbon atom.

At M ¹¹And L ¹¹, L ¹², L ¹³Or L ¹⁴Between the key that forms can be covalent linkage, ionic linkage or coordinate bond.Comprise L ¹¹, Y ¹², L ¹², Y ¹¹, L ¹³, Y ¹³And L ¹⁴Part anion ligand (being at least one negatively charged ion and the metal link of part) preferably.Negatively charged ion number in the anion ligand is 1-3 preferably, is more preferably 1 or 2, and being more preferably is 2.

L ¹¹, L ¹², L ¹³Or L ¹⁴Through carbon atom and M ¹¹Coordination is not particularly limited this.The example of these parts comprises imino-part, aromatic carbocyclic part (for example benzene, naphthalene, anthracene, benzene anthracene part), heterocyclic ligand (for example thiophene, pyridine, pyrazine, pyrimidine, thiazole, azoles, pyrroles, imidazoles, pyrazoles part, the condensed ring (for example quinoline, benzothiazole part) that contains these rings and the tautomer of these rings).

L ¹¹, L ¹², L ¹³Or L ¹⁴Through nitrogen-atoms and M ¹¹Coordination is not particularly limited this.The example of these parts comprises that (for example (Ding Yi tautomer also can comprise the tautomer of following example and common tautomer to the nitrogen heterocyclic ring part in the present invention for pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, azoles, pyrroles, imidazoles, pyrazoles, triazole, oxadiazole and thiadiazoles part, the condensed ring (for example quinoline, benzoxazole, benzoglyoxaline part) that comprises any these parts and the tautomer of these parts; 5 yuan of heterocyclic ligands of compound (24) for example; 5 yuan of heterocyclic ligands of the end of compound (64); and 5 yuan of heterocyclic ligands of compound (145) are defined as pyrroles's tautomer)); and amino ligands (for example the alkylamino part (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; especially preferably have those of 2-10 carbon atom; methylamino for example); virtue amino ligands (for example phenylamino); amido ligands (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; those of preferred especially 2-10 carbon atom; kharophen for example; benzamido); the alkoxycarbonyl ammonia ylidene ligands (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; especially preferably have those of 2-12 carbon atom; methoxycarbonyl amino for example); the aryloxycarbonyl amino ligands (preferably has 7-30 carbon atom; more preferably have 7-20 carbon atom; especially preferably have those of 7-12 carbon atom; phenyloxycarbonyl amino for example); the Herbicidal sulphonylamino ylidene ligands (preferably has 1-30 carbon atom; more preferably have 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, for example sulfonyl methane amino; phenylsulfonamido), imino-part).These parts can also be substituted base and replace.

L ¹¹, L ¹², L ¹³Or L ¹⁴Through Sauerstoffatom and M ¹¹Coordination is not particularly limited this.The example of these parts comprises that alkoxy ligand (preferably has 1-30 carbon atom, more preferably have 1-20 carbon atom, especially preferably have those of 1-10 carbon atom, methoxyl group for example, oxyethyl group, butoxy, the 2-ethyl hexyl oxy), aryloxy ligands (preferably has 6-30 carbon atom, more preferably have 6-20 carbon atom, especially preferably have those of 6-12 carbon atom, phenoxy group for example, the 1-naphthyloxy, the 2-naphthyloxy), the heterocyclic oxy group part (preferably has 1-30 carbon atom, more preferably has 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, pyridyloxy for example, pyrazoles oxygen base, 2-pyrimidinyl oxy, quinoline oxy), acyloxy (preferably has 2-30 carbon atom, more preferably have 2-20 carbon atom, especially preferably have those of 2-10 carbon atom, for example acetoxyl group, benzoyloxy), silyloxy (preferably has 3-40 carbon atom, more preferably has 3-30 carbon atom, especially preferably have those of 3-24 carbon atom, trimethylammonium silyloxy for example, the triphenyl silyloxy), carbonyl ligands (ketone part for example, ester part, amide ligands), with ether part (for example dialkyl ether part, diaryl ether part, furyl part).

L ¹¹, L ¹², L ¹³Or L ¹⁴Through sulphur atom and M ¹¹Coordination is not particularly limited this.The example of these parts comprises that the alkylthio part (preferably has 1-30 carbon atom, more preferably have 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, methyl sulphur for example, ethyl sulphur), aryl sulfo-part (preferably has 6-30 carbon atom, more preferably has 6-20 carbon atom, especially preferably have those of 6-12 carbon atom, phenyl sulphur for example), heterocycle sulfo-part (preferably has 1-30 carbon atom, more preferably has 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, pyridine sulphur for example, 2-benzoglyoxaline sulphur, 2-benzoxazole sulphur, 2-[4-morpholinodithio sulphur), thiocarbonyl part (for example thioketones part, thioester part) and thioether part (dialkyl sulfide part for example, the diaryl sulfide part, sulphur furans part).And these parts can also be substituted base and replace.

Preferably, L ¹¹And L ¹⁴Each is the aromatic carbocyclic part naturally, alkoxy ligand, aryloxy ligands, ether part, alkylthio part, aryl sulfo-part, alkylamino part, fragrant amino ligands, amido ligands, with nitrogen heterocyclic ring part (pyridine for example, pyrazine, pyrimidine, pyridazine, triazine, thiazole, azoles, pyrroles, imidazoles, pyrazoles, triazole ， oxadiazole, with the thiadiazoles part, contain arbitrarily the condensation part of these parts (for example quinoline, benzoxazole, benzoglyoxaline part); Tautomer with any these parts).In these parts, more preferably aromatic carbocyclic part, aryloxy ligands, aryl sulfo-part, fragrant amino ligands, pyridine ligand, the pyrazine part, imidazole ligands contains arbitrarily the condensation part of these parts (for example quinoline, quinoxaline, benzoglyoxaline part); Tautomer with any these parts.Be more preferably the aromatic carbocyclic part, aryloxy ligands, aryl sulfo-part and fragrant amino ligands, most preferably aromatic carbocyclic part and aryloxy ligands.

L ¹²And L ¹³Separately preferably with M ¹¹Form the part of coordinate bond.As with M ¹¹Form the part of coordinate bond, preferred pyridine ring, the pyrazine ring, pyrimidine ring, triazine ring, thiazole ring, the azoles ring, pyrrole ring, triazole ring contains the condensed ring (for example, quinoline, benzoxazole, benzoglyoxaline and pseudo-indole ring) of these rings arbitrarily; Tautomer with any these rings.Wherein preferred pyridine ring, the pyrazine ring, pyrimidine ring, pyrrole ring contains arbitrarily the condensed ring of these rings (for example quinoline, indole ring); Tautomer with any these rings.Be more preferably pyridine ring, the pyrazine ring, pyrimidine ring contains the condensed ring (for example quinoline ring) of these rings arbitrarily.Preferred especially pyridine ring and the condensed ring (for example quinoline ring) that contains pyridine ring.

L ¹⁵Representative and M ¹¹The coordinate part.L ¹⁵Preferably monodentate is more preferably anionic monodentate to tetradentate ligand to tetradentate ligand.This anionic monodentate to tetradentate ligand is had no particular limits, but halogen ligands preferably, 1,3-diketonate ligand (for example acetyl acetone ligands), the single anion bidentate ligand (for example pyridine carboxylic acid, 2-(2-hydroxy phenyl)-pyridine ligand) and and the L that contain pyridine ligand ¹¹, Y ¹², L ¹², Y ¹¹, L ¹³, Y ¹³And L ¹⁴The tetradentate ligand that forms; More preferably 1,3-diketonate ligand (for example acetyl acetone ligands) contains the single anion bidentate ligand (for example pyridine carboxylic acid, 2-(2-hydroxy phenyl)-pyridine ligand) and and the L of pyridine ligand ¹¹, Y ¹², L ¹², Y ¹¹, L ¹³, Y ¹³And L ¹⁴The tetradentate ligand that forms; Be more preferably 1,3-diketonate ligand (for example acetyl acetone ligands) contains the single anion bidentate ligand (for example pyridine carboxylic acid, 2-(2-hydroxy phenyl)-pyridine ligand) of pyridine ligand; Especially preferred 1,3-diketonate ligand (for example acetyl acetone ligands).Ligancy and part number are no more than the ligancy of metal.L ¹⁵All not with L ¹¹And L ¹⁴Be joined together to form the ring-type part.

Y ¹¹, Y ¹²And Y ¹³Represent linking group separately, singly-bound or two key.Linking group is not particularly limited.The example of linking group comprises carbonyl linking, thiocarbonyl linking group, alkylidene group, alkenylene, arylidene, heteroarylidene, Sauerstoffatom linking group, nitrogen-atoms linking group, Siliciumatom linking group and contain the linking group of the combination of these groups.L ¹¹And Y ¹²Between key, Y ¹²And L ¹²Between key, L ¹²And Y ¹¹Between key, Y ¹¹And L ¹³Between key, L ¹³And Y ¹³Between key, and Y ¹³And L ¹⁴Between key represent singly-bound separately, or two key.

Y ¹¹, Y ¹²And Y ¹³Singly-bound preferably separately, two keys, carbonyl linking, alkylidene group linking group or alkenylene.Y ¹¹Be more preferably singly-bound or alkylidene group, being more preferably is alkylidene group.Y ¹²And Y ¹³Preferably singly-bound or alkenylene separately, being more preferably is singly-bound.

By Y ¹², L ¹¹, L ¹²And M ¹¹The ring that forms is by Y ¹¹, L ¹², L ¹³And M ¹¹The ring that forms, and by Y ¹³, L ¹³, L ¹⁴And M ¹¹The number of members of the ring that forms is preferably 4-10 separately, is more preferably 5-7, is preferably 5 or 6 especially.

n ¹¹Represent 0 to 4.Work as M ¹¹Be when to have ligancy be 4 metal, n ¹¹Be 0.Work as M ¹¹Be when to have ligancy be 6 metal, n ¹¹Preferably 1 or 2, being more preferably is 1.Work as M ¹¹Be that to have ligancy be 6 metal and n ¹¹Be 1 o'clock, L ¹⁵Represent bidentate ligand.Work as M ¹¹Be that to have ligancy be 6 metal and n ¹¹Be 2 o'clock, L ¹⁵Represent monodentate ligand.Work as M ¹¹Be when to have ligancy be 8 metal, n ¹¹1-4 preferably, being more preferably is 1 or 2, especially preferably 1.Work as M ¹¹Be that to have ligancy be 8 metal and n ¹¹Be 1 o'clock, L ¹⁵Represent tetradentate ligand, and work as n ¹¹Be 2 o'clock, L ¹⁵Represent bidentate ligand.Work as n ¹¹Be 2 or when bigger, a plurality of L ¹⁵Can be same to each other or different to each other.

Next, the compound of being represented by formula (2) will be described.

M ²¹Have and aforementioned M ¹¹Identical implication and identical preferable range.

Q ²¹And Q ²²Representative formation nitrogen heterocyclic ring (contains and M separately ²¹The ring of coordinate nitrogen-atoms) group.To by Q ²¹Or Q ²²The nitrogen heterocyclic ring that forms has no particular limits, and the example comprises pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, thiazole ring, the azoles ring, pyrrole ring, triazole ring contains arbitrarily the condensed ring of these rings (for example quinoline benzoxazole, benzoglyoxaline and pseudo-indole ring), and the tautomer of these rings.

