CN111548350A

CN111548350A - Polycyclic aromatic hydrocarbon aza-naphthalene derivative, synthetic method and electronic device thereof

Info

Publication number: CN111548350A
Application number: CN202010301079.7A
Authority: CN
Inventors: 崔林松; 朱向东; 张业欣; 陈华
Original assignee: Suzhou Jiuxian New Material Co ltd
Current assignee: Suzhou Jiuxian New Material Co ltd
Priority date: 2020-04-16
Filing date: 2020-04-16
Publication date: 2020-08-18

Abstract

The invention relates to the technical field of organic photoelectric materials, in particular to polycyclic aromatic hydrocarbon and aza-naphthalene derivatives, a synthesis method thereof and an electronic device containing the polycyclic aromatic hydrocarbon and aza-naphthalene derivatives, which are represented by a general formula (1): wherein Z represents CR¹Or N. The polycyclic aromatic hydrocarbon aza-naphthalene derivative has excellent film forming property and thermal stability by introducing a polycyclic aromatic hydrocarbon aza-naphthalene rigid structure, and can be preparedThe preparation method is used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. In addition, the polycyclic aromatic hydrocarbon-aza-naphthalene derivative of the present invention can be used as a constituent material of a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer, and can reduce a driving voltage, improve efficiency, luminance, lifetime, and the like.

Description

Polycyclic aromatic hydrocarbon aza-naphthalene derivative, synthetic method and electronic device thereof

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to polycyclic aromatic hydrocarbon and aza-naphthalene derivatives, a synthesis method thereof and an electronic device containing the polycyclic aromatic hydrocarbon and aza-naphthalene derivatives.

Background

The organic electroluminescent device has a series of advantages of self-luminescence, low-voltage driving, full curing, wide viewing angle, simple composition and process and the like, and compared with a liquid crystal display, the organic electroluminescent device does not need a backlight source. Therefore, the organic electroluminescent device has wide application prospect.

Organic electroluminescent devices generally comprise an anode, a metal cathode and an organic layer sandwiched therebetween. The organic layer mainly comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In addition, a host-guest structure is often used for the light-emitting layer. That is, the light emitting material is doped in the host material at a certain concentration to avoid concentration quenching and triplet-triplet annihilation, improving the light emitting efficiency. Therefore, the host material is generally required to have a higher triplet energy level and, at the same time, a higher stability.

At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a large number of organic electroluminescent materials with excellent performance have been developed. In view of the above, the future direction of organic electroluminescent devices is to develop high efficiency, long lifetime, low cost white light devices and full color display devices, but the industrialization of the technology still faces many key problems. Therefore, designing and searching a stable and efficient compound as a novel material of an organic electroluminescent device to overcome the defects of the organic electroluminescent device in the practical application process is a key point in the research work of the organic electroluminescent device material and the future research and development trend.

Disclosure of Invention

The polycyclic aromatic hydrocarbon aza-naphthalene derivative has high thermal stability, good transmission performance and simple preparation method, and an organic light-emitting device prepared from the polycyclic aromatic hydrocarbon aza-naphthalene derivative has the advantages of high light-emitting efficiency, long service life and low driving voltage, and is an organic electroluminescent material with excellent performance.

It is another object of the present invention to provide an electronic device using the polycyclic aromatic hydrocarbon-azanaphthalene derivative, which has advantages of high efficiency, high durability and long life.

In order to achieve the above purpose, the invention provides the following technical scheme:

a polycyclic aromatic hydrocarbon azanaphthalene derivative represented by the following general formula (1):

wherein Z represents CR¹Or N;

the ring M represents a group represented by any one of the following structural formulae (A) to (D):

wherein the dotted line represents a bond;

L₁～L₄each independently represents one or more of a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;

A₁～A₄each independently represents Ar₁、Ar₂、Ar₃、Ar₄、

One or more of;

Ar₁～Ar₈each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;

R¹represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃One or more of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;

R²represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms;

z in the formulae (A) to (D) has the meaning as defined for the formula (1).

Specifically, the compound is further represented by the following general formula (I) or (II):

said L₁～L₄And Ar₁～Ar₈Have the meaning as defined in claim 1.

Specifically, Ar is₁～Ar₈Each independently selected from the following groups:

wherein the dotted line represents the same as L₁、L₂、L₃、L₄Or a N-bonded bond, R¹Has the meaning as defined for the general formula (1).

Specifically, the R is¹And R²Each independently represents one or more of phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron group, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, or tetraphenyl silicon group.

