CN116082114A - Fused ring compound and application thereof - Google Patents

Fused ring compound and application thereof Download PDF

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CN116082114A
CN116082114A CN202310059983.5A CN202310059983A CN116082114A CN 116082114 A CN116082114 A CN 116082114A CN 202310059983 A CN202310059983 A CN 202310059983A CN 116082114 A CN116082114 A CN 116082114A
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substituted
unsubstituted
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aryl
alkyl
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曹建华
徐先锋
王志杰
张九敏
何连贞
唐怡杰
邸庆童
张昊
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Beijing Bayi Space LCD Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
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    • C07—ORGANIC CHEMISTRY
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Abstract

The present invention relates to a condensed-cyclic compound and application thereof, and an organic electroluminescent device having improved driving voltage and/or current efficiency characteristics can be provided by including the condensed-cyclic compound according to the present disclosure.

Description

Fused ring compound and application thereof
Technical Field
The invention belongs to the technical field of organic electroluminescence, and particularly relates to a condensed ring compound and application thereof in organic electroluminescent materials and luminescent elements.
Background
Most of the materials used in the organic electroluminescent element are pure organic materials or organometallic complexes of organic materials and metals, and they are classified into hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, and the like, depending on the application. Here, an organic substance having a relatively small ionization energy is mainly used as the hole injection substance or the hole transport substance, and an organic substance having a relatively large electronegativity is mainly used as the electron injection substance or the electron transport substance. Further, the substance used as the light-emitting auxiliary layer preferably satisfies the following characteristics:
first, the materials used in the organic electroluminescent element need to have good thermal stability because joule heat is generated by charge transfer inside the organic electroluminescent element, and conventionally, the glass transition temperature of the materials generally used as hole transport layers is low, and thus, a phenomenon occurs in which light emission efficiency is lowered due to crystallization occurring at the time of driving at low temperature. Second, in order to reduce the driving voltage, it is necessary that the organic material adjacent to the cathode and anode is designed to have a small charge injection barrier and a high charge mobility. Third, there is always an energy barrier at the interface of the electrode and the organic layer, and at the interface of the organic layer and the organic layer, and some charges are inevitably accumulated, so that it is necessary to use a substance excellent in electrochemical stability.
The light-emitting layer is composed of two substances, i.e., a host light-emitting body and a dopant, and the dopant needs to have high quantum efficiency, and the host light-emitting body needs to have a larger energy gap than the dopant, so that energy transfer to the dopant is likely to occur. Displays for televisions, mobile devices, etc. realize full colors according to three primary colors of red, green, blue, and the light emitting layer is composed of a red main light emitter/dopant, a green main light emitter/dopant, and a blue main light emitter/dopant, respectively. At present, the blue light material still has the problems of low luminous quantum efficiency and poor color purity. The main reason for this situation is that blue light comes from the transition between energy levels with wider energy gaps, while organic compounds with wide forbidden bands have certain difficulties in molecular design, and secondly, blue light materials have stronger pi-pi bond interaction and have strong charge transfer characteristics in the system, so that more non-radiative relaxation channels exist in the wide energy gaps, fluorescence quenching among molecules is aggravated, and quantum yield of the blue light system is reduced.
The present invention has been made in view of the above-mentioned circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a condensed-cyclic compound, an organic electroluminescent material, a light-emitting element and a consumer product, wherein the condensed-cyclic compound is blue to deep blue and has high light-emitting efficiency.
The first object of the present invention is to provide a fused ring compound.
The second object of the present invention is to provide an organic electroluminescent material.
A third object of the present invention is to provide an organic electroluminescent element.
A fourth object of the present invention is to provide a consumer product.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a condensed-cyclic compound has a structural general formula shown in a formula (I):
Figure BDA0004061082960000011
wherein L is 1 、L 2 Each independently selected from single bond, substituted or unsubstituted C 6 -C 60 Arylene, substituted or unsubstituted C 2 -C 60 One of heteroarylene groups;
m and n are each independently selected from integers of 0 to 5;
Ar 1 selected from substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstitutedC 6 -C 60 Arylamine group, substituted or unsubstituted C 10 -C 60 Condensed aryl, substituted or unsubstituted C 2 -C 60 Heteroaryl;
R 1 、R 2 、R 3 、R 4 each at each occurrence is identically or differently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 2 -C 60 Heteroaryl; any adjacent two or more groups may be optionally cyclic or fused to each other to form a substituted or unsubstituted ring;
R 1 、R 2 、R 3 、R 4 respectively representing one or more to saturated substitutions.
The alkyl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. As non-limiting examples thereof, there are methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, and the like;
aryl groups in the sense of the present invention contain 6 to 60 carbon atoms, heteroaryl groups contain 2 to 60 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. In this case, two or more rings of the heteroaryl group may be attached to each other simply or in a condensed form, or may further include a condensed form with the aryl group. As non-limiting examples of aryl and heteroaryl groups, in particular groups selected from the following: phenyl, naphthyl, anthryl, benzanthraceyl, phenanthryl, pyrenyl,
Figure BDA0004061082960000021
Group, perylene group, fluoranthryl group, naphthacene group, pentacene group, benzopyrene group, biphenyl group, terphenyl group, tripolyphenyl group, tetrabiphenyl group, fluorenyl group, spirobifluorenyl group, dihydrophenanthryl group, triphenylene group, dihydropyrenyl group, tetrahydropyrenyl group, cis-or trans-indenofluorenyl group, cis-or trans-indenocarbazolyl group, indolocarbazolyl group, benzofuran group Carbazolyl, benzothiophenocarzolyl, benzocarbazolyl, dibenzocarbazolyl, azadibenzo [ g, id ]]Naphtho [2,1,8-cde]Azulene, triindenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo [5,6 ]]Quinolinyl, benzo [6,7]Quinolinyl, benzo [7,8]Quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthamidinyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthazolyl, anthracoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthracenyl, 2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl, 1, 8-diazapyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl phenazinyl, phenoxazinyl, phenothiazinyl, fluororubenyl, naphthyridinyl, azacarbazolyl, benzocarboline, carboline, phenanthroline, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazole, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 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, naphthyridinyl, quinazolinyl, and benzothiadiazolyl or combinations thereof.