By Q ²¹Or Q ²²The nitrogen heterocyclic ring that forms is pyridine ring preferably, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, the pyrazoles ring, imidazole ring, azoles ring, pyrrole ring, indole ring, contain arbitrarily the condensed ring of these rings (for example quinoline, benzoxazole and benzoglyoxaline ring), and the tautomer of these rings arbitrarily.By Q ²¹Or Q ²²It is pyridine ring that the nitrogen heterocyclic ring that forms is more preferably, the pyrazine ring, and pyrimidine ring, imidazole ring, pyrrole ring contains the condensed ring (for example quinoline ring) of these rings arbitrarily, and the tautomer of these rings arbitrarily.By Q ²¹Or Q ²²The nitrogen heterocyclic ring that forms is pyridine ring especially preferably, contains the condensed ring (for example quinoline ring) of pyridine ring, especially preferably pyridine ring.

X ²¹And X ²²Sauerstoffatom preferably separately, sulphur atom, or replacement or unsubstituted nitrogen-atoms.They are more preferably separately is Sauerstoffatom, sulphur atom, or the nitrogen-atoms that replaces, further preferably Sauerstoffatom or sulphur atom, especially preferably Sauerstoffatom.

Y ²¹Have and aforementioned Y ¹¹Identical implication and identical preferable range.

Y ²²And Y ²³Represent singly-bound or linking group separately, preferably singly-bound.Linking group is had no particular limits.The example of linking group comprises carbonyl linking, thiocarbonyl linking group, alkylidene group, alkenylene, arylidene, heteroarylidene, Sauerstoffatom linking group, nitrogen-atoms linking group and contain the linking group that these groups make up arbitrarily.

As above-mentioned linking group, preferred carbonyl linking, alkylidene group linking group, alkenylene linking group.Wherein more preferably carbonyl linking and alkenylene linking group are more preferably carbonyl linking.

R ²¹, R ²², R ²³And R ²⁴Represent hydrogen atom or substituting group separately.Substituting group is had no particular limits.Substituent example comprises that alkyl (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-10 carbon atom; methyl for example, ethyl, sec.-propyl; the tertiary butyl, n-octyl, positive decyl; n-hexadecyl, cyclopropyl, cyclopentyl; cyclohexyl), alkenyl (preferably has 2-30 carbon atom, is more preferably and has 2-20 carbon atom; especially preferably have 2-10 carbon atom, vinyl for example, allyl group; crotyl, the 3-pentenyl), alkynyl (preferably has 2-30 carbon atom; be more preferably and have 2-20 carbon atom, especially preferably have 2-10 carbon atom, for example propargyl; the 3-pentynyl), aryl (preferably has 6-30 carbon atom, is more preferably and has 6-20 carbon atom; especially preferably have 6-12 carbon atom, phenyl for example, p-methylphenyl; naphthyl, anthryl), amino (preferably have 0-30 carbon atom; be more preferably and have 0-20 carbon atom, especially preferably have 0-10 carbon atom, for example amino; methylamino, dimethylamino, diethylamino; dibenzyl amino, diphenyl amino, dimethylbenzene amino); alkoxyl group (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-10 carbon atom; methoxyl group for example, oxyethyl group, butoxy; the 2-ethyl hexyl oxy), aryloxy (preferably has 6-30 carbon atom, is more preferably and has 6-20 carbon atom; especially preferably have 6-12 carbon atom, phenoxy group for example, 1-naphthyloxy; the 2-naphthyloxy), heterocyclic oxy group (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom; especially preferably have 1-12 carbon atom, pyridyloxy for example, pyrazine oxygen base; 2-pyrimidinyl oxy, quinoline oxy), acyl group (preferably has 1-30 carbon atom; be more preferably and have 1-20 carbon atom, especially preferably have 1-12 carbon atom, for example ethanoyl; benzoyl, formyl radical, valeryl); carbalkoxy (preferably has 2-30 carbon atom, is more preferably and has 2-20 carbon atom, especially preferably have 2-12 carbon atom; methoxycarbonyl for example, ethoxycarbonyl), aryloxy carbonyl (preferably has 7-30 carbon atom; be more preferably and have 7-20 carbon atom, especially preferably have 7-12 carbon atom, for example carbobenzoxy); acyloxy (preferably has 2-30 carbon atom, is more preferably and has 2-20 carbon atom, especially preferably have 2-10 carbon atom; acetoxyl group for example, benzoyloxy), amido (preferably has 2-30 carbon atom; be more preferably and have 2-20 carbon atom, especially preferably have 2-10 carbon atom, for example kharophen; benzamido), alkoxycarbonyl amido (preferably has 2-30 carbon atom, is more preferably and has 2-20 carbon atom; especially preferably have 2-12 carbon atom, for example methoxycarbonyl amino), aryloxy carbonyl amino (preferably has 7-30 carbon atom; be more preferably and have 7-20 carbon atom, especially preferably have 7-12 carbon atom, for example phenyloxycarbonyl amino); sulfonamido (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-12 carbon atom; sulfonyl methane amino for example, phenylsulfonamido), sulfamyl (preferably has 0-30 carbon atom; be more preferably and have 0-20 carbon atom, especially preferably have 0-12 carbon atom, for example sulfamyl; the methyl sulfamyl, dimethylamino alkylsulfonyl, phenyl sulfamoyl base); formamyl (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-12 carbon atom; formamyl for example, methylamino formyl radical, diethylamino formyl radical; the phenyl amino formyl radical), alkyl thio-base (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom; especially preferably have 1-12 carbon atom, methyl sulfenyl for example, ethyl sulfenyl); the aryl thio group (preferably has 6-30 carbon atom, is more preferably and has 6-20 carbon atom, especially preferably have 6-12 carbon atom; phenyl sulfenyl for example), the heterocycle thio group (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom; especially preferably have 1-12 carbon atom, pyridine sulfenyl for example, 2-benzoglyoxaline sulfenyl; 2-benzoxazole sulfenyl, the 2-[4-morpholinodithio sulfenyl), alkylsulfonyl (preferably has 1-30 carbon atom; be more preferably and have 1-20 carbon atom, especially preferably have 1-12 carbon atom, for example methylsulfonyl; tosyl group), sulfinyl (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom; especially preferably have 1-12 carbon atom, methanesulfinyl for example, benzenesulfinyl); urea groups (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-12 carbon atom; urea groups for example, methyl urea groups, phenyl urea groups); the phosphoamide base (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-12 carbon atom; diethyl phosphinylidyne amido for example, phenyl phosphinylidyne amido), hydroxyl; sulfydryl, halogen atom (fluorine for example, chlorine; bromine; iodine), cyano group, sulfo group; carboxyl; nitro, hydroxamic acid base, sulfino; diazanyl; imino-, heterocyclic radical (preferably has 1-30 carbon atom, is more preferably and has 1-12 carbon atom; and contain heteroatoms such as nitrogen; oxygen and sulphur, specific examples are imidazolyl, pyridyl; quinolyl; furyl, thienyl, piperidyl; morpholino base benzoxazolyl, benzimidazolyl-, benzothiazolyl; carbazyl; the azepine base), silyl (preferably has 3-40 carbon atom, is more preferably and has 3-30 carbon atom; especially preferably have 3-24 carbon atom; trimethyl silyl for example, the triphenyl silyl), silyloxy (preferably has 3-40 carbon atom; be more preferably and have 3-30 carbon atom; especially preferably have 3-24 carbon atom, trimethylammonium silyloxy for example, triphenyl silyloxy).These substituting groups can also be substituted.

Preferably, R ²¹, R ²², R ²³And R ²⁴Each alkyl naturally, aryl is by at R ²¹And R ²², or R ²³And R ²⁴Between become key to form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Be more preferably R ²¹, R ²², R ²³And R ²⁴Each passes through naturally at R ²¹And R ²², or R ²³And R ²⁴Between become key to form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).

L ²⁵Have and aforementioned L ¹⁵Identical implication and identical preferable range.

n ²¹Have and aforementioned n ¹¹Identical implication and identical preferable range.

In the metal complex by formula (2) representative, wherein by Q ²¹The ring that forms and by Q ²²Each pyridine ring naturally of the ring that forms, and Y ²¹Represent linking group; Wherein by Q ²¹The ring that forms and by Q ²²Each pyridine ring naturally of the ring that forms, and Y ²¹Represent singly-bound or two key, and X ²¹And X ²²Represent sulphur atom or replacement or unsubstituted nitrogen-atoms separately; Wherein by Q ²¹The ring that forms and by Q ²²Each nitrogenous naturally 5 yuan of heterocycle of the ring that forms or the nitrogenous 6 yuan of heterocycles that contain two or more nitrogen-atoms all are preferred.

Next, the compound of being represented by formula (3) is described.

M ³¹Have and aforementioned M ¹¹Identical implication and identical preferable range.

Z ³¹, Z ³², Z ³³, Z ³⁴, Z ³⁵And Z ³⁶Representative replaces or unsubstituted carbon atom or nitrogen-atoms separately, wherein preferred the replacement or unsubstituted carbon atom.Substituent example on carbon atom is included in aforementioned R ²¹Middle those that explain.In addition, Z ³¹And Z ³², Z ³²And Z ³³, Z ³³And Z ³⁴, Z ³⁴And Z ³⁵, Z ³⁵And Z ³⁶Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring, pyridine condensed ring).Perhaps Z ³¹And T ³¹, Z ³⁶And T ³⁸Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring, pyridine condensed ring).

As aforementioned substituting group on carbon atom, preferred alkyl, alkoxyl group, alkylamino, aryl forms the group and the halogen atom of condensed ring (for example fused benzo ring, pyridine condensed ring).Wherein, be more preferably alkylamino, aryl and form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Further preferred aryl groups and form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Most preferably form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).

T ³¹, T ³², T ³³, T ³⁴, T ³⁵, T ³⁶, T ³⁷And T ³⁸Representative replaces or unsubstituted carbon atom or nitrogen-atoms separately, wherein preferred the replacement or unsubstituted carbon atom.Substituent example is included in aforementioned R on carbon atom ²¹Middle those that explain.T ³¹And T ³², T ³²And T ³³, T ³³And T ³⁴, T ³⁵And T ³⁶, T ³⁶And T ³⁷, T ³⁷And T ³⁸Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring).

As aforementioned substituting group on carbon atom, preferred alkyl, alkoxyl group, alkylamino, aryl forms the group and the halogen atom of condensed ring (for example fused benzo ring, pyridine condensed ring).Wherein, be more preferably aryl, form the group of condensed ring (for example fused benzo ring, pyridine condensed ring), and halogen atom.Further preferred aryl groups and halogen atom.Aryl most preferably.

X ³¹And X ³²Have and aforementioned X ²¹And X ²²Identical implication and identical preferable range.

Next, the compound of being represented by formula (5) is described.

M ⁵¹Have and aforementioned M ¹¹Identical implication and identical preferable range.

Q ⁵¹And Q ⁵²Have and aforementioned Q ²¹And Q ²²Identical implication and identical preferable range.