Specifically, the polycyclic aromatic hydrocarbon and azanaphthalene derivative represented by the general formula (1) is selected from the following compounds:

the synthetic method of the polycyclic aromatic hydrocarbon aza-naphthalene derivative comprises the following synthetic route:

in particular to application of polycyclic aromatic hydrocarbon aza-naphthalene derivatives in electronic devices.

Specifically, the electronic device is an organic electroluminescent device, an organic field effect transistor or an organic solar cell;

wherein the organic electroluminescent device comprises: the organic electroluminescence device includes a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains a polycyclic aromatic hydrocarbon-azanaphthalene derivative.

Specifically, the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.

Furthermore, the polycyclic aromatic hydrocarbon aza-naphthalene compound has a special biphenyl structure, has high thermal stability, chemical stability and carrier transport property, and more importantly, has proper singlet state, triplet state and molecular orbital energy level. Therefore, the organic electroluminescent material is introduced into molecules with electroluminescent characteristics, so that the stability and the luminous efficiency of a device are improved, and the driving voltage of the device is reduced.

The invention has the beneficial effects that:

(1) the polycyclic aromatic hydrocarbon and aza-naphthalene derivative has good film forming property and thermal stability by introducing a polycyclic aromatic hydrocarbon and aza-naphthalene rigid structure, can be used for preparing electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, particularly as a constituent material of a hole injection layer, a hole transmission layer, a light emitting layer, an electron blocking layer, a hole blocking layer or an electron transmission layer in the organic electroluminescent devices, can show the advantages of high luminous efficiency, long service life and low driving voltage, and is obviously superior to the existing organic electroluminescent devices;

(2) the preparation method of the polycyclic aromatic hydrocarbon aza-naphthalene derivative is simple, raw materials are easy to obtain, and the development requirement of industrialization can be met;

(3) the polycyclic aromatic hydrocarbon aza-naphthalene derivative has good application effect in electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, and has wide industrialization prospect;

(4) the polycyclic aromatic hydrocarbon aza-naphthalene derivative has high electron injection and moving speed. Therefore, the organic electroluminescent device having an electron injection layer and/or an electron transport layer prepared using the polycyclic aromatic hydrocarbon-azanaphthalene derivative of the present invention improves the electron transport efficiency from the electron transport layer to the light emitting layer, thereby improving the light emitting efficiency. And, the driving voltage is reduced, thereby enhancing the durability of the resulting organic electroluminescent device;

(5) the polycyclic aromatic hydrocarbon aza-naphthalene derivative has excellent capacity of blocking holes, excellent electron transport performance and stability in a thin film state. Therefore, the organic electroluminescent device having the hole blocking layer prepared using the polycyclic aromatic hydrocarbon and aza-naphthalene derivative of the present invention has high luminous efficiency, reduced driving voltage, and improved current tolerance, so that the maximum luminous brightness of the organic electroluminescent device is increased;

(6) the polycyclic aromatic hydrocarbon aza-naphthalene derivative can be used as a constituent material of a hole injection layer, a hole transport layer, a light-emitting layer, an electron blocking layer, a hole blocking layer or an electron transport layer of an organic electroluminescent device. With the organic electroluminescent device of the present invention, excitons generated in the light emitting layer can be confined, and the possibility of recombination of holes and electrons can be further increased to obtain high luminous efficiency. In addition, the driving voltage is so low that high durability can be achieved.

Drawings

FIG. 1 is a fluorescence spectrum (PL) of example 2 (compounds 1 to 34) of the present invention in a dichloromethane solution;

FIG. 2 is an electroluminescence spectrum of example 4 of the present invention and comparative example 1;

fig. 3 is a structural view of an organic electroluminescent device according to the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the following embodiments, unless otherwise specified, the technical means used are conventional means well known to those skilled in the art.

The polycyclic aromatic hydrocarbon azanaphthalene derivative of the present invention is a novel compound having a fluorene ring structure and is represented by the following general formula (1):

further, the polycyclic aromatic hydrocarbon azanaphthalene derivative has the following general formula (I) or (II):

in the above general formulae (1), (I) and (II),

A₁～A₄each independently represents Ar₁、Ar₂、Ar₃、Ar₄、

One or more of;

Ar₁～Ar₈each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹One or more of substituted aromatic heterocyclic groups having 5 to 30 carbon atomsA plurality of;

R²represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

<L₁To L₄>

L₁～L₄Each independently represents one or more of a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms.