"halogen" or "halogen atom" as used herein means a member selected from fluorine, chlorine, bromine or iodine.
Further, the Ar 1 Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, andsubstituted or unsubstituted tetralyphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted benzanthracenyl, substituted or unsubstituted pyrenyl
Figure BDA0004061082960000022
A group consisting of a group, a substituted or unsubstituted perylene group, a substituted or unsubstituted fluoranthene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophene group.
The substituents of the substituted alkyl, substituted aryl, substituted heteroaryl, substituted arylamine, substituted condensed aryl, substituted arylene, substituted heteroarylene described herein are each independently selected from at least one of the group consisting of: deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, C 1 -C 40 Alkyl, C 1 -C 40 Haloalkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 1 -C 40 Alkylthio, C 3 -C 40 Cycloalkyl, C 3 -C 40 Cycloalkenyl, 3-to 7-membered heterocycloalkyl, C 6 -C 60 Aryloxy, C 6 -C 60 Arylthio, unsubstituted or substituted by one or more C 6 -C 60 Aryl-substituted 3-to 30-membered heteroaryl, unsubstituted or deuterated, one or more C 1 -C 40 C substituted with at least one of an alkyl group and one or more 3-to 30-membered heteroaryl groups 6 -C 60 Aryl, tris (C) 1 -C 40 ) Alkylsilyl, tri (C) 6 -C 60 ) Aryl silicon based, di (C) 1 -C 40 ) Alkyl (C) 6 -C 60 ) Aryl silicon base, C 1 -C 40 Alkyldi (C) 6 -C 60 ) Aryl silicon base, C 1 -C 40 Alkylcarbonyl group,C 1 -C 40 Alkoxycarbonyl group, C 6 -C 60 Arylcarbonyl, di (C) 6 -C 60 ) Arylborocarbonyl groups of di (C) 1 -C 40 ) Alkyl boron carbonyl, C 1 -C 40 Alkyl (C) 6 -C 60 ) Arylborocarbonyl, C 6 -C 60 Aryl (C) 1 -C 40 ) Alkyl, C 1 -C 40 Of alkyl (C) 6 -C 60 ) Aryl groups.
Heteroalkyl in the sense of the present invention means a hydrogen atom or-CH on an alkyl radical 2 Substituted with at least one heteroatom selected from halogen, nitrile, N, O, S or silicon, as non-limiting examples, difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl, nitrile, acetonitrile, methoxymethyl, methoxyethyl, trimethylsilyl, triisopropylsilyl and the like. Haloalkyl refers to the partial substitution or total substitution of a hydrogen atom on an alkyl group with a halogen, and as non-limiting examples there are fluorotoluene, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, trifluoroethyl, pentafluoroethyl and the like.
Alkenyl or alkynyl groups useful in the present invention contain at least two carbon atoms, and are preferably considered to mean, by way of non-limiting example, the following groups: cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, or octynyl.
Alkoxy, alkylthio, preferably alkoxy or alkylthio having 1 to 40 carbon atoms, as used in the present invention is understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octoxy, cyclooctoxy, 2-ethylhexyloxy, pentafluoroethoxy and 2, 2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2-trifluoroethylthio, ethyleneoxy, ethylenethio, propyleneoxy, propylenethio, butyleneoxy, pentyleneoxy, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexene oxy, cyclohexene thio, ethynyloxy, ethynylthio, propynyloxy, propynylthio, butynyloxy, butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio.
In general, cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, wherein one or more-CH 2 The radical may be replaced by N, O or S to form heterocycloalkyl, heterocycloalkenyl, e.g. one of the cyclopentyl groups-CH 2 -the radical is replaced by O to form one of the groups-CH in the tetrahydrofuranyl, cyclohexyl 2 -the group is replaced by O to form tetrahydropyranyl, etc.; in addition, one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups.
Aryloxy as used herein refers to R' O - The monovalent functional group represented by R' is an aryl group having 6 to 60 carbon atoms. As non-limiting examples of such aryloxy groups, there are phenoxy, naphthoxy, biphenyloxy, and the like.
Arylthio as used herein means R "S - The monovalent functional group represented by R' is an aryl group having 6 to 60 carbon atoms. As non-limiting examples of such arylthio groups, phenylthio, naphthylthio, biphenylthio and the like are mentioned.
The alkylsilyl group used in the present invention means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and the number of carbon atoms constituting the alkylsilyl group is at least 3, and as non-limiting examples of the alkylsilyl group, there are trimethylsilyl group, triethylsilyl group and the like. Aryl silicon group refers to alkyl silicon group substituted with at least one aryl group having 6 to 60 carbon atoms, and examples of the alkyl silicon group include phenyl dimethyl silicon group, naphthyl dimethyl silicon group, phenyl diethyl silicon group, diphenyl methyl silicon group, diphenyl ethyl silicon group, triphenyl silicon group, and the like.
