CN108101898B - Novel organic electroluminescent compound and organic electroluminescent device comprising same - Google Patents

Novel organic electroluminescent compound and organic electroluminescent device comprising same Download PDF

Info

Publication number
CN108101898B
CN108101898B CN201711430623.2A CN201711430623A CN108101898B CN 108101898 B CN108101898 B CN 108101898B CN 201711430623 A CN201711430623 A CN 201711430623A CN 108101898 B CN108101898 B CN 108101898B
Authority
CN
China
Prior art keywords
organic electroluminescent
toluene
layer
compound
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711430623.2A
Other languages
Chinese (zh)
Other versions
CN108101898A (en
Inventor
金振禹
钱超
王晓维
聂金龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Topto Materials Co Ltd
Original Assignee
Nanjing Topto Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Topto Materials Co Ltd filed Critical Nanjing Topto Materials Co Ltd
Priority to CN201711430623.2A priority Critical patent/CN108101898B/en
Publication of CN108101898A publication Critical patent/CN108101898A/en
Application granted granted Critical
Publication of CN108101898B publication Critical patent/CN108101898B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Abstract

The present invention provides a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound has the following structure:

Description

Novel organic electroluminescent compound and organic electroluminescent device comprising same
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same.
Background
Organic electroluminescent Devices (Organic L light-emitting Devices, O L ED) are spontaneous light-emitting Devices that use the principle that when an electric field is applied, fluorescent substances emit light by recombination of holes injected from a positive electrode and electrons injected from a negative electrode.
The organic electroluminescent device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers or among the different electrode film layers, and the different functional materials are mutually overlapped together according to the application to form the organic electroluminescent device. When the organic electroluminescent device is used as a current device, voltage is applied to two end electrodes of the organic electroluminescent device, positive and negative charges are generated in the organic layer functional material film layer under the action of an electric field, the positive and negative charges are further compounded in the light emitting layer to generate light, and the process is electroluminescence.
The research on the improvement of the performance of the organic electroluminescent device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the organic electroluminescent device, not only the innovation of the structure and the manufacturing process of the organic electroluminescent device is required, but also the continuous research and innovation of the organic electro-photoelectric functional material are required, and the organic electroluminescent functional material with higher performance is created.
In terms of the actual requirements of the current organic electroluminescent industry, the development of the current organic electroluminescent materials is far from enough and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as material type enterprises.
Disclosure of Invention
The first objective of the present invention is to overcome the disadvantages of the prior art and to provide an organic electroluminescent compound, which can be used as a hole transport layer material or an electron blocking layer material for an organic electroluminescent device, and can reduce driving voltage, improve luminous efficiency, brightness, thermal stability, color purity and device lifetime.
It is a second object of the present invention to provide an organic electroluminescent device comprising the organic electroluminescent compound of the present invention.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
an organic electroluminescent compound having the following structure:
Figure GDA0002416056250000021
wherein, in the formula (I), R1,R2Independently selected from hydrogen or deuterium, C1-C20 straight chain or branched chain alkyl, phenyl, anilino, diphenylamino, 2-Phenyl, 3-aminopyridyl, 4-aminobipyridyl, 2-phenyl-1-naphthylamino, 2-aminodinaphthyl, 2-phenyl-1-aminophenanthryl, 3-aminodiphenanthryl, 2-phenyl-1-aminoanthracenyl, 2-aminodibenzanthracenyl, phenanthridinyl, biphenyl, pyridyl, pyrimidyl, or triazinyl;
wherein R is1、R2Each independently may form a fused ring with a substituted phenyl group;
R3，R4each independently is selected from C1-C20 straight chain or branched chain alkyl, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl;
m and n are each independently an integer of 0 to 4.
Preferably, in the organic electroluminescent compounds according to the invention, R is1,R2Independently selected from phenyl, anilino, diphenylamino, 2-phenyl, 3-aminopyridyl, 4-aminobipyridyl, 2-phenyl-1-naphthylamino, 2-aminodinaphthyl, 2-phenyl-1-aminophenanthryl, 3-aminodiphenanthryl, 2-phenyl-1-aminoanthracenyl, 2-aminodibenzanthracene, phenanthridinyl, biphenyl, pyridyl, pyrimidyl, or triazinyl, wherein more than one hydrogen is substituted or unsubstituted by C1-C10 straight chain or branched chain alkyl, C3-C12 cycloalkyl, C1-C10 oxyalkyl, halogen, cyano, trifluoromethyl, trimethylsilyl, naphthyl, anthryl, phenanthryl, dibenzofuranyl, benzofuranyl, carbazolyl, spirofluorenyl and 5-20 nuclear heteroaryl.