Q ⁵³And Q ⁵⁴Representative formation nitrogen heterocyclic ring (contains and M separately ⁵¹The ring of coordinate nitrogen-atoms) group.To by Q ⁵³Or Q ⁵⁴The nitrogen heterocyclic ring that forms has no particular limits, but the tautomer of pyrrole derivative preferably, the tautomer of imdazole derivatives (for example 5 yuan of heterocyclic ligands of compound (29)), the tautomer (for example 5 yuan of heterocyclic ligands of compound (31)) of tautomer of thiazole derivative (for example 5 yuan of heterocyclic ligands of compound (30)) and oxazole derivatives, be more preferably the tautomer of pyrrole derivative, the tautomer of imdazole derivatives, tautomer with thiazole derivative, the tautomer of further preferred pyrrole derivative and the tautomer of imdazole derivatives, the tautomer of preferred especially pyrrole derivative.

Y ⁵¹Have and aforementioned Y ¹¹Identical implication and identical preferable range.

L ⁵⁵Have and aforementioned L ¹⁵Identical implication and identical preferable range.

n ⁵¹Have and aforementioned n ¹¹Identical implication and identical preferable range.

W ⁵¹And W ⁵²Preferably replace separately or unsubstituted carbon atom or nitrogen-atoms.They are more preferably separately is unsubstituted carbon atom or nitrogen-atoms, further preferably unsubstituted carbon atom.

The compound of next, description formula (9) representative.

M ^A1, Q ^A1, Q ^A2, Y ^A1, Y ^A2, Y ^A3, R ^A1, R ^A2, R ^A3, R ^A4, L ^A5And n ^A1Have respectively separately and the middle M of aforementioned formula (2) ²¹, Q ²¹, Q ²², Y ²¹, Y ²², Y ²³, R ²¹, R ²², R ²³, R ²⁴, L ²⁵And n ²¹Identical implication and identical preferable range.

The compound of next, description formula (6) representative.

M ⁶¹Have and aforementioned M ¹¹Identical implication and identical preferable range.

Q ⁶¹And Q ⁶²Representative forms the group of ring separately.To by Q ⁶¹Or Q ⁶²The ring that forms has no particular limits.As described ring, for example benzene, pyridine, pyridazine, pyrimidine, thiophene, isothiazole, furans ， isoxazole ring and their condensed ring.

By Q ⁶¹Or Q ⁶²The ring that forms is benzene preferably, pyridine, and thiophene, or thiazole ring, or their condensed ring, being more preferably is benzene or pyridine ring, or their condensed ring, further preferably phenyl ring and its condensed ring.

Y ⁶¹Have and aforementioned Y ¹¹Identical implication and identical preferable range.

Y ⁶²And Y ⁶³Represent linking group or singly-bound separately.Linking group is had no particular limits.The example of linking group comprises carbonyl linking, thiocarbonyl linking group, alkylidene group, alkenylene, arylidene, heteroarylidene, Sauerstoffatom linking group, nitrogen-atoms linking group and by the linking group that is combined to form of these linking groups.

Preferred Y ⁶²And Y ⁶³Each singly-bound naturally, carbonyl linking, alkylidene group linking group, or alkenylene, be more preferably them each singly-bound or alkenylene naturally, further singly-bound preferably.

L ⁶⁵Have and aforementioned L ¹⁵Identical implication and identical preferable range.

n ⁶¹Have and aforementioned n ¹¹Identical implication and identical preferable range.

z ⁶¹, z ⁶², z ⁶³, z ⁶⁴, z ⁶⁵, z ⁶⁶, z ⁶⁷And z ⁶⁸Representative replaces or unsubstituted carbon atom or nitrogen-atoms separately, wherein preferred the replacement or unsubstituted carbon atom.Substituent example comprises aforementioned R on the carbon atom ²¹Middle those that explain.In addition, z ⁶¹And z ⁶², z ⁶²And z ⁶³, z ⁶³And z ⁶⁴, z ⁶⁵And z ⁶⁶, z ⁶⁶And z ⁶⁷, z ⁶⁷And z ⁶⁸Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring, pyridine condensed ring).By Q ⁶¹Or Q ⁶²The ring that forms can be bonded to z by linking group separately ⁶¹Or z ⁶⁸To form ring.

As aforementioned substituting group on carbon atom, preferred alkyl, alkoxyl group, alkylamino, aryl forms the group and the halogen atom of condensed ring (for example fused benzo ring, pyridine condensed ring).Wherein, be more preferably arylamino, aryl forms the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Further preferred aryl groups and form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Most preferably form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).

The compound of next, description formula (7) representative.

M ⁷¹Have and aforementioned M ¹¹Identical implication and identical preferable range.

Y ⁷¹, Y ⁷²And Y ⁷³Have separately and aforementioned Y ⁶²Identical implication and identical preferable range.

L ⁷⁵Have and aforementioned L ¹⁵Identical implication and identical preferable range.

n ⁷¹Have and aforementioned n ¹¹Identical implication and identical preferable range.

z ⁷¹, z ⁷², z ⁷³, z ⁷⁴, z ⁷⁵And z ⁷⁶Representative replaces or unsubstituted carbon atom or nitrogen-atoms separately, wherein preferred the replacement or unsubstituted carbon atom.Substituent example comprises aforementioned at R on the carbon atom ²¹Middle those that explain.In addition, z ⁷¹And z ⁷², and z ⁷³And z ⁷⁴Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring, pyridine condensed ring).

R ⁷¹, R ⁷², R ⁷³And R ⁷⁴Separately with the middle R of aforementioned formula (2) ²¹, R ²², R ²³And R ²⁴Have identical implication and identical preferable range.

Next, the compound of being represented by formula (11) is described.

R ^C1And R ^C2Represent hydrogen atom or substituting group separately.Substituting group is suc as formula R in (2) ²¹To R ²⁴The cited alkyl or aryl of substituting group.R ^C3, R ^C4, R ^C5And R ^C6The substituting group of representative also with formula (2) in R ²¹To R ²⁴Cited have an identical implication.n ^C3And n ^C6Represent 0 to 3 integer separately; n ^C4And n ^C5Represent 0 to 4 integer separately.When there being two or more R ^C3, R ^C4, R ^C5Or R ^C6The time, they can be same to each other or different to each other, and they separately each other bonding to form ring.R ^C3, R ^C4, R ^C5And R ^C6Preferably alkyl, aryl, heteroaryl and halogen atom separately.

Next, the compound of being represented by formula (10) is described.

M ^B1, Y ^B2, Y ^B3, R ^B1, R ^B2, R ^B3, R ^B4, L ^B5, n ^B3, X ^B1And X ^B2Have separately and the middle M of aforementioned formula (2) ²¹, Y ²², Y ²³, R ²¹, R ²², R ²³, R ²⁴, L ²⁵, n ²¹, X ²¹And X ²²Identical implication and identical preferable range.Y ^B1Representative and the middle Y of formula (2) ²¹Identical linking group, the vinyl that on 1-and 2-position, replaces preferably, phenylene, pyridine ring, pyrazine ring, pyrimidine ring or have the alkylidene group of 2 to 8 carbon atoms.R ^B5And R ^B6Represent hydrogen atom or substituting group separately.Described substituting group is R in the formula (2) ²¹To R ²⁴The alkyl that substituting group is cited, aryl or heterocyclic radical.Yet Y ^B1Not with R ^B5Or R ^B6Connect.n ^B1And n ^B2Represent 0 to 1 integer separately.

Next, the compound of being represented by formula (12) is described.

R ^D1, R ^D2, R ^D3And R ^D4The substituting group of representative and the R in the formula (10) ^B5And R ^B6Have identical implication and identical preferable range.n ^D1And n ^D2Represent 0 to 4 integer separately.Y ^D1Representative has vinyl, phenylene, pyridine ring, pyrazine ring, the pyrimidine ring of replacement in 1-and 2-position or has the alkylidene group of 1 to 8 carbon atom.

According to the present invention, the preferred implementation that contains the metal complex of tridentate ligand is exemplified by formula (8).

Next, the compound of being represented by formula (8) is described.

M ⁸¹Have and aforementioned M ¹¹Identical implication and identical preferable range.

L ⁸¹, L ⁸²And L ⁸³Have separately and aforementioned L ¹¹, L ¹²And L ¹⁴Identical implication and identical preferable range.

Y ⁸¹And Y ⁸²Have separately and aforementioned Y ¹¹And Y ¹²Identical implication and identical preferable range.

L ⁸⁵Representative and M ⁸¹The coordinate part.L ⁸⁵Preferably monodentate ligand is more preferably monodentate to three tooth anion ligand to tridentate ligand.Described monodentate to three tooth anion ligand is not particularly limited, but halogen ligands preferably, by L ⁸¹, Y ⁸¹, L ⁸², Y ⁸²And L ⁸³The tridentate ligand that forms, being more preferably is by L ⁸¹, Y ⁸¹, L ⁸², Y ⁸²And L ⁸³The tridentate ligand that forms.L ⁸⁵Not directly and L ⁸¹Or L ⁸³Bonding, but pass through metal link.Ligancy and part number are no more than the ligancy of metal.

n ⁸¹Represent 0 to 5.Work as M ⁸¹Be when to have ligancy be 4 metal, n ⁸¹Be 1 and L ⁸⁵It is monodentate ligand.Work as M ⁸¹Be when to have ligancy be 6 metal, n ⁸¹Preferably 1 to 3, be more preferably 1 or 3, further preferably 1.Work as M ⁸¹Be that to have ligancy be 6 metal and n ⁸¹Be 1 o'clock, L ⁸⁵It is tridentate ligand.Work as M ⁸¹Be that to have ligancy be 6 metal and n ⁸¹Be 2 o'clock, L ⁸⁵Be monodentate ligand and bidentate ligand.Work as M ⁸¹Be that to have ligancy be 6 metal and n ⁸¹Be 3, L ⁸⁵It is monodentate ligand.Work as M ⁸¹Be when to have ligancy be 8 metal, n ⁸¹Preferably 1 to 5, be more preferably 1 or 2, further preferably 1.Work as M ⁸¹Be that to have ligancy be 8 metal and n ⁸¹Be 1 o'clock, L ⁸⁵It is quinquidentate ligand; Work as n ⁸¹Be 2 o'clock, L ⁸⁵Be tridentate ligand and bidentate ligand; Work as n ⁸¹Be 3 o'clock, L ⁸⁵Be a tridentate ligand and two monodentate ligands, or two bidentate ligands and a monodentate ligand; Work as n ⁸¹Be 4 o'clock, L ⁸⁵Be a bidentate ligand and three monodentate ligands; Work as n ⁸¹Be 5 o'clock, L ⁸⁵Be five monodentate ligands.Work as n ⁸¹Be 2 or when bigger, a plurality of L ⁸⁵Can be same to each other or different to each other.