"alkylcarbonyl", "alkoxycarbonyl", "arylcarbonyl", "arylborocarbonyl", "alkylborocarbonyl" in the sense of the present invention means a substituted carbonyl (-COR) wherein R is preferably selected from the group consisting of alkyl, alkoxy, cycloalkyl, aryl, heteroaryl, arylboronyl, alkylboronyl.
The arylphosphorus group used in the present invention means a diarylphosphorus group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylphosphorus group, there are diphenylphosphorus group, bis (4-trimethylsilylbenzene) phosphorus group and the like. The phosphorus atom of the aryl phosphorus oxide group is the diaryl phosphorus group is oxidized to the highest valence state.
The arylboron group used in the present invention means a diarylboroyl group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylboron group, there are diphenyl boron group, bis (2, 4, 6-trimethylbenzene) boron group and the like. The alkylboryl group means a dialkylboryl group substituted with an alkyl group having 1 to 40 carbon atoms, and as non-limiting examples of the alkylboryl group, there are di-t-butylboryl group, diisobutylboryl group and the like.
The arylalkyl group according to the present invention means an alkyl group in which at least one hydrogen atom of a straight or branched saturated hydrocarbon having from 1 to 40 carbon atoms is substituted with an aryl group having from 6 to 60 carbon atoms, and as a non-limiting example, phenylmethyl group, diphenylmethyl group, triphenylmethyl group, 2-phenylethyl group, 3-phenylpropyl group and the like can be mentioned.
Alkylaryl according to the present invention refers to an aryl group in which at least one hydrogen atom of the aryl group having from 6 to 60 carbon atoms is substituted with a straight or branched saturated hydrocarbon having from 1 to 40 carbon atoms, and as a non-limiting example, methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl, isopropylphenyl and the like can be mentioned.
Arylene in the present invention means a divalent functional group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 60 carbon atoms. As non-limiting examples thereof, there are phenylene, naphthylene, phenanthrylene, anthrylene, fluorenylene, spirobifluorenylene and the like.
The heteroarylene or heteroarylene in the present invention means a divalent functional group obtained by removing two hydrogen atoms from a heteroarene having 2 to 60 carbon atoms. As non-limiting examples thereof, there are a pyridyl group, a quinolyl group, an isoquinolyl group, a carbolinyl group, a pyrimidyl group, a triazinyl group and the like.
Arylene and heteroarylene as divalent functional groups and Ar according to the foregoing 1 And anthracene linkage, preferably, the L 1 、L 2 Each independently selected from a single bond or from the group consisting of groups III-1 to III-25:
Figure BDA0004061082960000031
Figure BDA0004061082960000041
wherein X is selected from O, S, se, CR ' R ', siR ' R ' or NAr ';
Z 11 、Z 12 、Z 13 、Z 14 Each independently selected from the group consisting of hydrogen, deuterium, halogen atoms, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 60 Alkyl, C of (2) 2 -C 60 Alkenyl, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Is C 3 -C 60 Cyclic olefin group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
y1 represents an integer of 1 to 4; y2 represents an integer of 1 to 6; y3 represents an integer of 1 to 3; y4 represents an integer of 1 to 5; y5 represents an integer of 1 or 2;
r ', R' are each independently selected from C 1 -C 60 Alkyl, C of (2) 1 -C 60 Is optionally substituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl, R' and R "may optionally be joined or fused to form one or more additional substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R "is methyl, phenyl or fluorenyl;
ar' is selected from C 1 -C 60 Alkyl, C of (2) 1 -C 60 Heteroalkyl of (C) 3 -C 60 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups; preferably, ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
wherein the dotted line represents the attachment site of the group.
Preferably, X is selected from O or S.
Preferably, the L 1 、L 2 Each independently selected from a single bond or a group consisting of groups III-1 to III-15, III-25:
Figure BDA0004061082960000042
Figure BDA0004061082960000051
preferably, said Z 11 、Z 12 、Z 13 、Z 14 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile groups. Further, the fused ring compound is selected from one or more of the following CJHB 950-CJHB 1090 structures:
Figure BDA0004061082960000052
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Figure BDA0004061082960000061
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Figure BDA0004061082960000071
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Figure BDA0004061082960000081
/>
Figure BDA0004061082960000091
/>
Figure BDA0004061082960000101
Figure BDA0004061082960000111
wherein, (D) n Represents hydrogen, partial or complete substitution by deuterium in the molecular structure, and n represents an integer of 0 or more.
As used herein, "combination thereof" or "group" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can contemplate from the applicable list. For example, the alkyl and deuterium atoms can combine to form a partially or fully deuterated alkyl group; halogen and alkyl groups may combine to form haloalkyl substituents such as trifluoromethyl and the like; and halogen, alkyl and aryl may combine to form a haloaralkyl.
An organic electroluminescent material comprising the fused ring compound.
The organic electroluminescent material may be constituted by using the condensed-cyclic compound of the present invention alone, or may contain other compounds at the same time.
The condensed-cyclic compound of the present invention contained in the organic electroluminescent material of the present invention can be used as, but is not limited to, a light-emitting layer material, a carrier transporting layer material, or a capping layer material.
An organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the condensed ring compound provided by the invention.