In the present invention, the hetero atom in the aromatic heterocyclic group having 5 to 18 carbon atoms is preferably selected from N, O and/or S. In the present invention, the number of hetero atoms may be 1 to 5. An aromatic hydrocarbon group or aromatic heterocyclic group in the sense of the present invention means a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-hydrogen atoms), which may be, for example, carbon atoms, nitrogen atoms, oxygen atoms or carbonyl groups. For example, systems of 9, 9' -spirobifluorenes, 9, 9-diarylfluorenes, triarylamines, diaryl ethers, etc., as well as systems in which two or more aryl groups are interrupted, for example by linear or cyclic alkyl groups or by silyl groups, are also intended to be considered aromatic hydrocarbon groups in the sense of the present invention. Furthermore, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as biphenyl, terphenyl or quaterphenyl, are likewise intended to be regarded as aromatic hydrocarbon groups or aromatic heterocyclic groups.

From L₁～L₄The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, hydropyranyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, perylenyl, anthryl, benzopyrenyl, terphenylenyl, terphenylindenyl, etc, Phenanthridinyl, benzo-5, 6-quinolinyl, benzo-6, 7-quinolinyl, benzo-7, 8-quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinylimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazenanthrayl, 2, 7-diazapyranyl, 2, 3-diazapyranyl, 1, 6-diazapyranyl, 1, 8-diazapyranyl, 4, 5-diazapyryl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorerynyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxazalylOxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, and the like.

In the present invention, preferably, L₁～L₄Each independently represents one or more of a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 5 to 12 carbon atoms. More preferably, L₁～L₄Each independently represents one or more of a single bond, a carbonyl group, a phenyl group, a triazinyl group or a biphenyl group.

From L₁～L₄The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be unsubstituted, but may also have a substituent. The substituents may be exemplified by the following: a deuterium atom; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, or a n-hexyl group; alkoxy having 1 to 6 carbon atoms such as methoxy, ethoxy or propoxy; alkenyl, such as vinyl or allyl; aryloxy groups such as phenoxy or tolyloxy; arylalkoxy, such as benzyloxy or phenethyloxy; aromatic hydrocarbon radicals or condensed polycyclic aromatic radicals, e.g. phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthryl, benzo [9,10 ] benzo]Phenanthryl or spirobifluorenyl; an aromatic heterocyclic group such as pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuryl, dibenzothienyl, azafluorenyl, diazafluorenyl, carbolinyl, azaspirobifluorenyl or diazaspiro-bifluorenyl; arylethenyl, such as styryl or naphthylethenyl; and acyl radicals, e.g. acetyl orBenzoyl and the like.

The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be linear or branched. Any of the above substituents may be further substituted with the above exemplary substituents. The above substituents may be present independently of each other, but may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

<A₁To A₄>

A₁～A₄Each independently represents Ar₁、Ar₂、Ar₃、Ar₄、

One or more of the above.

(Ar₁To Ar₈)

Ar₁～Ar₈Each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms.

From Ar₁～Ar₈The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, anthryl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, biphenylyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzofuranyl, triphenylphenanthryl, triphenylanthryl, triphenylBenzothienyl, dibenzothienyl, benzothiophenocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, terpyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, benzoxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, benzpyridazinyl, Pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazananthracenyl, diazpyrenyl, tetraazaperylenyl, naphthyridinyl, pyrazinyl, phenazinyl, phenothiazinyl, fluoresceinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboranyl, triphenylphoxy, diphenylphosphinyloxy, triphenylsilyl, tetraphenyl and the like.

In the present invention, preferably, Ar₁～Ar₈Each independently selected from the following groups:

wherein the dotted line represents and L₁、L₂、L₃、L₄Or an N-bonded bond; r¹Have the meaning as defined above.

From Ar₁～Ar₈The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from Ar₁～Ar₈The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by¹Substituted, aromatic hydrocarbon radicals having 5 to 30 carbon atoms or substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms.

(R¹)

R¹Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms.

From R¹The alkyl group having 1 to 20 carbon atoms represented may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.

From R¹Having 1 to 20 carbon atomsThe alkyl groups of the molecule may be unsubstituted, but may also have substituents. Preferably, from R¹Alkyl having 1 to 20 carbon atoms represented by one or more of the following R²And (4) substitution. In addition, one or more non-adjacent CH in the alkyl group₂The group can be represented by R²C＝CR²、C≡C、Si(R²)₃、C＝O、C＝NR²、P(＝O)R²、SO、SO₂、NR²O, S or CONR²And wherein one or more hydrogen atoms may be replaced with deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group.

From R¹The alkenyl group having 2 to 20 carbon atoms represented may be exemplified by: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, cyclohexenyl and the like. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.