Preferably, in the organic electroluminescent compounds according to the invention, when R is3，R4Independently selected from phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl, wherein more than one hydrogen is substituted or unsubstituted by a C1-C20 linear or branched alkyl group, a C3-C24 cycloalkyl group, a C1-C20 alkoxy group, a halogen, a cyano group, a trifluoromethyl group, a trimethylsilyl group, a naphthyl group, an anthryl group, a phenanthryl group, a benzofuranyl group, a dibenzofuranyl group, a fluorenyl group, a carbazolyl group, a spirofluorenyl group and a heteroaryl group with a nuclear atom number of 5-20.
Preferably, the organic electroluminescent compound is any one of the following compounds:
Figure GDA0002416056250000031
Figure GDA0002416056250000041
Figure GDA0002416056250000051
Figure GDA0002416056250000061
Figure GDA0002416056250000071
Figure GDA0002416056250000081
Figure GDA0002416056250000091
Figure GDA0002416056250000101
Figure GDA0002416056250000111
Figure GDA0002416056250000121
Figure GDA0002416056250000131
Figure GDA0002416056250000141
Figure GDA0002416056250000151
Figure GDA0002416056250000161
Figure GDA0002416056250000171
Figure GDA0002416056250000181
Figure GDA0002416056250000191
Figure GDA0002416056250000201
Figure GDA0002416056250000211
meanwhile, the invention also provides an organic electroluminescent device containing the organic electroluminescent compound.
Preferably, the organic electroluminescent device of the present invention comprises: a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially stacked;
wherein, an electron blocking layer is optionally arranged between the anode and the luminescent layer; a hole blocking layer is optionally arranged between the cathode and the light-emitting layer; the cathode surface is optionally also provided with a cover layer.
Preferably, in the organic electroluminescent device according to the present invention, at least one of the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer, the light-emitting layer, and the cover layer includes the organic electroluminescent compound according to the present invention.
Also, the present invention provides an organic electroluminescent display device comprising the organic electroluminescent device according to the present invention.
Furthermore, the invention also provides application of the organic electroluminescent compound in preparing organic electroluminescent devices.
Meanwhile, the invention also provides application of the organic electroluminescent compound in preparing organic electroluminescent display equipment.
Compared with the prior art, the invention has the beneficial effects that:
the organic electroluminescent compound can reduce driving voltage, and improve efficiency, brightness, thermal stability, color purity, service life and other effects. In addition, an organic electroluminescent device manufactured using the organic compound has excellent properties of high efficiency and long life.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In view of the fact that organic electroluminescent compounds have great influence on the performance, service life and the like of devices and display devices, and the actual problem that the existing organic electroluminescent compounds cannot meet the actual use requirements, the invention particularly provides a novel organic electroluminescent compound, and a device comprising the same.
Specifically, the organic electroluminescent compound provided by the invention has the following structure:
Figure GDA0002416056250000221
wherein, in the formula (I), R1,R2Each independently selected from hydrogen or deuterium, straight chain or branched chain alkyl of C1-C20, phenyl, anilino, diphenylamino, 2-phenyl, 3-aminopyridyl, 4-aminobipyridyl, 2-phenyl-1-naphthylamino, 2-aminodinaphthyl, 2-phenyl-1-aminophenanthryl, 3-aminodiphenanthryl, 2-phenyl-1-aminophenanthryl, 2-aminodibenzenyl, phenanthridinyl, biphenyl, pyridyl, pyrimidyl or triazinyl;
when R is1,R2Wherein when any R group is phenyl, anilino, diphenylamino, 2-phenyl, 3-aminopyridyl, 4-aminobipyridyl, 2-phenyl-1-naphthylamino, 2-aminodinaphthyl, 2-phenyl-1-aminophenanthryl, 3-aminodiphenanthryl, 2-phenyl-1-aminoanthracenyl, 2-aminodianthranyl, phenanthridinyl, biphenyl, pyridyl, pyrimidyl, or triazinyl, at least one hydrogen of the groups may be substituted by a C1-C10 linear or branched alkyl group, a C3-C12 cycloalkyl group, a C1-C10 oxyalkyl group, halogen, cyano, trifluoromethyl, trimethylsilyl, naphthyl, anthracenyl, phenanthryl, dibenzofuranyl, benzofuranyl, carbazolyl, spirofluorenyl group, or a heteroaryl group having 5 to 20 nuclear atoms, thereby forming a phenyl, anilino, diphenylamino, 2-phenyl, 3-aminopyridyl, 4-aminobipyridyl, 2-phenyl-1-naphthylamino, 2-aminodinaphthyl, 2-phenyl-1-aminophenanthryl, 3-aminodiphenanthryl, 2-phenyl-1-aminoanthracenyl, 2-aminodibenzanthryl, phenanthridinyl, biphenyl, pyridyl, pyrimidyl, or triazinyl group, with or without a substituent;
further, R1、R2Any R group in (a) may also be attached to and substituted with phenyl (i.e., directly attached to the nitrogen atom and substituted with R)1Or R2Substituted phenyl) is fused into a ring, and the phenyl is enabled to form fused ring substituent groups such as naphthalene, anthracene, phenanthrene and pyrene, or fused ring substituent groups with heteroatoms such as carbazole and N-phenylcarbazole.