The organic electroluminescent device comprises a cathode, an anode and at least one light emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two light-emitting layers. It should be noted, however, that not every one of these layers need be present. The organic electroluminescent device described herein may comprise one light emitting layer, or it may comprise a plurality of light emitting layers. I.e. a plurality of luminescent compounds capable of emitting light are used in the luminescent layer. A system with three light emitting layers is preferred, wherein the three layers can display blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises the fused ring compound of the present invention according to the present invention.
Further, the organic electroluminescent device according to the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light emitting layer is directly adjacent to the hole injection layer or anode and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.
In the other layers of the organic electroluminescent device according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in the manner generally used according to the prior art. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination with the luminescent layer according to the invention without inventive effort.
Furthermore, organic electroluminescent devices are preferred, which apply one or more layers by means of sublimation methods, wherein the sublimation is performed in a vacuum at less than 10 -5 Pa, preferably below 10 -6 The material is applied by vapor deposition at an initial pressure of Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa。
Preference is likewise given to organic electroluminescent devices which apply one or more layers by means of an organic vapor deposition process or by means of carrier gas sublimation, where at 10 -5 The material is applied at a pressure between Pa and 1 Pa. A particular example of this method is the organic vapor jet printing method, wherein the material is applied directly through a nozzle and is thus structured.
Furthermore, organic electroluminescent devices are preferred in which one or more layers are produced from a solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexography, lithography, photoinitiated thermal imaging, thermal transfer, inkjet printing or nozzle printing. Soluble compounds the soluble compounds are obtained, for example, by suitable substitution of the fused ring compounds of formula I. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more further layers are applied by vapor deposition.
These methods are generally known to those of ordinary skill in the art and they can be applied to the organic electroluminescent element comprising the condensed-cyclic compound according to the present invention without the inventive effort.
The invention therefore also relates to a method for manufacturing an organic electroluminescent device according to the invention, which applies at least one layer by means of a sublimation method and/or at least one layer by means of an organic vapour deposition method or by means of carrier gas sublimation and/or at least one layer from a solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to a pharmaceutical composition comprising at least one compound of the invention as indicated above. The same preferences as indicated above in relation to the organic electroluminescent device apply to the compounds of the invention. In particular, the compounds may furthermore preferably comprise further compounds. Treatment of the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires preparations of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchyl, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylbenzene, 3, 5-dimethylbenzene, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol, triethylene glycol, 1, 2-dimethyl benzene ether, 1-dimethyl-n-butyl ether, 1-dimethyl-butyl benzene, 1-dimethyl-n-butyl benzene, 1-dimethyl-butyl benzene, n-butyl benzene, dimethyl benzene, n-butyl benzene, dimethyl benzene, or a mixture of these solvents.
Further, the organic layer is selected from one or more of an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer and a light emitting layer.
Further, the electron transporting layer and the light emitting layer comprise the condensed cyclic compound of the present invention.
Still further, the light-emitting layer comprises the condensed cyclic compound of the present invention.
Further, the light-emitting layer comprises a dopant and a light-emitting host, wherein the dopant comprises a material selected from the group consisting of anthracene, naphthalene, anthracene, pyrene, perylene, phenanthrene, fluoranthene, and combinations thereof,
Figure BDA0004061082960000121
In addition, various metal complexes, bisstyrylbenzene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, heterocyclic compounds having an indole ring as a partial structure of a condensed ring, heterocyclic compounds having a carbazole ring as a partial structure of a condensed ring, carbazole derivatives, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, and the like can be used. In addition, as a dopant material, other than this, it is also possible to use: pyrene derivatives having a pyrene skeleton in the molecule, heterocyclic compounds having an indole ring as a partial structure of a condensed ring, heterocyclic compounds having a carbazole ring as a partial structure of a condensed ring, carbazole derivatives, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, quinacridones, coumarins, rubrene, perylenes and derivatives thereof, benzopyran derivatives, indenofenanthrene derivatives, rhodamine derivatives, aminostyryl derivatives and the like. These may be used alone, as a single layer formed by mixing with other materials, or as a laminated structure of layers formed alone, between layers formed by mixing, or between layers formed alone and layers formed by mixing.
In addition, phosphorescent emitters may also be used as dopants. As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. Ir (ppy) may be used 3 Blue phosphorescent emitters such as green phosphorescent emitters, firpic, fir6 and Btp 2 Red phosphorescent emitters such as Ir (acac) and the like are preferably used as the host material in this case. In addition, as a host for hole injection and transport propertiesExamples of the material include carbazole derivatives such as 4,4' -bis (N-Carbazolyl) Biphenyl (CBP), TCTA, and mCP. As the electron-transporting host material, p-bis (triphenylsilyl) benzene (UGH 2), 2',2"- (1, 3, 5-phenylene) -tris (1-phenyl-1H-benzimidazole) (TPBI), or the like can be used, and a high-performance light-emitting element can be manufactured.
In order to avoid concentration quenching, the phosphorescent light-emitting material is doped into the host material, preferably by co-evaporation in a range of 1 to 10 wt% relative to the entire light-emitting layer.
As the light-emitting dopant, a material that emits delayed fluorescence, such as CDCB derivatives, e.g., PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, may be used.
Further, the light-emitting host comprises the fused ring compound of the present invention.
Further, the mass ratio of the dopant to the light-emitting main body is 1:99-50:50.
A consumer product made from the organic electroluminescent device, the consumer product comprising the organic electroluminescent device provided by the invention.
The consumer product described in the present invention may be one of the following products: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cellular telephones, tablet computers, tablet handsets, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays with a diagonal of less than 2 inches, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising a plurality of displays tiled together, theatre or gym screens, phototherapy devices, and billboards.