By the preferred implementation of the compound of formula (8) representative is L in the formula (8) ⁸¹, L ⁸²And L ⁸³Represent separately by carbon atom and M ⁸¹Coordinate aromatic carbocyclic or heterocycle, or by nitrogen-atoms and M ⁸¹Coordinate nitrogen heterocyclic ring, prerequisite are L ⁸¹, L ⁸²And L ⁸³At least one be described nitrogen heterocyclic ring.By carbon atom and M ⁸¹Coordinate aromatic carbocyclic or heterocycle and by nitrogen-atoms and M ⁸¹Cited carbon atom and the M of passing through in nitrogenous heterocyclic example of coordinate and the formula (1) ¹¹Coordinate part and by nitrogen-atoms and M ¹¹The example of coordinate part is identical, has identical preferable range.Y ⁸¹And Y ⁸²Preferably singly-bound or methylene radical separately.

By other preferred implementation of the compound of formula (8) representative is by those of formula (13) or (14) representative.

Formula (13)

Formula (14)

Next, the compound of being represented by formula (13) is described.

M ⁹¹Have and aforementioned M ⁸¹Identical implication and identical preferable range.

Q ⁹¹And Q ⁹²Representative formation nitrogen heterocyclic ring (contains and M separately ⁹¹The ring of coordinate nitrogen-atoms) group.To by Q ⁹¹Or Q ⁹²The nitrogen heterocyclic ring that forms has no particular limits, but pyridine preferably, pyrazine, pyrimidine, pyridazine, triazine, thiazole, azoles, pyrroles, pyrazoles, imidazoles, or triazole ring, or contain arbitrarily the condensed ring of these rings (for example quinoline, benzoxazole, benzoglyoxaline and pseudo-indole ring); Or the tautomer of these rings arbitrarily.

By Q ⁹¹Or Q ⁹²The nitrogen heterocyclic ring that forms is pyridine preferably, pyrazoles, thiazole, imidazoles, or pyrrole ring, or contain arbitrarily the condensed ring of these rings (quinoline for example, benzothiazole, benzoglyoxaline and pseudo-indole ring), or the tautomer of these rings arbitrarily, being more preferably is pyridine or pyrrole ring, or contains the arbitrarily condensed ring (for example quinoline ring) of these rings, or the tautomer of these rings arbitrarily, further pyridine ring and contain the condensed ring of pyridine ring, especially preferred pyridine ring preferably.

Q ⁹³Representative forms nitrogen heterocyclic ring and (contains and M ⁹¹The ring of coordinate nitrogen-atoms) group.To by Q ⁹³The nitrogen heterocyclic ring that forms has no particular limits, but pyrroles's tautomer preferably, imidazoles or triazole ring perhaps contain the condensed ring (for example benzopyrrole ring) of these rings arbitrarily, being more preferably is the tautomer of pyrrole ring, or contains the tautomer of the condensed ring of pyrrole ring

(for example benzopyrrole ring).

W ⁹¹And W ⁹²Have separately and aforementioned W ⁵¹And W ⁵²Identical implication and identical preferable range.

L ⁹⁵Have and aforementioned L ⁸⁵Identical implication and identical preferable range.

n ⁹¹Have and aforementioned n ⁸¹Identical implication and identical preferable range.

Next, the compound of being represented by formula (14) is described.

M ¹⁰¹Have and aforementioned M ⁸¹Identical implication and identical preferable range.

Q ¹⁰²Have and aforementioned Q ²¹Identical implication and identical preferable range.

Q ¹⁰¹Have and aforementioned Q ⁹¹Identical implication and identical preferable range.

Q ¹⁰³Representative forms the group of aromatic ring.To by Q ¹⁰³The aromatic ring that forms has no particular limits, but benzene preferably, furans, and thiophene, or pyrrole ring or contain the condensed ring (for example naphthalene nucleus) of these rings arbitrarily, being more preferably is phenyl ring or the condensed ring that contains phenyl ring (for example naphthalene nucleus), especially preferably phenyl ring.

Y ¹⁰¹And Y ¹⁰²Have separately and aforementioned Y ²²Identical implication and identical preferable range.

L ¹⁰⁵Have and aforementioned L ⁸⁵Identical implication and identical preferable range.

n ¹⁰¹Have and aforementioned n ⁸¹Identical implication and identical preferable range.

X ¹⁰¹Have and aforementioned X ²¹Identical implication and identical preferable range.

Compound of the present invention can be a low molecular compound, or the weight-average molecular weight that oligopolymer or have calculates with polystyrene is 1,000-5,000, the polymkeric substance of 000 scope is more preferably at 2,000-1,000,000 scope, further preferably 3,000-100,000 scope.With respect to polymkeric substance, by the structure example of formula (1) representative as in the main chain that can be included in polymkeric substance, perhaps in the side chain of polymkeric substance.In addition, polymkeric substance can be homopolymer or multipolymer.Compound of the present invention is low molecular compound preferably.

Another preferred implementation with metal complex of tridentate ligand of the present invention is the metal complex by formula (X1) representative.In metal complex,, be more preferably metal complex by formula (X3) representative preferably by the metal complex of formula (X2) representative by formula (X1) representative.

Next, the compound of being represented by formula (X1) is described.

M ^X1Representation metal ion.This metal ion is had no particular limits, but preferably monovalence is to trivalent metal ion, being more preferably is divalence or trivalent metal ion, further preferred trivalent metal ion.Concrete preferred platinum, iridium, rhenium, palladium, rhodium, ruthenium, copper, europium, gadolinium, and terbium ion.Wherein be more preferably platinum, iridium, and europium ion, further preferred platinum and iridium ion, especially preferred iridium ion.

Q ^X11, Q ^X12, Q ^X13, Q ^X14, Q ^X15And Q ^X16Represent separately and M ^X1Coordinate atom or have and M ^X1The atomic group of coordinate atom.Work as Q ^X11, Q ^X12, Q ^X13, Q ^X14, Q ^X15Or Q ^X16Representative and M ^X1The coordinate atomic time, its specific examples comprises carbon atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, phosphorus atom, and sulphur atom; Preferred this atom is a nitrogen-atoms, Sauerstoffatom, and sulphur atom, or phosphorus atom, and being more preferably is nitrogen-atoms or Sauerstoffatom.

Work as Q ^X11, Q ^X12, Q ^X13, Q ^X14, Q ^X15Or Q ^X16Representative has and M ^X1During the atomic group of coordinate atom, through carbon atom and M ^X1The specific examples of coordinate atomic group comprises imino-, aromatic hydrocarbon cyclic group (for example benzene, naphthalene), heterocyclic group (for example thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, azoles, pyrroles, imidazoles, pyrazoles, triazole), contain the condensed ring of these rings arbitrarily and the tautomer of these rings arbitrarily.

Through nitrogen-atoms and M ^X1The specific examples of coordinate atomic group comprises nitrogen heterocyclic ring group (pyridine for example; pyrazine; pyrimidine; pyridazine; triazine; thiazole; azoles; the pyrroles; imidazoles; pyrazoles; triazole); it is amino that (for example alkylamino (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; especially preferably have those of 2-10 carbon atom; methylamino for example); virtue amino (for example phenyl amino); amido (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; those of preferred especially 2-10 carbon atom; kharophen for example; benzamido); alkoxycarbonyl amino (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; especially preferably have those of 2-12 carbon atom; methoxycarbonyl amino for example); aryloxycarbonyl amino (preferably has 7-30 carbon atom; more preferably have 7-20 carbon atom, especially preferably have those of 7-12 carbon atom, for example phenyloxycarbonyl amino); sulfuryl amino (preferably has 1-30 carbon atom; more preferably have 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, for example sulfonyl methane amino; and imino-phenylsulfonamido).These groups can also be substituted base and replace.

Through Sauerstoffatom and M ^X1The specific examples of coordinate atomic group comprises that alkoxyl group (preferably has 1-30 carbon atom, more preferably have 1-20 carbon atom, especially preferably have those of 1-10 carbon atom, methoxyl group for example, oxyethyl group, butoxy, the 2-ethyl hexyl oxy), aryloxy (preferably has 6-30 carbon atom, more preferably have 6-20 carbon atom, especially preferably have those of 6-12 carbon atom, phenoxy group for example, 1-naphthyloxy, the 2-naphthyloxy), heterocyclic oxy group (preferably has 1-30 carbon atom, more preferably has 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, pyridyloxy for example, pyrazoles oxygen base, 2-pyrimidinyl oxy, quinoline oxy), acyloxy (preferably has 2-30 carbon atom, more preferably have 2-20 carbon atom, especially preferably have those of 2-10 carbon atom, for example acetoxyl group, benzoyloxy), silyloxy (preferably has 3-40 carbon atom, more preferably has 3-30 carbon atom, especially preferably have those of 3-24 carbon atom, trimethylammonium silyloxy for example, the triphenyl silyloxy), carbonyl (ketone group for example, ester group, amide group), and ether (for example dialkyl group ether, diaryl ether, furyl).

Through sulphur atom and M ^X1The specific examples of coordinate atomic group comprises that alkyl thio-base (preferably has 1-30 carbon atom, more preferably have 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, methylthio group for example, ethylmercapto group), arylthio (preferably has 6-30 carbon atom, more preferably has 6-20 carbon atom, especially preferably have those of 6-12 carbon atom, thiophenyl for example), the heterocycle sulfenyl (preferably has 1-30 carbon atom, more preferably has 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, pyridine sulfenyl for example, 2-benzoglyoxaline sulfenyl, 2-benzoxazole sulfenyl, the 2-[4-morpholinodithio sulfenyl), thiocarbonyl (for example thioketones base, thioester), and thioether group (dialkyl sulfide base for example, the diaryl sulfide base, the sulphur furyl).

Through phosphorus atom and M ^X1The specific examples of coordinate atomic group comprises the dialkyl group phosphino-, diarylphosphino, trialkyl phosphino-, triaryl phosphino-, phosphino-.These groups can also be substituted.

As by Q ^X11, Q ^X12, Q ^X13, Q ^X14, Q ^X15Or Q ^X16The atomic group of representative, preferably by carbon atom coordinate aromatic hydrocarbon cyclic group, by carbon atom coordinate aromatic heterocyclic group, by the nitrogenous aromatic heterocyclic group of nitrogen-atoms coordinate, alkoxy grp, aryloxy group, alkane thio group, arylthio group, the dialkyl group phosphino-, be more preferably by carbon atom coordinate aromatic hydrocarbon cyclic group, by carbon atom coordinate aromatic heterocyclic group and nitrogenous aromatic heterocyclic group.

L ^X11, L ^X12, L ^X13And L ^X14Represent singly-bound separately, two keys or linking group.Linking group is not particularly limited.The preferred embodiment of linking group comprises and contains carbon, nitrogen, oxygen, arbitrary linking group of sulphur and Siliciumatom.The specific examples of linking group is as follows, but the present invention is not limited to this.

These linking groups can also be substituted base and replace.Described substituent example comprises in the formula (2) by R ²¹To R ²⁴Those that the substituting group of representative is explained, and have identical preferable range.As L ^X11, L ^X12, L ^X13Or L ^X14, singly-bound preferably, dimethylated methylene base, dimethylated methylene silylation.

Being more preferably by the metal complex of formula (X1) representative is metal complex by formula (X2) representative.Next, the metal complex of being represented by formula (X2) is described.