From R¹The alkenyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

From R¹The alkynyl group having 2 to 20 carbon atoms represented may be exemplified by: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl and the like.

From R¹The alkynyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the formula are exemplified by the groups represented by the above formula Ar₁～Ar₈The same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms are shown.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents. In addition, two adjacent R¹Substituents or two adjacent R²The substituents optionally may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R²Substitution; where two or more substituents R¹May be connected to each other and may form a ring.

Preferably represented by R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by (a) may be exemplified by: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, tetraphenyl silicon group, and the like. The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms may be substituted with one or more R²And (4) substitution.

(R²)

R²Represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,One or more of a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From R²The alkyl group having 1 to 20 carbon atoms represented by R can be enumerated by¹The alkyl groups represented by the formulae having 1 to 20 carbon atoms represent the same groups.

From R²The aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented by the formula R¹The same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From R²The alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, or may also have a substituent. The substituents may be exemplified by: a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; cyano, and the like.

(Z)

Z represents CR¹Or N.

R¹Have the meaning as defined above.

(M)

Ring M represents a group represented by any one of the following structural formulae (a) to (D):

wherein the dotted line represents a bond.

< production method >

The polycyclic aromatic azanaphthalene derivative of the present invention can be produced, for example, by the following method:

the obtained compound can be purified by, for example, purification by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, or the like, recrystallization or crystallization using a solvent, sublimation purification, or the like. Identification of compounds can be carried out by mass spectrometry, elemental analysis.

In the polycyclic aromatic azanaphthalene derivative of the present invention, preferred specific examples of the compounds are shown below, but the present invention is by no means limited to these compounds.

< electronic device >

Various electronic devices containing the polycyclic aromatic hydrocarbon-aza-naphthalene derivatives of the present invention can be produced using the polycyclic aromatic hydrocarbon-aza-naphthalene derivatives according to the present invention for producing organic materials which can be configured in particular in the form of layers. In particular, the polycyclic aromatic hydrocarbon aza-naphthalene derivative can be used for organic electroluminescent devices, organic solar cells, organic diodes, especially organic field effect transistors. Particularly in the case of an organic electroluminescent device or a solar cell, the assembly may have a plug structure (the device has one or more p-doped hole transport layers and/or one or more n-doped electron transport layers) or an inverted structure (from the light emitting layer, the upper electrode and the hole transport layer are located on the same side while the substrate is on the opposite side), without being limited to these structures. The injection layer, the transport layer, the light-emitting layer, the blocking layer, and the like can be fabricated, for example, by forming a layer containing or composed of the polycyclic aromatic hydrocarbon-aza-naphthalene derivative according to the present invention between electrodes. However, the use of the polycyclic aromatic hydrocarbon-azanaphthalene derivative according to the present invention is not limited to the above-described exemplary embodiments.

< organic electroluminescent device >

The organic electroluminescent device of the present invention comprises: the organic electroluminescence device includes a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer includes the polycyclic aromatic hydrocarbon-azanaphthalene derivative of the present invention.

Referring to fig. 3, in the organic electroluminescent device of the present invention, for example, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are sequentially disposed on a substrate.

The organic electroluminescent device of the present invention is not limited to such a structure, and for example, some organic layers may be omitted in the multi-layer structure. For example, there may be a configuration in which a hole injection layer between the anode and the hole transport layer, a hole blocking layer between the light emitting layer and the electron transport layer, and an electron injection layer between the electron transport layer and the cathode are omitted, and the anode, the hole transport layer, the light emitting layer, the electron transport layer, and the cathode are provided in this order on the substrate.

The organic electroluminescent device according to the present invention may be manufactured by materials and methods well known in the art, except that the above organic layer contains the compound represented by the above general formula (1). In addition, in the case where the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

For example, the organic electroluminescent device according to the present invention may be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, the following can be made: an anode is formed by depositing metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and a substance which can be used as a cathode is deposited on the organic layer. However, the production method is not limited thereto.

In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

The anode of the organic electroluminescent device of the present invention may be made of a known electrode material. For example, an electrode material having a large work function, such as a metal of vanadium, chromium, copper, zinc, gold, or an alloy thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; such as ZnO, Al or SNO₂A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]And conductive polymers such as PEDOT, polypyrrole, and polyaniline. Among these, ITO is preferable.