Compared with the prior art, the invention has the beneficial effects that:
the fused ring compound has a novel rigid structure of large-plane conjugated dibenzo [4,5,6,7] cyclohepta [1,2,3-d ] anthracene and anthracene, and has large mobility of carriers (1) in the case of the compound shown in the general formula (I); (2) high internal quantum efficiency; (3) stable film state; (4) The organic electroluminescent element is excellent in heat resistance and therefore suitable as a constituent material of a light-emitting layer of the organic electroluminescent element.
In the organic electroluminescent element using the condensed-cyclic compound represented by the general formula (I) of the present invention as a host material for a light-emitting layer, the compound of the present invention has a higher carrier mobility, a higher internal quantum efficiency, an excellent amorphous property, and a stable thin film state than conventional materials, and therefore, the organic electroluminescent element can realize a high efficiency, a low driving voltage, and a long lifetime.
Further, in the present invention, the light-emitting layer is formed by the condensed-cyclic compound of the general formula (I), so that the high quantum efficiency performance and heat resistance of the compound can be utilized to the maximum extent, and a long-life organic electroluminescent element can be realized with higher efficiency.
In the present invention, at least one of the light-emitting layers and the laminated film having two or more light-emitting layers is formed of the condensed-cyclic compound represented by the general formula (I) as a constituent material, and the organic electroluminescent element has high carrier mobility, high internal quantum efficiency, excellent amorphous property, and thin film state stability characteristics based on the compound, so that it is possible to realize an organic electroluminescent element having high efficiency, low driving voltage, and long lifetime.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 shows a schematic diagram of an organic light emitting device 100. The illustrations are not necessarily drawn to scale. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 may be fabricated by sequentially depositing the layers described.
Fig. 2 shows a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first emissive layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second emissive layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 may be prepared by sequentially depositing the layers described. Because the most common OLED device has one light emitting layer, and device 200 has a first light emitting layer and a second light emitting layer, the light emitting peaks of the first and second light emitting layers may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of device 200, materials similar to those described with respect to device 100 may be used. Fig. 2 provides one example of how some layers may be added from the structure of the device 100.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
In the invention, the preparation methods are all conventional methods unless otherwise specified. All materials used, unless otherwise indicated, are commercially available from the disclosure and percentages such as percentages by mass unless otherwise indicated. The novel series of organic compounds provided by the present invention, all of which are carried out under well known suitable conditions, involve some simple organic preparation, for example the preparation of phenylboronic acid derivatives, can be synthesised by skilled operating skills and are not described in detail in the present invention.
Any range recited in the invention includes any numerical value between the endpoints and any sub-range of any numerical value between the endpoints or any numerical value between the endpoints.
The following examples are examples of the test apparatus and method for testing the performance of OLED materials and devices as follows:
OLED element performance detection conditions:
luminance and chromaticity coordinates: photoresearch PR-715 was tested using a spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: using the NEWPORT 1931-C test;
life test: LTS-1004AC life test apparatus was used.
Example 1
The preparation method of the compound CJHB950 comprises the following steps:
the first step: preparation of Compound CJHB950
Figure BDA0004061082960000131
20.0mmol of 8-bromo-dibenzo [4,5,6,7 ] under nitrogen]Cyclohepta [1,2,3-d ]]Anthracene (CAS: 2758116-54-8, reactant 1), 22.0mmol of pinacol ester of (3- (10- (1-naphthyl) anthracene-9-yl) phenyl) borate (CAS: 1227290-28-9, reactant 2) were mixed with 60mL of toluene, 40.0mmol of anhydrous sodium carbonate and 1.0mg of Pd132 catalyst were added, 40mL of ethanol and 40mL of water were further added, the mixture was heated to reflux and stirred for reaction for 10 hours, cooled to room temperature, 50mL of water was added, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was concentrated under reduced pressure, and recrystallized from toluene/THF to give the compound CJHB950', a yellow solid, yield: 77, MS (TOF): m/z 707.27[ M+H ] ] + 。
And a second step of: preparation of Compound CJHB950
Figure BDA0004061082960000141
20.0mmol firstThe compound CJHB950' prepared in the step is dissolved in 300mL of benzene-D6, 40.0mmol of trifluoromethanesulfonic acid is added dropwise under the protection of nitrogen, and the mixture is stirred at room temperature for reaction for 5 hours, and 20mL of D is added dropwise 2 O quench reaction, add 48.0mmol potassium phosphate deionized water solution, separate out the camera, extract water with dichloromethane, collect organic phase and dry and filter, concentrate filtrate under reduced pressure, separate and purify with silica gel column to obtain compound CJHB950 (sum of all n is 30-34), yellow solid, yield: 98%, MS (TOF): m/z741.27[ M+H ]] + 。
Example 2
The preparation of compound CJHB968, comprising the steps of:
the first step: preparation of Compound Int-1
Figure BDA0004061082960000142
15.0mmol of 9-bromoanthracene-d 9 are mixed with 60mL of toluene under the protection of nitrogen, 18.0mmol of phenylboronic acid, 54.0mmol of anhydrous sodium carbonate and 173.0mg of Pd (PPh) 3 ) 4 Adding 30mL of ethanol and 30mL of water into the catalyst, heating to reflux, stirring for reaction for 12 hours, cooling to room temperature, adding 50mL of water, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure, and separating and purifying with a silica gel column to obtain a compound Int-1 as a white solid, wherein the yield is as follows: 78%.