R3，R4Each independently selected from C1-C20 straight chain or branched chain alkyl, phenyl, pyridylNaphthyl, phenanthryl, anthracyl, phenanthridinyl, biphenyl, pyrimidinyl, or triazinyl;
wherein when R is3，R4When any R group is phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl, more than one hydrogen may be substituted by C1-C20 linear or branched alkyl, C3-C24 cycloalkyl, C1-C20 alkoxy, halogen, cyano, trifluoromethyl, trimethylsilyl, naphthyl, anthryl, phenanthryl, benzofuranyl, dibenzofuranyl, fluorenyl, carbazolyl, spirofluorenyl and 5-20 nuclear heteroaryl, thereby forming phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl with or without substituent;
m and n are each independently integers of 0 to 4, for example m and n are each independently 0, 1, 2, 3 or 4.
The organic electroluminescent compound can be further applied to an organic electroluminescent device as a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, a light emitting layer (a host material or a doping material), or a covering layer material, and the preparation method of the organic electroluminescent device can refer to the following steps:
step 1, evaporating an anode material on the surface of a substrate by using a conventional method to form an anode, wherein the adopted substrate is a glass substrate or a transparent plastic substrate with good transparency, surface smoothness, operability and waterproofness, and the anode material can be transparent ITO, IZO or SnO with excellent conductivity2ZnO, etc.
And 2, performing vacuum thermal deposition or spin coating on the surface of the anode by using a conventional method to obtain a hole injection layer material (HI L), wherein the hole injection layer material can be CuPc, m-MTDATA, m-MTDAPB, TCTA of star amines, 2-TNATA or IDE406 commercially available from Nippon Kyowa Co.
And 3, carrying out vacuum evaporation or spin coating on a hole transport layer material (HT L) on the surface of the hole injection layer by adopting a conventional method to form the hole transport layer, wherein the hole transport layer material can be α -NPD, NPB or TPD besides the organic compound.
Step 4, adopting a conventional method to carry out vacuum evaporation or spin coating on the light-emitting layer material (EM L) on the surface of the hole transport layer to form a light-emitting layer, wherein the light-emitting layer material and the light-emitting main substance can use the compound disclosed by the invention, namely tris (8-hydroxyquinoline) aluminum (Alq)3) Balq, DPVBi series compounds, spiro-DPVBi, &lTtT transition = L "&gTt L &lTt/T &gTt iPBO, bis (diphenylethylene) benzene, aluminum-quinoline metal complexes, imidazole, thiazole, oxazole metal complexes, and the like.
In the light-emitting layer, a dopant substance used together with a light-emitting host substance, which is blue light, can be used; in addition, IDE102 and IDE105 of Nippon Kagaku K.K.; phosphorescent dopants Ir (ppy)3FIrpic (reference [ Chihaya Adachi et al, appl. Phys. L et al, 2001,79,3082-]) PtOEP, TBE002(Cobion Co.), etc.
Further, an electron blocking layer (EB L) may be added between the hole transporting layer and the light-emitting layer, and the material of the electron blocking layer is not particularly limited, and the organic compound according to the present invention may be used.
Step 5, adopting a conventional method to carry out vacuum thermal deposition or spin coating on the surface of the luminescent layer to form the electron transport layer (ET L). the electron transport layer is not particularly limited, and the organic compound and Alq related to the invention can be used3And the like.