As the hole injection layer of the organic electroluminescent device of the present invention, a known material having a hole injection property can be used. Examples thereof include: porphyrin compounds represented by copper phthalocyanine, naphthalenediamine derivatives, star-shaped triphenylamine derivatives, triphenylamine trimers such as arylamine compounds having a structure in which 3 or more triphenylamine structures are connected by a single bond or a divalent group containing no heteroatom in the molecule, tetramers, receptor-type heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the hole transport layer of the organic electroluminescent device of the present invention, a compound containing the polycyclic aromatic hydrocarbon and azanaphthalene derivative of the present invention is preferably used. In addition, other known materials having a hole-transporting property can be used. Examples thereof include: a compound containing a m-carbazolylphenyl group; benzidine derivatives such as N, N ' -diphenyl-N, N ' -di (m-tolyl) benzidine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -tetrakisbiphenylylbenzidine, and the like; 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9 ', 9 "-triphenyl-9H, 9' H, 9" H-3,3 ': 6', 3 "-tricarbazole (Tris-PCz), and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

In addition, in the hole injection layer or the hole transport layer, a material obtained by further P-doping tribromoaniline antimony hexachloride, an axial olefin derivative, or the like to a material generally used in the layer, a polymer compound having a structure of a benzidine derivative such as TPD in a partial structure thereof, or the like may be used.

As the electron blocking layer of the organic electroluminescent device of the present invention, a compound containing the polycyclic aromatic hydrocarbon and azanaphthalene derivative of the present invention is preferably used. In addition, other known compounds having an electron blocking effect may be used. For example, there may be mentioned: carbazole derivatives such as 4,4', 4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), 9-bis [4- (carbazol-9-yl) phenyl ] fluorene, 1, 3-bis (carbazol-9-yl) benzene (mCP), and 2, 2-bis (4-carbazol-9-ylphenyl) adamantane (Ad-Cz); a compound having a triphenylsilyl and triarylamine structure represented by 9- [4- (carbazol-9-yl) phenyl ] -9- [4- (triphenylsilyl) phenyl ] -9H-fluorene; and compounds having an electron-blocking effect, such as monoamine compounds having a high electron-blocking property and various triphenylamine dimers. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the light-emitting layer of the organic electroluminescent element of the present invention, it is preferableOptionally, polycyclic aromatic hydrocarbon and aza-naphthalene derivatives containing the invention are used. In addition to this, Alq can also be used₃Various metal complexes such as metal complexes of a first hydroxyquinoline derivative, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like.

The light emitting layer may be composed of a host material and a dopant material. As the host material, the polycyclic aromatic hydrocarbon-azanaphthalene derivative of the present invention is preferably used. In addition to these, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, heterocyclic compounds having a partial structure in which an indole ring is a condensed ring, and the like can be used.

As the doping material, an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a metal complex, or the like can be used. Examples thereof include pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrenes, perylenes and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirobifluorene derivatives, and the like. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the hole blocking layer of the organic electroluminescent device of the present invention, a compound containing the polycyclic aromatic hydrocarbon and azanaphthalene derivative of the present invention is preferably used. In addition, the hole-blocking layer may be formed using another compound having a hole-blocking property. For example, a phenanthroline derivative such as 2,4, 6-tris (3-phenyl) -1,3, 5-triazine (T2T), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), Bathocuproine (BCP), a metal complex of a quinolyl derivative such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenate (BAlq), and a compound having a hole-blocking effect such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives can be used. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

The above-described material having a hole-blocking property can also be used for formation of an electron transport layer described below. That is, by using the known material having a hole-blocking property, a layer which serves as both a hole-blocking layer and an electron-transporting layer can be formed.

As the electron transport layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the polycyclic aromatic hydrocarbon and azanaphthalene derivative of the present invention. In addition, the compound may be formed using other compounds having an electron-transporting property. For example, Alq can be used₃Metal complexes of quinolinol derivatives including BAlq; various metal complexes; a triazole derivative; a triazine derivative; an oxadiazole derivative; a pyridine derivative; bis (10-hydroxybenzo [ H ]]Quinoline) beryllium (Be (bq)₂) (ii) a Such as 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl]Benzimidazole derivatives such as-1-phenyl-1H-benzimidazole (ZADN); a thiadiazole derivative; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the electron injection layer of the organic electroluminescent device of the present invention, a material known per se can be used. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of quinolinol derivatives such as lithium quinolinol; and metal oxides such as alumina.

In the electron injection layer or the electron transport layer, a material obtained by further N-doping a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used as a material generally used for the layer.

As the cathode of the organic electroluminescent device of the present invention, an electrode material having a low work function such as aluminum, magnesium, or an alloy having a low work function such as magnesium-silver alloy, magnesium-indium alloy, aluminum-magnesium alloy is preferably used as the electrode material.

As the substrate of the present invention, a substrate in a conventional organic light emitting device, such as glass or plastic, can be used. In the present invention, a glass substrate is selected.