M ^X2Have with aforementioned formula (X1) in M ^X1Identical implication and identical preferable range.Y ^X21, Y ^X22, Y ^X23, Y ^X24, Y ^X25And Y ^X26Represent separately and M ^X2The coordinate atom.Y ^X21And M ^X2Between key, Y ^X22And M ^X2Between key, Y ^X23And M ^X2Between key, Y ^X24And M ^X2Between key, Y ^X25And M ^X2Between key, and Y ^X26And M ^X2Between key each coordinate bond or covalent linkage naturally.Y ^X21, Y ^X22, Y ^X23, Y ^X24, Y ^X25Or Y ^X26Specific examples comprise carbon atom, nitrogen-atoms, Sauerstoffatom, sulphur atom, phosphorus atom, and Siliciumatom are more preferably carbon atom and nitrogen-atoms.Each Q ^X21, Q ^X22, Q ^X23, Q ^X24, Q ^X25And Q ^X26Represent necessary atomic group with respectively with each Y ^X21, Y ^X22, Y ^X23, Y ^X24, Y ^X25And Y ^X26Form aromatic hydrocarbon ring or aromatic heterocycle.The aromatic hydrocarbon ring that is formed by these groups or the specific examples of aromatic heterocycle comprise benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrroles, pyrazoles, imidazoles, triazole, azoles, thiazole ， oxadiazole, thiadiazoles, thiophene, and furan nucleus.Benzene preferably, pyridine, pyrazine, pyrimidine, pyrazoles, imidazoles, and triazole ring, being more preferably is benzene, pyridine, pyrazine, pyrazoles, and triazole ring, especially preferred benzene and pyridine ring.These rings can also comprise condensed ring, maybe can also have substituting group.

L ^X21, L ^X22, L ^X23And L ^X24Have with aforementioned formula (X1) in L ^X11, L ^X12, L ^X13And L ^X14Identical implication and identical preferable range.

By the metal complex of formula (X1) representative further preferably by the metal complex of formula (X3) representative.Next, the metal complex of being represented by formula (X3) is described.

M ^X3Have with aforementioned formula (X1) in M ^X1Identical implication and identical preferable range.Y ^X31, Y ^X32, Y ^X33, Y ^X34, Y ^X35And Y ^X36Represent separately and M ^X3The coordinate atom.Y ^X31 and M ^X3Between key, Y ^X32And M ^X3Between key, Y ^X33And M ^X3Between key, Y ^X34And M ^X3Between key, Y ^X35And M ^X3Between key, and Y ^X36And M ^X3Between key each coordinate bond or covalent linkage naturally.Y ^X31, Y ^X32, Y ^X33, Y ^X34, Y ^X35Or Y ^X36Specific examples comprise carbon atom, nitrogen-atoms, and phosphorus atom, preferably carbon atom and nitrogen-atoms.L ^X31, L ^X32, L ^X33And L ^X34Have with aforementioned formula (X1) in L ^X11, L ^X12, L ^X13And L ^X14Identical implication and identical preferable range.

The specific examples of compound of the present invention is as follows, but the present invention is not limited to these compounds.

Compound (1) compound (7)

Compound (2) compound (8)

Compound (3) compound (9)

Compound (4) compound (10)

Compound (5) compound (11)

Compound (6) is changed can thing (12)

Compound (13) compound (18)

Compound (14) compound (19)

Compound (15) compound (20)

Compound (16) compound (21)

Compound (17) compound (22)

Compound (23)

Compound (24) compound (29)

Compound (25) compound (30)

Compound (26) compound (31)

Compound (27) compound (32)

Compound (28)

Compound (33) compound (38)

Compound (34) compound (39)

Compound (35) compound (40)

Compound (36) compound (41)

Compound (37) compound (42)

Compound (43)

Compound (44)

Compound (45)

Compound (46)

Compound (47)

Compound (48)

Compound (49) compound (55)

Compound (50) compound (56)

Compound (51) compound (57)

Compound (52) compound (58)

Compound (53) compound (59)

Compound (54) compound (60)

Compound (61) compound (63)

Compound (62) compound (64)

Compound (65)

Compound (66) compound (72)

Compound (67) compound (73)

Compound (68) compound (74)

Compound (69) compound (75)

Compound (70) compound (76)

Compound (71) compound (77)

Compound (78) compound (83)

Compound (79) compound (84)

Compound (80) compound (85)

Compound (81) compound (86)

Compound (82) compound (87)

Compound (88) compound (93)

Compound (89) compound (94)

Compound (90) compound (95)

Compound (91) compound (96)

Compound (92) compound (97)

Compound (98) compound (103)

Compound (99) compound (104)

Compound (100) compound (105)

Compound (101) compound (106)

Compound (102) compound (107)

Compound (108) compound (113)

Compound (109) compound (114)

Compound (110) compound (115)

Compound (111) compound (116)

Compound (112) compound (117)

Compound (118) compound (123)

Compound (119) compound (124)

Compound (120) compound (125)

Compound (121) compound (126)

Compound (122) compound (127)

Compound (128) compound (133)

Compound (129) compound (134)

Compound (130) compound (135)

Compound (131) compound (136)

Compound (132) compound (137)

Compound (138) compound (141)

Compound (139) compound (142)

Compound (140) compound (143)

Compound (144) compound (147)

Compound (145) compound (148)

Compound (146) compound (149)

Compound (150) compound (152)

Compound (151) compound (153)

Compound (154) compound (158)

Compound (155) compound (159)

Compound (156) compound (160)

Compound (161)

Compound (162) compound (166)

Compound (163) compound (187)

Compound (164) compound (168)

Compound (165) compound (169)

Compound (170) compound (174)

Compound (171) compound (175)

Compound (172) compound (176)

Compound (173) compound (177)

Compound (178) compound (184)

Compound (179) compound (185)

Compound (180) compound (186)

Compound (181) compound (187)

Compound (182) compound (188)

Compound (183) compound (189)

Compound (190) compound (196)

Compound (191) compound (197)

Compound (192) compound (198)

Compound (193) compound (199)

Compound (194) compound (200)

Compound (195) compound (201)

Compound (202) compound (207)

Compound (208)

Compound (204) compound (209)

Compound (205) compound (210)

Compound (206) compound (211)

Compound (212) compound (213) compound (214)

Compound (215) compound (216) compound (217)

Compound (218) compound (219) compound (220)

Compound (221) compound (222) compound (223)

Compound (224) compound (225) compound (226)

Compound (227) compound (228) compound (229)

Compound (230) compound (231) compound (232)

Compound (233) compound (234)

Compound (235) compound (236)

Compound (237) compound (238)

Compound (239)

Compound (240) compound (241)

Compound (242)

(synthetic method of metal complex of the present invention)

Metal complex of the present invention (promptly by formula (1) to (14) and formula (X1) compound to (X3) arbitrary representative) can be synthetic by the whole bag of tricks.

For example, described compound can obtain by the following method, at solvent (halogen-kind solvent for example, alcohol-kind solvent, ether-kind solvent, ester-kind solvent, ketone-kind solvent, nitrile-kind solvent, acid amides-kind solvent, sulfone-kind solvent, sulfoxide-kind solvent and water) exist down, perhaps there not being solvent at alkali (various inorganic or organic basess, for example sodium methylate, potassium tert.-butoxide, triethylamine and salt of wormwood) existence under, perhaps there not being alkali under room temperature or lower temperature, perhaps by heating (except that common heating, heating means by microwave also are effective), part or its dissociating product metallizing thing are reacted.

The activity of the synthetic applied reaction times of metal complex of the present invention according to raw material changes, and the reaction times is had no particular limits, but the preferred reaction times is from 1 minute to 5 days, more preferably from 5 minutes to 3 days, further preferably from 10 minutes to 1 day.

The synthetic applied temperature of reaction of metal complex of the present invention changes according to reactive behavior, temperature of reaction is had no particular limits, but preferred temperature of reaction is from 0-300 ℃, more preferably from 5-250 ℃, more preferably from 10-200 ℃.

Metal complex of the present invention, as by formula (1) to (14) and formula (X1) compound to (X3) arbitrary representative, the part of part-structure that can be by selecting to form the target complex compound suitably synthesizes.For example, compound by formula (3) representative can followingly synthesize, with part as 6,6 '-two (2-hydroxy phenyls)-2, (part is as 2 for 2 '-dipyridyl or derivatives thereof, 9-two (2-hydroxy phenyl)-1,10-phenanthroline, 2,9-two (2-hydroxy phenyl)-4,7-phenylbenzene-1,10-phenanthroline and 6,6 '-two (2-hydroxyls-5-tert-butyl-phenyl)-2,2 '-dipyridyl) to be preferably 0.1-10,0.3-6 more preferably, more preferably the equivalents of 0.5-4 is added into respectively in the metallic compound, identical by described in aforementioned the synthesizing of applied reaction times in the synthetic method of the compound of formula (3) representative and temperature of reaction and metal complex of the present invention.

6,6 '-two (2-hydroxy phenyls)-2, the derivative of 2 '-bipyridine ligand can be synthetic by various known methods.For example with 2,2 '-dipyridyl derivatives (for example 1,10-phenanthroline) and methyl-phenoxide derivative (for example 4-fluoroanisole) are according to Journal of Organic Chemistry, and the method described in 741,11 (1946) is reacted.Perhaps with halogenated 2; 2 '-dipyridyl derivatives (for example 2; 9-two bromo-1; the 10-phenanthroline) and 2-methoxyphenyl boric acid derivatives (for example 2-methoxyl group-5-fluorophenyl boric acid) carry out the Suzuki coupled reaction as starting raw material; pass through then according to Journal of Organic Chemistry, the method described in 741,11 (1946); or in the presence of pyridine hydrochloride the method for reacting by heating mixture, methyl is discharged as blocking group.Perhaps; can be with 2; 2 '-dipyridyl boric acid derivatives (for example 6; 6 '-two (4; 4; 5; 5-tetramethyl--1,3,2-dioxy borine (dioxaboroly1)-2; 2 '-dipyridyl) and halogenated methyl-phenoxide derivative (for example 2-bromoanisole) carry out the Suzuki coupled reaction as starting raw material; pass through then according to Journal ofOrganic Chemistry, the method described in 741,11 (1946); or in the presence of pyridine hydrochloride the method for reacting by heating mixture, methyl is discharged as blocking group.

The light-emitting device that comprises metal complex of the present invention is described below.

To light-emitting device of the present invention for example their system, driving method and type of service have no particular limits, as long as wherein use metal complex of the present invention.As typical light-emitting device, what can mention is organic EL (electroluminescent) device.

El light emitting device of the present invention is the Organnic electroluminescent device that comprises pair of electrodes and at least one organic layer that comprises luminescent layer between described pair of electrodes.Described organic layer preferably comprises hole transmission layer and luminescent layer, further preferably at least one deck be to be selected from exciton barrier-layer, hole injection layer, the layer of hole blocking layer and electron transfer layer.

El light emitting device of the present invention preferably has the layer of inclusion compound between negative pole and luminescent layer, the ionization potential of described compound is 5.9eV or higher (6.0eV or higher more preferably); More preferably, having ionization potential is 5.9eV or higher electron transfer layer.