And a second step of: preparation of Compound Int-2
Figure BDA0004061082960000143
Under the protection of nitrogen, 20.0mmol of Int-1 is dissolved in 80mL of dichloromethane, the temperature is reduced to 0 ℃, 22.0mmol of N-bromosuccinimide is added in batches, stirring is carried out for 5 hours, 100mL of water is added, an organic phase is separated, drying, filtering and decompression concentration are carried out on filtrate, and the compound Int-5 is obtained through separation and purification by a silica gel column, white solid and yield: 92%.
And a third step of: preparation of Compound Int-3
Figure BDA0004061082960000144
10.0mmol of Int-2 was mixed with 40mL of toluene under nitrogen, and 12.0mmol of m-chlorobenzeneboronic acid, 25.0mmol of anhydrous sodium carbonate and 10.0mg of Pd (PPh) were added 3 ) 4 Adding 20mL of ethanol and 20mL of water into the catalyst, heating to reflux, stirring for reaction for 12 hours, cooling to room temperature, adding 50mL of water, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure, and separating and purifying with a silica gel column to obtain a compound Int-3, a white solid, and obtaining the yield: 76%.
Fourth step: preparation of Compound Int-4
Figure BDA0004061082960000151
Under nitrogen protection, 20.0mmol of Int-3 was dissolved in 50mL of dry DMF and 24.0mmol of pinacol biborate, 30.0mmol of potassium acetate and 0.2mmol of PdCl were added 2 (dppf), heating to 90deg.C, stirring for reaction for 15 hr, cooling to room temperature, adding 150mL ice water, extracting with ethyl acetate, drying the organic phase, filtering, concentrating the filtrate under reduced pressure, and separating and purifying with silica gel column to obtain compound Int-4 as white solid with yield: 87%.
Fifth step: preparation of Compound Int-5
Figure BDA0004061082960000152
Referring to the synthesis of the second step of example 1, compound Int-5 was prepared as a yellow solid in 100% yield by replacing only CJHB950' in the second step of example 1 with SM 0.
Sixth step: preparation of Compound Int-6
Figure BDA0004061082960000153
Mixing 10.0mmol of Int-5 with 40mL of toluene, adding 12.0mmol of 3-hydroxynaphthalene boric acid, 25.0mmol of anhydrous sodium carbonate and 0.01mmol of Pd132 catalyst under the protection of nitrogen, adding 20mL of ethanol and 20mL of water, heating to reflux and stirring for reaction for 12 hours, cooling to room temperature, adding 50mL of water, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure, separating and purifying with a silica gel column to obtain a compound Int-6 as a yellow solid, and obtaining the yield: 74%.
Seventh step: preparation of Compound Int-7
Figure BDA0004061082960000154
Dissolving 10.0mmol of Int-6 in 50mL of dichloromethane, cooling to 0 ℃ under the protection of nitrogen, adding 22.0mmol of pyridine, dropwise adding 12.0mmol of trifluoromethanesulfonic anhydride, heating to room temperature, stirring for reaction for 12 hours, adding 50mL of water, separating out an organic phase, extracting the aqueous phase with dichloromethane, collecting the organic phase, washing the organic phase with water, drying the organic phase, filtering, concentrating the filtrate under reduced pressure, separating and purifying by using a silica gel column to obtain a compound Int-7, and obtaining a yellow solid with the yield: 93%.
Eighth step: preparation of Compound CJHB968
Figure BDA0004061082960000161
10.0mmol of Int-7 is mixed with 40mL of toluene, under the protection of nitrogen, 11.0mmol of Int-4, 25.0mmol of anhydrous potassium carbonate and 0.01mmol of Pd132 catalyst are added, 20mL of ethanol and 20mL of water are added, the mixture is heated to reflux and stirred for reaction for 15 hours, cooled to room temperature, 50mL of water is added, dichloromethane is used for extraction, an organic phase is collected and dried, the filtrate is concentrated to dryness under reduced pressure, and the mixture is separated and purified by a silica gel column to obtain a compound CJHB968 (the sum of all n is 20-23), yellow solid is obtained, the yield is: 75%, MS (TOF): m/z806.44[ M+H ]] + 。
Referring to the above synthetic method, the following compounds were prepared:
Figure BDA0004061082960000162
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Figure BDA0004061082960000171
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Figure BDA0004061082960000181
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Figure BDA0004061082960000191
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Figure BDA0004061082960000201
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Figure BDA0004061082960000211
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Figure BDA0004061082960000221
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Figure BDA0004061082960000231
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Figure BDA0004061082960000241
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Figure BDA0004061082960000251
example 3
An OLED element, as shown in FIG. 1, comprises a substrate 101, an anode layer 102 provided on the substrate 101, a hole injection layer 103 provided on the anode layer 102, a hole transport layer 104 provided on the hole injection layer 103, an electron blocking layer 105 provided on the hole transport layer 104, an organic light emitting layer 106 provided on the electron blocking layer 105, a hole blocking layer 107 provided on the organic light emitting layer 106, an electron transport layer 108 provided on the hole blocking layer 107, an electron injection layer 109 provided on the electron transport layer 108, and a cathode 110 and a capping layer 111 provided on the cathode 110,
The preparation method of the OLED element comprises the following steps:
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, rinsed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dried, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the above ITO glass substrate in vacuum chamber, and vacuumizing to less than 1×10 -5 Pa, evaporating metallic silver as anode on the ITO film, and evaporating film thickness to be
Figure BDA0004061082960000252
Continuing to vapor deposit the compounds DNTPD and F4TCNQ respectively as hole injection layers, wherein F4TCNQ is 3% of DNTPD by mass, and the vapor deposition film thickness is +.>
Figure BDA0004061082960000253