Examples

The production of the compound represented by the above general formula (1) and the organic electroluminescent device comprising the same is specifically described in the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1: synthesis of Compounds 1-10

(Synthesis of intermediate M1)

The synthetic route for intermediate M1 is shown below:

to a 250mL single-neck flask were added p-bromobenzoyl hydrazide (4.3g, 20mmol), acenaphthenequinone (3.6g, 20mmol), ammonium acetate (11.8g, 200mmol), and 150mL of acetic acid in this order, and the reaction was stirred under reflux for 12 hours. After the reaction, the solid was collected by suction filtration and washed with a small amount of anhydrous ethanol. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). The solvent was distilled off, and after drying, 4.5g of an orange solid was obtained in a yield of 63%. Ms (ei): m/z: 360.08[ M ]⁺]。Anal.calcd forC₁₉H₁₀BrN₃(％)：C 63.35，H 2.80，N 11.67；found：C 63.33，H 2.85，N 11.64。

(Synthesis of intermediate M2)

The synthetic route for intermediate M2 is shown below:

5-bromopyrimidine (0.9g, 5.7mmol), M1(1.8g, 5.0mmol) and 50mL of toluene were sequentially added to a 100mL single-neck flask under an argon atmosphere, and then a 0.5M toluene solution of potassium bis (trimethylsilyl) amide (6.0mmol) was added dropwise to the reaction system. After 12 hours at 50 ℃, the reaction was quenched by addition of saturated ammonium chloride solution. The organic layer was extracted with ethyl acetate and Na₂SO₄Drying, filtering and collecting solid, and washing with a small amount of absolute ethyl alcohol. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). The solvent was distilled off, and after drying, 1.3g of a yellow solid was obtained in a yield of 63%. Ms (ei): m/z: 409.08[ M +]。Anal.calcd for C₂₃H₁₂BrN₃(％)：C 67.33，H 2.95，N 10.24；found：C67.21，H 2.85，N 10.20。

(Synthesis of Compounds 1 to 10)

The synthetic routes for compounds 1-10 are shown below:

under the protection of nitrogen, an intermediate M2(2.0g, 5mmol) and 5-phenyl-5, 7-indolino [2,3-b ] are sequentially added into a 250mL Schlenk bottle]Carbazole (1.7g, 5.2mmol), tris (dibenzylideneacetone) (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol) and 120mL of toluene were reacted under reflux for 12 hours. After completion of the reaction, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 3: 1 (V/V)). The solvent was evaporated and dried to give 2.2g of an orange-red solid with a yield of 66%. Ms (ei): m/z: 661.53[ M ]⁺]。Anal.calcd for C₄₃H₂₅N₅(％)：C 85.30，H 4.11，N 10.58；found：C 85.20，H 4.10，N10.52。

Example 2: synthesis of Compounds 1-34

(Synthesis of intermediate M3)

The synthetic route for intermediate M3 is shown below:

5-bromo-2-chloropyrimidine (1.1g, 5.7mmol), M1(1.8g, 5.0mmol) and 50mL of toluene were successively added to a 100mL single-neck flask under an argon atmosphere, and then a 0.5M toluene solution of potassium bis (trimethylsilyl) amide (6.0mmol) was dropwise added to the reaction system. After 12 hours at 50 ℃, the reaction was quenched by addition of saturated ammonium chloride solution. The organic layer was extracted with ethyl acetate and Na₂SO₄Drying, filtering and collecting solid, and washing with a small amount of absolute ethyl alcohol. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). The solvent was distilled off, and after drying, 1.4g of a yellow solid was obtained in a yield of 63%. Ms (ei): m/z: 443.08[ M +]。Anal.calcd for C₂₃H₁₁BrClN₃(％)：C 62.12，H 2.49，N 9.45；found：C 62.01，H 2.45，N 9.40。

(Synthesis of Compounds 1 to 34)

The synthetic routes for compounds 1-34 are shown below:

under nitrogen protection, intermediate M3(2.2g, 5mmol), carbazole (1.7g, 10.4mmol), tris (dibenzylideneacetone) (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol) and 120mL of toluene were added in sequence to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the reaction, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, the organic layers were combined, and after the solvent was distilled off, the residue wasSeparation by column chromatography (petroleum ether: dichloromethane ═ 3: 1 (V/V)). The solvent was evaporated and dried to give 2.2g of an orange-red solid with a yield of 66%. Ms (ei): m/z: 661.53[ M +]。Anal.calcd forC₄₇H₂₇N₅(％)：C 85.30，H 4.11，N 10.58；found：C 85.20，H 4.10，N 10.52。