Formation method for the organic layer of the light-emitting device that comprises metal complex of the present invention has no particular limits.As described method, can adopt the whole bag of tricks, as the vapor deposition method of resistive heating, electronic beam method, sputtering method, molecular layer is legal, coating method (as, spraying method, dip coating, pickling process, rolling method, intaglio plate coating method, oppositely coating method, roller brush method, airblade coating method, curtain coating method, spin-coating method, flow coat method, rod is coated with method, miniature intaglio plate coating method, gas scraper coating method, blade coating method, the extrusion coated method, angle stripper coating method, contact coating method, the curtain coating coating method, extrusion coated method, excellent coating method and screen cloth coating method wind the line), ink jet method, print process, and transfer method.Consider characteristic and production, vapor deposition method, coating method and the transfer method of preferred resistive heating.

Described positive pole provides the hole to hole injection layer, hole transmission layer, and luminescent layer, or the like; And can use metal for this reason, alloy, metal oxide, conductive compound, or the mixture of these materials preferably use work content to be 4eV or bigger material at this.The object lesson of described material comprises: conducting metal oxide, and as stannic oxide, zinc oxide, Indium sesquioxide, and tin indium oxide (ITO); Metal, as gold, silver, chromium, and nickel; The mixture of these metals and conducting metal oxide or laminated thing; The inorganic conductive material is as cupric iodide and cupric sulfide; The organic conductive material, as polyaniline, Polythiophene, and polypyrrole; And the laminated thing of these materials and ITO.Consider producibility, high conductivity and transparency are preferably used conducting metal oxide, especially preferably use ITO.The anodal film thickness can be selected arbitrarily according to material therefor, but its thickness is usually preferably from 10 nanometers to 5 micron, is more preferably from 50 nanometers to 1 micron, more preferably from 100 nanometer to 500 nanometers.

Described positive pole is generally comprised within one or more layers that forms on soda-lime glass, non-alkali glass or the transparent resin matrix.When using glass matrix,, preferably use non-alkali glass in order to reduce the wash-out of ion from glass.In addition, when using soda-lime glass, preferably provide barrier coat such as silicon-dioxide.As long as described matrix can keep enough physical strengths, its thickness is had no particular limits.When using glass, described thickness is generally 0.2 millimeter or bigger, preferred 0.7 millimeter or bigger.

According to the described positive pole of employed material preparation the time, can make and in all sorts of ways.Utilizing under the situation of ITO, for example, by electronic beam method, sputtering method, the resistive heating vapor deposition method, chemical reaction method (for example, sol-gel method), or the method for coating tin indium oxide dispersion forms one or more layers film.

Method by as positive pole is washed might reduce the driving voltage of device or element or increase its luminous efficacy.Under the situation of using ITO, for example UV-ozonize or Cement Composite Treated by Plasma are effective.

Described negative pole offers electron injecting layer with electronics, electron transfer layer, and luminescent layer etc., and consider negative pole and its adjacent layer such as electron injecting layer, and electron transfer layer, or the clinging power of luminescent layer, ionization potential and stability wait selects negative pole.As the material of negative pole, can use metal, alloy, metal halide, metal oxide, conductive compound, or these mixtures of material.Concrete example comprises: basic metal (for example, lithium, sodium, potassium) or its fluorochemical or oxide compound, alkaline-earth metal (for example magnesium, calcium) or its fluorochemical or oxide compound, gold, silver, lead, aluminium, sodium-potassium-sodium alloy or its hybrid metal, lithium-aluminium alloy or its hybrid metal, magnesium-silver alloys or its hybrid metal, and rare earth metal, as indium, ytterbium or the like; Preferred work content is 4eV or littler material, more preferably aluminium, lithium-aluminium alloy or its hybrid metal, and magnesium-silver alloys or its hybrid metal.Negative pole structure not only can be the individual layer of above-claimed cpd or its mixture, but also can be the laminated thing that comprises above-claimed cpd or its mixture.For example, preferred aluminium/lithium fluoride, or the laminated thing of aluminium/Lithium Oxide 98min.The thickness of negative pole can be selected arbitrarily according to material therefor, but its thickness is usually preferably from 10 nanometers to 5 micron, is more preferably from 50 nanometers to 1 micron, more preferably from 100 nanometers to 1 micron.

Operable method such as electronic beam method when making negative pole, sputtering method, the resistive heating vapor deposition method, coating method, and transfer method can the single metals of gas deposition or two or more components of gas deposition simultaneously.In addition, simultaneously the multiple metal of gas deposition to be forming alloy electrode, but the perhaps pre-prepd alloy of gas deposition.

Preferably, sheet resistance (sheet resistance) anodal and negative pole is lower, is preferably hundreds of Ω/ or lower.

The material that is used for luminescent layer can be following material, it can form layers, described layer can rise when both having accepted when it applies electric field by positive pole, and hole injection layer or hole transmission layer injected holes can be accepted again by negative pole, electron injecting layer or electron transfer layer injected electrons; Perhaps make injection charge transfer wherein; Perhaps by reconfiguring to hole and electronics the position is provided and can be luminous.Except that compound of the present invention, described examples of material comprises: various metal complexs, and typical example is the metal complex or the rare-earth complex benzoxazole derivative of following material, benzimidizole derivatives, benzothiazole derivant, the styryl benzene derivative, the polyphenyl derivative, diphenyl diethylene derivative, tetraphenylbutadiene derivative, naphthalimide derivative, coumarin derivatives ， perylene derivative, perinone derivative oxadiazole derivative, the aldazine derivative, pyraridine derivative, cyclopentadiene derivant, the diphenylethyllene anthracene derivant, quinacridone derivative, Pyrrolopyridine derivatives, thiadiazoles pyridine derivate, cyclopentadiene derivant, the styrylamine derivative, aromatics two methylidyne compounds and oxine derivative; Polymkeric substance, as Polythiophene, polyphenylene, and polyphenylene vinylene; Organosilane; Transition metal complex (for example, triphenyl pyridine iridium and porphyrin platinum, and derivative).

Material of main part as luminescent layer, preferably cited amine compound (for example triarylamine compound), the accurate oxide compound of metal-chelating (metal chelate oxynoid compounds) (compound) with metal-oxygen key, wherein said metal is an aluminium, zinc or transition metal, with part be the oxine derivative, 2-(2-pyridyl) phenol derivatives etc., polyarylene compound (for example hexaphenyl benzene derivative), fused aromatic isocyclic compound and non-complexing aromatics nitrogen-containing heterocycle compound (for example carbazole derivative).The material of main part of described luminescent layer can be the mixture of at least two kinds of compounds.

Thickness to luminescent layer has no particular limits, but its thickness is usually preferably from 1 nanometer to 5 micron, is more preferably from 5 nanometers to 1 micron, more preferably from 10 nanometer to 500 nanometers.

Although the method that forms luminescent layer is had no particular limits, can use as the resistive heating vapor deposition method, electronic beam method, sputtering method, molecular layer is legal, coating method, ink jet method, print process, LB (Langmuir-Blodgett) facture, and transfer method.Preferably resistive heating vapor deposition method and coating method.

Luminescent layer can be by single compound formation, or by two or more compound formation.In addition, luminescent layer can have single layer structure, or the multilayered structure of two-layer at least composition.Each layer can be launched the light of different color, and therefore, luminescent layer can be launched for example white light.Single luminescent layer can be launched white light.When luminescent layer was multilayer, each layer can be formed by single-material, or formed by at least two kinds of compounds or material.

If the material of hole injection layer and hole transmission layer has (1) from anodal injected hole, (2) transporting holes and (3) stop that described material is enough by any of these three kinds of effects of negative pole injected electrons.The object lesson of described material comprises: carbazole derivative, triazole derivative, oxazole derivatives oxadiazole derivative, imdazole derivatives, poly-aryl alkane derivatives, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, aryl amine derivatives, the chalcone derivative of amino-replacement, styryl anthracene derivant, fluorenone derivatives, hydrazone derivative, stilbene derivatives, the silazane derivative, the aromatic uncle amine compound, styrylamine compound, aromatics two methyne compounds, porphyrins, the polysilanes compound, poly-(N-vinylcarbazole) derivative, phenyl amines multipolymer, the conducting polymer weight oligomers is as thiophene oligomers and Polythiophene; Organic silane compound, carbon film, and compound of the present invention.Thickness to hole injection layer has no particular limits, but its thickness is usually preferably from 1 nanometer to 5 micron, is more preferably from 5 nanometers to 1 micron, more preferably from 10 nanometer to 500 nanometers.Thickness to hole transmission layer has no particular limits, but its thickness is usually preferably from 1 nanometer to 5 micron, is more preferably from 5 nanometers to 1 micron, more preferably from 10 nanometer to 500 nanometers.Hole injection layer or hole transmission layer can have the single layer structure of one or both or multiple above-mentioned materials, perhaps can be to comprise the multiwalled multilayered structure, and described multilayer has identical or different component.

As the material of hole injection layer, preferably copper phthalocyanine and star burst type (star-burst type) amine compound.

The example of the formation method of hole injection layer and hole transmission layer comprises: vacuum deposition method, the LB method is with the method that above-mentioned hole injection/transport material is dissolved or dispersed in solvent and is coated with, ink jet method, print process, and transfer method.Under the situation of coating method, hole injection/transport material usable resins component is dissolved or is disperseed.The example of described resin Composition comprises: polyvinyl chloride, polycarbonate, polystyrene, polymethylmethacrylate, poly-n-butyl methacrylate, polyester, polysulfones, polyphenylene oxide, polyhutadiene, poly-(N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polymeric amide, ethyl cellulose, vinyl-acetic ester, ABS resin, urethane, melamine resin, unsaturated polyester resin, Synolac, Resins, epoxy, silicone resin, or the like.

Inject electronics if the material of electron injecting layer and electron transfer layer has (1) from negative pole, (2) transmission electronic and (3) stop (as the blocking layer) by any of these three kinds of effects of anodal injected holes, and described material is enough.As the material of electron transfer layer, the accurate oxide compound of preferable alloy chelating, the aromatic heterocycle compounds of fused aromatic isocyclic compound and non-complexing.The specific examples of described material comprises triazole derivative, oxazole derivatives oxadiazole derivative, imdazole derivatives, fluorenone derivatives, anthraquinone bismethane (anthraquinodimethane) derivative, anthracyclinone derivatives, the phenylbenzene quinone derivative, the thiapyran dioxide derivative, carbodiimide derivative, fluorenylidene methane Derivatives, the diphenylethyllene pyrazines derivatives, aromatic ring such as naphthalene nucleus be with the Si Suo Suan of perylene, and phthalocyanine derivates is by the various metal complexs of the metal complex representative of oxine derivative, metal phthalocyanine and metal complex with benzoxazole or benzothiazole part, organic silane compound.Thickness to electron injecting layer and electron transfer layer has no particular limits, but its thickness is usually preferably from 1 nanometer to 5 micron, is more preferably from 5 nanometers to 1 micron, more preferably from 10 nanometer to 500 nanometers.Electron injecting layer and electron transfer layer can be the single layer structures that comprises one or both or multiple above-mentioned materials, perhaps can be to comprise the multiwalled multilayered structure, and described multilayer has identical or different component.

The example of the formation method of electron injecting layer and electron transfer layer comprises: vacuum deposition method, the LB method is with the method that above-mentioned hole injection/transport material is dissolved or dispersed in solvent and is coated with, ink jet method, print process, and transfer method.Under the situation of coating method, electronics injection/transport material usable resins component is dissolved or is disperseed.As resin Composition, for example can use those components of in hole injection layer and hole transmission layer, enumerating.