Continuously evaporating NPD as a hole transport layer on the hole injection layer film, wherein the evaporation film thickness is +.>
Figure BDA0004061082960000254
3) Continuously evaporating a layer of compound HT202 as electron blocking layer on the hole transport layer to obtain an evaporating film with a thickness of
Figure BDA0004061082960000255
4) Continuing to vapor deposit a layer of the inventive compound of formula I on the electron blocking layerThe compound and BD035 are used as organic light-emitting layers, wherein BD035 is a doping material and the compound shown in the formula (I) of the invention is used as a main material, the doping concentration of the compound shown in the formula (I) in BD035 is 10%, and the vapor deposition film thickness is
Figure BDA0004061082960000256
5) Continuously evaporating a layer of compound TPBi as a hole blocking layer material on the light-emitting layer, wherein the thickness of the evaporated film is
Figure BDA0004061082960000257
6) Evaporating a layer of compounds LiQ and ET210 on the hole blocking layer to serve as electron transport layers of the device, wherein the mass ratio of the LiQ to the ET210 is 1:1, and the evaporating film thickness is
Figure BDA0004061082960000258
7) Evaporating a layer of compound LiF on the electron transport layer to obtain an electron injection layer with a thickness of
Figure BDA0004061082960000259
8) Evaporating metal magnesium and silver on the electron injection layer to form a cathode layer of the element, wherein the mass ratio of magnesium to silver is 1:10, and the film thickness of the evaporated film is
Figure BDA00040610829600002510
Finally, the compound NPD is deposited on the cathode layer as a capping layer of the element, and the thickness of the deposited film is
Figure BDA00040610829600002511
The structure of the compound used in example 3 above is as follows:
Figure BDA00040610829600002512
example 4
An organic electroluminescent device 200 having a structure as shown in fig. 2, which comprises a substrate 201, an anode layer 202, a hole injection layer 203, a hole transport layer 204, a first light emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode layer 213, was prepared by vacuum evaporation of the respective layers according to the preparation method of example 3.
Comparative example 1
The same procedure as in example 3 was followed except that compound B01 (Σn: 40 to 44) was used instead of the compound represented by the formula (I). The structure of compound B01 is:
Figure BDA0004061082960000261
the driving voltage and current efficiency of the organic electroluminescent elements prepared in example 3 and comparative example 1 and the lifetime of the elements were measured using a digital source meter and a luminance meter at the same luminance. Specifically, the luminance of the organic electroluminescent element was measured to reach 1000cd/m by increasing the voltage at a rate of 0.1V per second 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; LT90% life test is as follows: at 1000cd/m using a luminance meter 2 The luminance decay of the organic electroluminescent element was measured to be 900cd/m while maintaining a constant current at luminance 2 Time in hours. All results are summarized in table 1, and test results were normalized against the data of comparative example 1 (bracketed data) for comparison.
TABLE 1 results of testing the performance of the elements
Figure BDA0004061082960000262
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Figure BDA0004061082960000271
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Figure BDA0004061082960000281
As can be seen from table 1, the compound of the present invention provides a blue organic electroluminescent element as a host material for a light-emitting layer, and the element exhibits excellent performance in terms of reduced driving voltage and improved current efficiency and also exhibits excellent LT90% lifetime.
The compound B01 of comparative example 1 is different from the compound of the present invention in that two anthracene linked via arylene group are weak in conjugation ability, while the compound of the present invention has a large conjugated, non-planar structure of seven-membered ring dibenzoanthracene linked via arylene group and anthracene, and reduces the formation of anthracene derivative molecular excimer, so that it is superior in molecular film formation and charge transfer to the compound B01, more balanced in charge transfer in element, and improved in element performance.
The organic electroluminescent device of the present invention can be applied to flat-panel light emitters such as wall-mounted televisions, flat-panel displays, and lighting, light sources such as copiers, printers, backlights for liquid crystal displays, and measuring instruments, display panels, and marker lamps.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (9)

1. The condensed-cyclic compound is characterized in that the structural general formula of the condensed-cyclic compound is shown as a formula (I):
Figure QLYQS_1
Wherein L is 1 、L 2 Each independently selected from single bond, substituted or unsubstituted C 6 -C 60 Arylene, substituted or unsubstituted C 2 -C 60 One of heteroarylene groups;
m and n are each independently selected from integers of 0 to 5;
Ar 1 selected from substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamine group, substituted or unsubstituted C 10 -C 60 Condensed aryl, substituted or unsubstituted C 2 -C 60 Heteroaryl;
R 1 、R 2 、R 3 、R 4 each at each occurrence is identically or differently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 2 -C 60 Heteroaryl; any adjacent two or more groups may be optionally cyclic or fused to each other to form a substituted or unsubstituted ring;
R 1 、R 2 、R 3 、R 4 respectively representing one or more to saturated substitutions.
2. The fused ring compound according to claim 1, wherein Ar 1 Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetrabiphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted benzanthracenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted
Figure QLYQS_2
A group, a substituted or unsubstituted perylene group, a substituted or unsubstituted fluoranthene group, a substituted or unsubstituted carbazole group substituted or unsubstituted fluorenyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, and the likeSubstituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene.