Example 3: synthesis of Compounds 1-6

(Synthesis of intermediate M4)

The synthetic route for intermediate M4 is shown below:

in a 250mL single-neck flask, benzoyl hydrazine (2.7g, 20mmol), 5, 6-dibromoacenaphthenequinone (6.8g, 20mmol), sodium acetate (27g, 200mmol) and 150mL of acetic acid were added in this order, and the reaction was stirred under reflux for 12 hours. After the reaction, the solid was collected by suction filtration and washed with a small amount of anhydrous ethanol. After drying, 5.2g of an orange solid are obtained, yield 59%. Ms (ei): m/z: 439.02[ M ]⁺]。Anal.calcd for C₁₉H₉Br₂N₃(％)：C 51.97，H 2.07，N 9.57；found：C 51.95，H 2.10，N9.54。

(Synthesis of intermediate M5)

The synthetic route for intermediate M5 is shown below:

5-bromopyrimidine (0.9g, 5.7mmol), M4(2.2g, 5.0mmol) and 50mL of toluene were sequentially added to a 100mL single-neck flask under an argon atmosphere, and then a 0.5M toluene solution of potassium bis (trimethylsilyl) amide (6.0mmol) was added dropwise to the reaction system. After 12 hours at 50 ℃, the reaction was quenched by addition of saturated ammonium chloride solution. The organic layer was extracted with ethyl acetate and Na₂SO₄Drying, filtering and collecting solid, and washing with a small amount of absolute ethyl alcohol. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). The solvent was distilled off, and after drying, 1.3g of a yellow solid was obtained,the yield was 63%. Ms (ei): m/z: 409.08[ M +]。Anal.calcd for C₂₃H₁₂BrN₃(％)：C 67.33，H 2.95，N 10.24；found：C67.21，H 2.85，N 10.20。

(Synthesis of Compounds 1 to 6)

The synthetic routes for compounds 1-6 are shown below:

under the protection of nitrogen, an intermediate M5(2.0g, 5mmol) and 5-phenyl-5, 7-indolino [2,3-b ] are sequentially added into a 250mL Schlenk bottle]Carbazole (1.7g, 5.2mmol), tris (dibenzylideneacetone) (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol) and 120mL of toluene were reacted under reflux for 12 hours. After completion of the reaction, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 3: 1 (V/V)). The solvent was evaporated and dried to give 2.2g of an orange-red solid with a yield of 66%. Ms (ei): m/z: 661.53[ M ]⁺]。Anal.calcd for C₄₃H₂₅N₅(％)：C 85.30，H 4.11，N 10.58；found：C 85.20，H 4.10，N10.52。

Example 4: preparation of organic electroluminescent device containing the polycyclic aromatic Hydroazanaphthalene derivative of example 1

Referring to fig. 3, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are sequentially formed on a transparent anode formed on a glass substrate in advance.

Specifically, a glass substrate on which an ITO film having a film thickness of 100nm was formed was subjected to ultrasonic treatment in a Decon90 alkaline cleaning solution, rinsed in deionized water, washed three times in acetone and ethanol, baked in a clean environment to completely remove moisture, cleaned with ultraviolet light and ozone, and bombarded on the surface with a low-energy cation beam. The ITO electrodes are formedPlacing the glass substrate into a vacuum chamber, and vacuumizing to 4 × 10^-4-2×10^-5Pa. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN) was deposited on the ITO electrode-equipped glass substrate at a deposition rate of 0.2 nm/sec to form a layer having a film thickness of 10nm as a hole injection layer. N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vapor-deposited on the hole injection layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 40nm as a hole transport layer. 4,4' -tris (N-carbazolyl) triphenylamine (TCTA) was vapor-deposited on the hole transport layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 5nm as an Electron Blocking Layer (EBL). On the electron blocking layer, double-source co-evaporation was performed at a deposition rate of 0.2nm/s for the compound of example 1 (compound 1-10) as a host material and a deposition rate of 0.016nm/s for RD1 as a dopant material to form a layer with a thickness of 20nm as a light-emitting layer, and the doping weight ratio of RD1 was 2 wt%. On the light-emitting layer, aluminum (III) bis (2-methyl-8-quinolinolato) -4-phenylphenolate (BALq) was vapor-deposited at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 10nm as a Hole Blocking Layer (HBL). On the hole-blocking layer, BALq was deposited at a deposition rate of 0.2nm/s to form a layer having a thickness of 40nm as an electron-transporting layer (ETL). On the electron transport layer, 8-hydroxyquinoline-lithium (Liq) was vapor-deposited at a vapor deposition rate of 0.1nm/s to form a layer having a film thickness of 2nm as an electron injection layer. Finally, aluminum is vapor-deposited at a vapor deposition rate of 0.5nm/s or more to form a cathode having a film thickness of 100 nm.