Make the material of device or element accelerated deterioration such as the function in water or oxygen access to plant or the element if protective layer has to stop, this protective layer material enough.The object lesson of described material comprises as In, Sn, Pb, Au, Cu, Ag, Al, Ti and Ni; Metal oxide, as MgO, SiO, SiO ₂, Al ₂O ₃, GeO, NiO, CaO, BaO, Fe ₂O ₃, Y ₂O ₃And TiO ₂Metal fluoride is as MgF ₂, LiF, AlF ₃And CaF ₂Metal nitride is as SiN _xAnd SiO _xN _yPolyethylene, polypropylene, polymethylmethacrylate, polyimide, polyureas, tetrafluoroethylene, polychlorotrifluoroethylene, poly-dichloro difluoroethylene, the multipolymer of trifluorochloroethylene and dichloro difluoroethylene, the multipolymer that the monomer mixture copolymerization of tetrafluoroethylene and at least a comonomer makes, the fluorinated copolymer that on main chain, has ring texture, water-intake rate is at least 1% absorbent material, and water-intake rate is at most 0.1% water-repellent substance.

Formation method to protective layer also has no particular limits, and for example can adopt vacuum deposition method, sputtering method; reactive sputtering, MBE (molecular beam epitaxy) method, ion beam method; ion-plating method, plasma polymerization method (high frequency excitation ion plating method), plasma CVD (chemical vapor deposition) method; the laser CVD method; add the hot CVD method, source of the gas CVD method, coating method; print process, and transfer method.

Embodiment

Explain the present invention in more detail referring now to following embodiment, but should be understood that, implement concrete scheme of the present invention and be not construed as limiting the invention.

Synthesizing of compound (1)

To 6,6 '-two (2-hydroxy phenyls)-2,2 '-dipyridyl (0.1g) and PtCl ₂Add benzonitrile (10ml) (0.16g), then reflux 3 hours under nitrogen atmosphere.After reaction soln is cooled to room temperature, methyl alcohol is added to forms precipitation in the reaction soln, suction strainer should precipitation.Institute's solid that obtains obtains 0.06g compound (1) with silica gel chromatography (chloroform is as photographic developer) purifying.Structure with mass spectroscopy authenticating compound (1).The UV irradiation contains the chloroformic solution of compound (1) under nitrogen atmosphere, obtains reddish orange emission light (λ _Max=624nm).

Compound (1)

As 6,6 '-two (2-hydroxy phenyls)-2 of starting raw material, 2 '-dipyridyl can be according to Journal of Organic Chemistry in above-mentioned reaction, and the method described in 741,11 (1946) is synthetic.Perhaps this compound can be synthetic by following proposal.

Synthetic 6,6 '-two (2-p-methoxy-phenyls)-2,2 '-dipyridyl

To 6,6 '-two bromo-2,2 '-dipyridyl (1.15g), 2-anisole ylboronic acid (1.45g), PPh ₃(0.167g), salt of wormwood (2.2g) and Pd (OAc) ₂Add glycol dimethyl ether (10ml) and water (10ml) in the mixture (36mg), then reflux 4 hours under nitrogen atmosphere.After reaction soln is cooled to room temperature, chloroform (20ml) is added in the reaction soln with water (20ml) separates.Concentrate organic layer then.Carry out purifying with silica gel chromatography (chloroform is as photographic developer), obtain 0.9g 6,6 '-two (2-p-methoxy-phenyl)-2,2 '-dipyridyl.Synthetic 6,6 '-two (2-hydroxy phenyls)-2,2 '-dipyridyl

At nitrogen atmosphere, 160 ℃ of following heating 6,6 '-two (2-p-methoxy-phenyls)-2,2 '-bipyridine ligands (0.3g), and the mixture of pyridine hydrochloride (10g) 4 hours.After reaction soln is cooled to room temperature, chloroform (20ml) is added in the reaction soln with water (20ml) separates.Concentrate organic layer then.Carry out purifying with silica gel chromatography (chloroform is as photographic developer), obtain 0.2g6,6 '-two (2-hydroxy phenyls)-2,2 '-dipyridyl.

Synthetic schemes according to above-mentioned same procedure synthetic compound (79) and compound (88) is as follows.

Synthetic schemes-1

Compound (79)

Synthetic schemes-2

Compound (88)

The λ of the light of the compound in ethylene dichloride (79) emission _MaxBe 512nm, and the λ of the light of the compound in ethylene dichloride (88) emission _MaxBe 620nm.

By the compound of formula (11) or (12) representative, each alkyl naturally of substituting group wherein, aryl, heteroaryl or halogen atom also can be synthetic according to aforesaid method.

Comparative Examples 1

The ITO substrate of cleaning is placed vacuum-evaporator, and evaporation TPD (N, N-phenylbenzene-N, N-two (tolyl) p-diaminodiphenyl) formation has the film that thickness is 50nm on this substrate, coevaporation PtOEP (octaethylporphyrin platinum complex) and compd A (weight ratio is 1: 17) have the film that thickness is 36nm with formation then, evaporate compd A afterwards and have the film that thickness is 36nm with formation.Then, be provided with on the organic thin layer of Huo Deing in the above patterned mask (patterned mask) (each emitting area is adjusted to 4mm * 5mm), and in vacuum-evaporator further evaporation lithium fluoride, have film that thickness be 3nm thereby form thereon; And then the thick aluminium film of deposition 400nm.

By applying dc constant voltage on it, by by Toyo Technica Co., the source measuring apparatus (Model 2400 (trade(brand)name)) that Ltd. makes makes the EL device of producing thus luminous; And the photometer BM-8 (trade(brand)name) that utilizes Topcon Co. to make measures the brightness that the EL device demonstrates.As the result who measures, find that the emission luminance brightness of being sent by the EL device is 200cd/m ², its external quantum efficiency is 1.1%, and high-high brightness is 390cd/m ²

Embodiment 1

The ITO substrate of cleaning is placed vacuum-evaporator, and evaporation TPD (N, N-phenylbenzene-N, N-two (tolyl) p-diaminodiphenyl) formation has the film that thickness is 50nm on this substrate, coevaporation has the film that thickness is 36nm according to compound of the present invention (1) and compd A (weight ratio is 1: 17) with formation then, evaporates compd B afterwards and has the film that thickness is 36nm with formation.Then, be provided with on the organic thin layer of Huo Deing in the above patterned mask (each emitting area is adjusted to 4mm * 5mm), and in vacuum-evaporator further evaporation lithium fluoride, have film that thickness be 3nm thereby form thereon; And then the thick aluminium film of deposition 400nm.

By applying dc constant voltage on it, by by Toyo Technica Co., the source measuring apparatus (Model 2400 (trade(brand)name)) that Ltd. makes makes the EL device of producing thus luminous; And the photometer BM-8 (trade(brand)name) that utilizes Topcon Co. to make measures the brightness that the EL device demonstrates.As the result who measures, find that the emission luminance brightness of being sent by the EL device is 200cd/m ², its external quantum efficiency is 2.8%, and high-high brightness is 1090cd/m ²

Embodiment 2

The ITO substrate of cleaning is placed vacuum-evaporator, and evaporate TPD (N successively, N-phenylbenzene-N, N-two (tolyl) p-diaminodiphenyl) formation has the film that thickness is 50nm on this substrate, coevaporation has the film that thickness is 36nm according to compound of the present invention (1) and compd A (weight ratio is 1: 2) with formation then, evaporates compd B afterwards and has the film that thickness is 36nm with formation.Then, be provided with on the organic thin layer of Huo Deing in the above patterned mask (each emitting area is adjusted to 4mm * 5mm), and in vacuum-evaporator further evaporation lithium fluoride, have film that thickness be 3nm thereby form thereon; And then the thick aluminium film of deposition 400nm.

By applying dc constant voltage on it, by by Toyo Technica Co., the source measuring apparatus (Model 2400 (trade(brand)name)) that Ltd. makes makes the EL device of producing thus luminous; And the photometer BM-8 (trade(brand)name) that utilizes Topcon Co. to make measures the brightness that the EL device demonstrates.As the result who measures, find that the emission luminance brightness of being sent by the EL device is 200cd/m ², its external quantum efficiency is 4.4%, and high-high brightness is 3820cd/m ²

Comparative Examples 2

According to U.S. patent No.6,653, the method described in the embodiment 8 of 654B1 prepares EL device (device No-101).

Comparative Examples 3

The ITO substrate of cleaning is placed vacuum-evaporator, and evaporation α-NPD forms on this substrate and has the hole transmission layer that thickness is 50nm.Then separately with 0.4nm/sec and 0.02nm/sec coevaporation Bepp as main body ₂With as the compound (65) of luminescent material so that thickness is 40nm, form luminescent layer thus.Then, be provided with on the organic thin layer of Huo Deing in the above patterned mask (each emitting area is adjusted to 2mm * 2mm), and in vacuum-evaporator further evaporation lithium fluoride, have film that thickness be 1.5nm thereby form thereon; And then the thick aluminium film of deposition 200nm.Then, at this device of sealing after wherein adding siccative, with preparation EL device (device No-102).In addition, prepare another EL device (device No-103), just replace described luminescent material with compound (1) as above-mentioned identical mode.

Embodiment 3

Form luminescent layer with the method identical with Comparative Examples 3, just the thickness with main body changes 36nm into.Evaporating compd B then is the electron transfer layer of 36nm to form thickness.Then, be provided with on the organic thin layer of Huo Deing in the above patterned mask (each emitting area is adjusted to 2mm * 2mm), and in vacuum-evaporator further evaporation lithium fluoride, have film that thickness be 5nm thereby form thereon; And then the thick aluminium film of deposition 500nm.Then, at this device of sealing after wherein adding siccative, with preparation EL device (device No-104).In addition, prepare another EL device (device No-105), just replace described material of main part with compd A as above-mentioned identical mode.

Embodiment 4

The ITO substrate of cleaning is placed vacuum-evaporator, and the evaporation copper phthalocyanine is the film of 10nm to form thickness on this substrate, evaporates α-NPD then thereon and have the film that thickness is 20nm, form hole transmission layer thus with formation.Then separately with 0.4nm/sec and 0.02nm/sec coevaporation as the compd A of main body and as the compound (1) of luminescent material so that thickness is 30nm, form luminescent layer thus.On luminescent layer, evaporation BAlq has the hole blocking layer that thickness is 10nm with formation, evaporates Alq afterwards and has the electron transfer layer that thickness is 40nm with formation.Then, patterned mask is set on the organic thin layer of Huo Deing in the above (each emitting area is adjusted to 2mm * 2mm), and in vacuum-evaporator, further evaporate lithium fluoride, have film that thickness be 5nm thereby form thereon, and then the thick aluminium film of deposition 500nm.Then, at this device of sealing after wherein adding siccative, with preparation EL device (device No-201).In addition, preparing other EL device (device No-202 to 206) as above-mentioned identical mode, is change material of main part as shown in table 2.

Compd A

Next, the EL device for preparing thus of following evaluation.