3. The fused ring compound of claim 1, wherein the substituents of the substituted alkyl, substituted aryl, substituted heteroaryl, substituted arylamine, substituted fused aryl, substituted arylene, substituted heteroarylene are each independently selected from at least one of the group consisting of: deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, C 1 -C 40 Alkyl, C 1 -C 40 Haloalkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 1 -C 40 Alkylthio, C 3 -C 40 Cycloalkyl, C 3 -C 40 Cycloalkenyl, 3-to 7-membered heterocycloalkyl, C 6 -C 60 Aryloxy, C 6 -C 60 Arylthio, unsubstituted or substituted by one or more C 6 -C 60 Aryl-substituted 3-to 30-membered heteroaryl, unsubstituted or deuterated, one or more C 1 -C 40 C substituted with at least one of an alkyl group and one or more 3-to 30-membered heteroaryl groups 6 -C 60 Aryl, tris (C) 1 -C 40 ) Alkylsilyl, tri (C) 6 -C 60 ) Aryl silicon based, di (C) 1 -C 40 ) Alkyl (C) 6 -C 60 ) Aryl silicon base, C 1 -C 40 Alkyldi (C) 6 -C 60 ) Aryl silicon base, C 1 -C 40 Alkylcarbonyl, C 1 -C 40 Alkoxycarbonyl group, C 6 -C 60 Arylcarbonyl, di (C) 6 -C 60 ) Arylborocarbonyl groups of di (C) 1 -C 40 ) Alkyl boron carbonyl, C 1 -C 40 Alkyl (C) 6 -C 60 ) Arylborocarbonyl, C 6 -C 60 Aryl (C) 1 -C 40 ) Alkyl, C 1 -C 40 Of alkyl (C) 6 -C 60 ) Aryl groups.
4. The fused ring compound according to claim 1, wherein L 1 、L 2 Each independently selected from a single bond or from the group consisting of groups III-1 to III-25:
Figure QLYQS_3
Figure QLYQS_4
wherein X is selected from O, S, se, CR ’ R”、SiR ’ R' or NAr ’ ；
Z 11 、Z 12 、Z 13 、Z 14 Each independently selected from the group consisting of hydrogen, deuterium, halogen atoms, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 60 Alkyl, C of (2) 2 -C 60 Alkenyl, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Is C 3 -C 60 Cyclic olefin group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
y1 represents an integer of 1 to 4; y2 represents an integer of 1 to 6; y3 represents an integer of 1 to 3; y4 represents an integer of 1 to 5; y5 represents an integer of 1 or 2;
R ’ R' are each independently selected from C 1 -C 60 Alkyl, C of (2) 1 -C 60 Is optionally substituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl groupGroup R ’ And R "may optionally be joined or fused to form one or more additional substituted or unsubstituted rings with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R ’ R' is methyl, phenyl or fluorenyl;
Ar ’ selected from C 1 -C 60 Alkyl, C of (2) 1 -C 60 Heteroalkyl of (C) 3 -C 60 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups; preferably Ar ’ Methyl, ethyl, phenyl, biphenyl or naphthyl;
wherein the dotted line represents the attachment site of the group.
5. The fused ring compound according to any one of claims 1 to 4, wherein the fused ring compound is selected from one or more of the following CJHB950 to CJHB1090 structures:
Figure QLYQS_5
/>
Figure QLYQS_6
/>
Figure QLYQS_7
/>
Figure QLYQS_8
/>
Figure QLYQS_9
/>
Figure QLYQS_10
wherein, (D) n Represents hydrogen, partial or complete substitution by deuterium in the molecular structure, and n represents an integer of 0 or more.
6. An organic electroluminescent material, characterized in that the organic electroluminescent material comprises the condensed cyclic compound according to any one of claims 1 to 5.
7. An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, the organic layer comprising the fused ring compound of any one of claims 1-5.
8. The organic electroluminescent device according to claim 7, wherein the organic layer 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, an electron injection layer; wherein each organic layer is one, two or more layers; the condensed ring compound is contained in the light-emitting layer.
9. A consumer product comprising the organic electroluminescent device of any one of claims 7-8.
CN202310059983.5A 2023-01-16 2023-01-16 Fused ring compound and application thereof Pending CN116082114A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210082637A (en) * 2019-12-26 2021-07-06 솔루스첨단소재 주식회사 Manufacturing method of deuterated aromatic compound and the deuterated aromatic compound therefrom
CN113912471A (en) * 2021-10-21 2022-01-11 上海八亿时空先进材料有限公司 Anthracene derivative, organic electroluminescent material, light-emitting device and consumer product
CN115124433A (en) * 2022-07-12 2022-09-30 北京八亿时空液晶科技股份有限公司 Spirobifluorene derivative and application thereof
CN115322177A (en) * 2022-08-09 2022-11-11 北京八亿时空液晶科技股份有限公司 Fluorene derivative and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210082637A (en) * 2019-12-26 2021-07-06 솔루스첨단소재 주식회사 Manufacturing method of deuterated aromatic compound and the deuterated aromatic compound therefrom
CN113912471A (en) * 2021-10-21 2022-01-11 上海八亿时空先进材料有限公司 Anthracene derivative, organic electroluminescent material, light-emitting device and consumer product
CN115124433A (en) * 2022-07-12 2022-09-30 北京八亿时空液晶科技股份有限公司 Spirobifluorene derivative and application thereof
CN115322177A (en) * 2022-08-09 2022-11-11 北京八亿时空液晶科技股份有限公司 Fluorene derivative and application thereof

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