Examples 5 to 6: preparation of organic electroluminescent device containing the polycyclic aromatic Hydroazanaphthalene derivatives of examples 2 to 3

The organic electroluminescent device was prepared under the same conditions except that the compounds in table 1 below were used instead of the compounds in each layer of example 4, respectively.

Comparative examples 1 to 2: preparation of organic electroluminescent device comparative examples 1 to 2

The examples and comparative examples relate to the following structures of compounds:

table 1 shows the structures and film thicknesses of the respective layers of the organic electroluminescent devices prepared in examples 4 to 6 and comparative examples 1 to 2 as follows:

the current-luminance-voltage characteristics of the device were obtained from a Keithley source measuring system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes, the electroluminescence spectra were measured by a Photo research PR655 spectrometer, and the external quantum efficiencies of the devices were calculated by the method of the document adv. mater,2003,15, 1043-.

The lifetime of the device was measured as: the emission luminance (initial luminance) at the start of light emission was set to 10000cd/m²Constant current driving is performed until the light emission luminance decays to 9500cd/m²(corresponding to 95%, where the initial brightness is taken as 100%: 95% decay). Device lifetime with RD1 as dopant is 10000cd/m²For initial luminance, attenuation to 9500cd/m²(corresponding to 95%, where the initial brightness is taken as 100%: 95% decay). All devices were encapsulated in a nitrogen atmosphere.

Table 2 shows the results of comparing examples 4 to 6 of the present invention with comparative examples 1 to 2 when a DC voltage is applied to the atmosphere at normal temperature as follows:

as can be seen from table 2, the polycyclic aromatic hydrocarbon and azanaphthalene derivatives of the present invention obtained excellent performance data.

Comparative example 2 and example 5 employed RD1 as a dopant, and the host material constituent materials of example 5 were compounds 1-34 of the present invention. As can be seen from the comparison of the device performance data, example 5 has a lower operating voltage, the external quantum efficiency is relatively improved by nearly 20%, and the device lifetime (95%) is obviously longer.

Compared with the materials commonly used in the prior art, the polycyclic aromatic hydrocarbon aza-naphthalene derivative can effectively reduce the working voltage, improve the external quantum efficiency and prolong the service life of devices.

Industrial applicability

The polycyclic aromatic hydrocarbon aza-naphthalene derivative has excellent luminous efficiency, life property and low driving voltage. Therefore, an organic electroluminescent device having an excellent lifetime can be prepared from the compound.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the intention of all modifications, equivalents, improvements, and equivalents falling within the spirit and scope of the invention.

Claims

1. A polycyclic aromatic hydrocarbon azanaphthalene derivative represented by the following general formula (1):

wherein Z represents CR¹Or N;

wherein the dotted line represents a bond;

A₁～A₄each independently represents Ar₁、Ar₂、Ar₃、Ar₄、

One or more of;

z in the structural formulae (A) to (D) has the meaning as defined in the general formula (1).

2. The polycyclic aromatic azanaphthalene derivative according to claim 1, further represented by the following general formula (I) or (II):

said L₁～L₄And Ar₁～Ar₈Have the meaning as defined in claim 1.

3. Polycyclic aromatic hydrocarbon and aza-naphthalene derivative according to claim 1, wherein Ar is Ar₁～Ar₈Each independently selected from the following groups:

wherein the dotted line represents and L₁、L₂、L₃、L₄Or a N-bonded bond, R¹Has the meaning as defined for the general formula (1).

4. A polycyclic aromatic hydrocarbon azanaphthalene derivative according to any one of claims 1 to 3, wherein R is¹And R²Each independently represents one or more of phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron group, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, or tetraphenyl silicon group.

5. A polycyclic aromatic hydrocarbon and azanaphthalene derivative according to any one of claims 1 to 4, wherein the polycyclic aromatic hydrocarbon and azanaphthalene derivative represented by the general formula (1) is selected from the group consisting of:

。

6. the synthetic method of the polycyclic aromatic hydrocarbon aza-naphthalene derivative comprises the following synthetic route:

。

7. use of a polycyclic aromatic hydrocarbon and azanaphthalene derivative according to any one of claims 1 to 5 in an electronic device.

8. The electronic device according to claim 7, wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;

9. The electronic device of claim 8, wherein the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.