By applying dc constant voltage on it, by by Toyo Technica Co., the source measuring mechanism (Model 2400 (trade(brand)name)) that Ltd. makes makes EL device of the present invention and comparison luminous; And the photometer BM-8 (trade(brand)name) that utilizes Topcon Co. to make measures the brightness that each EL device demonstrates and the spectrum analyzer PMA-11 (trade(brand)name) that uses Hamamatsu Photonics KK to make measures wavelength of transmitted light to obtain luminous efficiency.Next, following evaluation persistence is at first at 1mA/4mm ²Speed under drive this device, measure original intensity.Then, with 1mA/4mm ²Speed under after low current drives this device 200h, measure brightness.By the brightness of 200h is compared the conservation rate that obtains brightness with original intensity.The results are shown in table 1 and 2.

Table 1

The device number	Luminescent material (doping content)	Material of main part (thickness)	Electron transfer layer (thickness)	The brightness conservation rate	Comment
The device number	Luminescent material (doping content)	Material of main part (thickness)	Electron transfer layer (thickness)	The brightness conservation rate	Comment	101	Compound (65) 2%	Bepp ₂ (40nm)	-	6％	Comparative Examples (device described in US6653564B1)
102	Compound (65) 5%	Bepp ₂ (40nm)	-	11％	Comparative Examples (device described in US6653564B1)	101	Compound (65) 2%	Bepp ₂ (40nm)	-	6％	Comparative Examples (device described in US6653564B1)
102	Compound (65) 5%	Bepp ₂ (40nm)	-	11％	Comparative Examples (device described in US6653564B1)	103	Compound (1) 5%	Bepp ₂ (40nm)	-	8％	Comparative Examples (device described in US6653564B1)
104	Compound (1) 5%	Bepp ₂ (36nm)	Compd B (36nm)	21％	The present invention	103	Compound (1) 5%	Bepp ₂ (40nm)	-	8％	Comparative Examples (device described in US6653564B1)
104	Compound (1) 5%	Bepp ₂ (36nm)	Compd B (36nm)	21％	The present invention	105	Compound (1) 5%	Compd A (36nm)	Compd B (36nm)	32％	The present invention

Device is formed: ITO/NPD (50nm)/5 weight % luminescent material-material of main part/electron transport material/LiF-Al

The result confirms that the device of the present invention contain electron transfer layer compares with the device in the Comparative Examples, shows the enhanced brightness conservation rate, thereby realizes the persistence of the excellence of this device.In addition, aromatic heterocycle compounds by material of main part being changed into non-complexing such as compd A and further put forward the persistence of this device.

Table 2

The device number	Luminescent material	Material of main part	Emission light λ _max	The brightness conservation rate	Comment
The device number	Luminescent material	Material of main part	Emission light λ _max	The brightness conservation rate	Comment	201	Compound (1)	Compd A	615nm	81％	The present invention
202	Compound (15)	Compd A	586nm	88％	The present invention	201	Compound (1)	Compd A	615nm	81％	The present invention
202	Compound (15)	Compd A	586nm	88％	The present invention	204	Compound (79)	Compd A	509nm	83％	The present invention
205	Compound (88)	Compd A	620nm	79％	The present invention	204	Compound (79)	Compd A	509nm	83％	The present invention
205	Compound (88)	Compd A	620nm	79％	The present invention	206	Compound (15)	BAlq	585nm	92％	The present invention

Device is formed: ITO/CuPc (10nm)/NPD (20nm)/5 weight % luminescent material-material of main part (30nm)/BAlq (10nm)/Alq (40nm)/LiF-Al

In addition, the result confirms to use copper phthalocyanine (CuPc) further to improve the persistence of this device as hole injection layer and BAlq as hole blocking layer, and compound of the present invention makes the ruddiness of emission and green glow have excellent colour purity.And compound of the present invention makes that also radiative wavelength is shorter.

Industrial applicibility

Light-emitting device of the present invention is all very excellent aspect external quantum efficiency and maximum luminousing brightness, and has the excellent characteristics of luminescence (performance).In addition, the persistence of this light-emitting device is also very excellent.Light-emitting device of the present invention preferably is suitable for following field, as display unit, and indicating meter, backlight, electrophotography, searchlighting light source, recording light source, exposure light source, reading lamp source, signal, annunciator, interior lighting, and optical communication.In addition, compound of the present invention can be used for electroluminescent device, and medical usage, brightener, photographic material, UV light absorber, laser dyes, recording medium material, ink-jet pigment, colour filter dyestuff, color correction filter etc.New complex compound of the present invention is suitable for preparing the light-emitting device of aforesaid excellence.

Although invention has been described in conjunction with embodiment of the present invention, except as otherwise noted, the present invention is not limited to described arbitrary details, and the present invention is limited by the scope of listing in as appended claims in its spirit and scope.

Claims

1. Organnic electroluminescent device, it comprises pair of electrodes and at least one organic layer that comprises luminescent layer between described pair of electrodes, and wherein at least one layer between described pair of electrodes comprises at least a metal complex with three toothed chain structure parts or higher multiple tooth chain structure part.

2. Organnic electroluminescent device as claimed in claim 1, the metal ion in the wherein said metal complex is selected from platinum, iridium, rhenium, palladium, rhodium, ruthenium and cupric ion.

3. Organnic electroluminescent device as claimed in claim 1 or 2, wherein said metal complex does not have carbon-to-metal bond.

4. as each described Organnic electroluminescent device of claim 1-3, wherein said metal complex is phosphorescent metal complex, and described metal complex is contained in the described luminescent layer.

5. as each described Organnic electroluminescent device of claim 1-4, wherein said metal complex is the compound by formula (1) representative:

Formula (1)

6. as each described Organnic electroluminescent device of claim 1-5, wherein said metal complex is the compound by formula (2) representative:

Formula (2)

7. Organnic electroluminescent device as claimed in claim 6, wherein said metal complex are the compounds by formula (2) representative, wherein by Q ²¹The ring that forms and by Q ²²Each pyridine ring naturally of the ring that forms, and Y ²¹The linking group that representative is made up of at least one atom.

8. Organnic electroluminescent device as claimed in claim 6, wherein said metal complex are the compounds by formula (2) representative, wherein by Q ²¹The ring that forms and by Q ²²Each pyridine ring naturally of the ring that forms, and Y ²¹Represent singly-bound or two key, and X ²¹And X ²²Represent sulphur atom or replacement or unsubstituted nitrogen-atoms separately.

9. Organnic electroluminescent device as claimed in claim 6, wherein said metal complex are the compounds by formula (2) representative, wherein by Q ²¹The ring that forms and by Q ²²Each 5 member heterocyclic ring containing nitrogen naturally of the ring that forms.

10. Organnic electroluminescent device as claimed in claim 6, wherein said metal complex are the compounds by formula (2) representative, wherein by Q ²¹The ring that forms and by Q ²²Each contains 6 yuan of heterocycles of at least two nitrogen-atoms naturally the ring that forms.

11. Organnic electroluminescent device as claimed in claim 1 or 2, wherein said metal complex are the compounds by formula (9) representative:

Formula (9)

Wherein, M ^A1Representation metal ion; Q ^A1And Q ^A2Representative forms the atomic group of nitrogen heterocyclic ring necessity separately; R ^A1, R ^A2, R ^A3And R ^A4Represent hydrogen atom or substituting group separately; R ^A1And R ^A2, and R ^A3And R ^A4Can be respectively each other bonding to form ring; Y ^A2And Y ^A3Represent linking group or singly-bound separately; Y ^A1Represent linking group, singly-bound or two key so that two bidentate ligands in bracket are linked together; L ^A5Representative and M ^A1The coordinate part; n ^A1Represent 0 to 4 integer.

12. Organnic electroluminescent device as claimed in claim 1 or 2, wherein said metal complex are the compounds by formula (10) representative,

Formula (10)

13. as each described Organnic electroluminescent device of claim 1-4, wherein said metal complex is the compound by formula (8) representative,

Formula (8)

Wherein, M ⁸¹Representation metal ion; L ⁸¹, L ⁸², L ⁸³And L ⁸⁵Represent separately and M ⁸¹The coordinate part; L ⁸¹And L ⁸³Be not joined together to form ring-type part or tetradentate ligands or higher polydentate ligand by atomic group; L ⁸⁵Not directly and L ⁸¹Or L ⁸³Bonding, but pass through metal link; Y ⁸¹And Y ⁸²Represent linking group, singly-bound or two key separately; n ⁸¹Represent 0 to 3 integer.

14. Organnic electroluminescent device as claimed in claim 13, wherein said metal complex are the compound by formula (8) representative, wherein L ⁸¹, L ⁸²And L ⁸³Represent separately by carbon atom and M ⁸¹Coordinate aromatic carbocyclic or heterocycle, or by nitrogen-atoms and M ⁸¹The coordinate nitrogen heterocyclic ring; And L ⁸¹, L ⁸²And L ⁸³In be described nitrogen heterocyclic ring one of at least.

15. Organnic electroluminescent device as claimed in claim 1 or 2, wherein said metal complex are the compounds by formula (X1) representative:

Formula (X1)

16. Organnic electroluminescent device as claimed in claim 15, wherein said metal complex by formula (X1) representative are the compounds by formula (X2) representative:

Formula (X2)

17. Organnic electroluminescent device as claimed in claim 15, wherein said metal complex by formula (X1) representative are the compounds by formula (X3) representative:

Formula (X3)

18. as each described Organnic electroluminescent device of claim 1-17, wherein said organic layer comprises at least one luminescent layer and hole transmission layer, and described organic layer also comprises the layer that at least one is selected from exciton barrier-layer, hole injection layer, hole blocking layer and electron transfer layer.

19. as each described Organnic electroluminescent device of claim 1-18, wherein said organic layer comprises at least one luminescent layer, and the material of main part of described luminescent layer is selected from amine compound, the accurate oxide compound of metal-chelating, wherein said metal is aluminium, zinc or transition metal, polyarylene compound, fused aromatic isocyclic compound and non-complexing aromatic heterocycle compounds.

20. as each described Organnic electroluminescent device of claim 1-19, wherein said organic layer comprises at least one electron transfer layer, and wherein electron transport material is selected from the accurate oxide compound of metal-chelating, polyarylene compound, fused aromatic isocyclic compound and non-complexing aromatic heterocycle compounds.

21. as each described Organnic electroluminescent device of claim 1-20, wherein said organic layer comprises at least one luminescent layer, the material of main part of described luminescent layer is made up of at least two kinds of compounds.

22. compound by formula (11) representative:

Formula (11)

23. compound by formula (12) representative:

Formula (12)

Wherein, R ^D3And R ^D4Represent hydrogen atom or substituting group separately; R ^D1And R ^D2Represent substituting group separately; n ^D1And n ^D2Represent 0 to 4 integer separately; When there being a plurality of R ^D1The time, each R ^D1Can be same to each other or different to each other, and a plurality of R ^D1Bonding is to form ring each other; When there being a plurality of R ^D2The time, each R ^D2Can be same to each other or different to each other, and a plurality of R ^D2Bonding is to form ring each other; Y ^D1Representative has vinyl, phenylene, pyridine ring, pyrazine ring, the pyrimidine ring of replacement in 1-and 2-position or has the alkylidene group of 1 to 8 carbon atom.