Step 6, adopting a conventional method to thermally deposit or spin-coat an electron injection layer material (EI L) on the surface of the electron transport layer in vacuum to form an electron injection layer, wherein the electron injection layer material can be L iF, L iq, L i2O, BaO, NaCl, CsF, etc.
And 7, carrying out vacuum thermal deposition or spin coating on a cathode material on the electron injection layer by adopting a conventional method to form a cathode, wherein the cathode material can be L i, Al, Al-L i, Ca, Mg, Mg-In, Mg-Ag and the like, and In addition, Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO) can be used for preparing a light-transmitting transparent cathode.
The surface of the cathode may be further provided with a coating layer (CP L). the coating layer material is not particularly limited, and the organic compound according to the present invention may be used.
The hole blocking layer material (HB L) is formed on the surface of the luminescent layer by vacuum thermal deposition or spin coating by adopting a conventional method, and the hole blocking layer material is not particularly limited, and the organic compound related to the invention, L iq, 2-methyl-8-hydroxyquinoline p-hydroxybiphenyl aluminum, BCP, L iF and the like can be used.
The organic electroluminescent device prepared by the method has the advantages of low starting voltage, long service life and the like.
Example 1
Synthesis of Compound 71
Synthesis of intermediate-1
[ reaction formula 1]
Figure GDA0002416056250000251
20.4g (100mmol,1.0eq.) of 5-phenyl-2-thiopheneboronic acid and 24.8g (100mmol,1.0eq.) of 4-bromo-4' -aminobiphenyl were charged into a 2L three-necked flask, dissolved in 900ml of toluene and 90ml of ethanol, purged with nitrogen for 15 minutes, charged with 150ml of a 2M aqueous solution containing 41.5g (300mmol,3.0eq.) of K2CO3, and finally charged with 2.3g of Pd (PPh3)4(2 mol%). warmed to 100 ℃ C.after the reaction was over night, adsorbed with activated carbon, filtered with suction, the solvent was removed, dried, and recrystallized from toluene and ethanol to give 27.2g of intermediate-1 in 83% yield.
Synthesis of intermediate-2
[ reaction formula 2]
Figure GDA0002416056250000252
In a dry 2L three-necked flask were added 27.2g (83mmol, 1.1eq.) of intermediate-1 and 24.3g (75.5mmol, 1.0eq.) of 3-bromo-9-phenylCarbazole, adding dried and degassed 1000ml of toluene as a solvent, and introducing nitrogen for 15 minutes. Further, 14.5g (151mmol,2.0eq.) of sodium tert-butoxide and 1.4g (2% mol) of Pd as a catalyst were added2(dba)3And 6.1ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 32.2g of intermediate-2 with the yield of 75%.
Synthesis of intermediate-3
[ reaction formula 3]
Figure GDA0002416056250000261
A dry 2L three-necked flask was charged with 32.2g (56.6mmol, 1.0eq.) of intermediate-2 and 22.4g (62.3mmol, 1.1eq.) of 4-bromo-4' -iodobiphenyl, and 1100ml of dry degassed toluene as solvent was added, nitrogen was passed through for 15 minutes, 10.9g (113.2mmol,2.0eq.) of sodium tert-butoxide, 1.0g (2% mol) of catalyst Pd were added2(dba)3And 4.6ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 37.6g of intermediate-3 with the yield of 83%.
Synthesis of intermediate-4
[ reaction formula 4]
Figure GDA0002416056250000262
23.9g (100mmol,1.0eq.) of 2-bromo-5-phenylthiophene and 15.1g (110mmol,1.1eq.) of p-aminobenzoic acid were charged into a 2L three-neck flask, dissolved in 800ml of toluene and 80ml of ethanol, purged with nitrogen for 15 minutes, and then 150ml of 2M aqueous solution containing 41.5g (300mmol,3.0eq.) of K2CO3To the aqueous solution of (1), and finally 2.3g of Pd (PPh) was added3)4(2 mol%). The temperature was raised to 100 ℃ and the reaction was terminated overnight. Adding active carbon for adsorption, suction filtering, removing solvent, drying, and adding toluene and ethanol for heavy precipitationCrystallization gave 20.1g of intermediate-4 in 80% yield.
Synthesis of intermediate-5
[ reaction formula 5]
Figure GDA0002416056250000271
In a dry 2L three-necked flask, 20.1g (80mmol, 1.1eq.) of intermediate-4 and 19.9g (72.7mmol, 1.0eq.) of 2-bromo-9, 9' -dimethylfluorene were charged, followed by addition of dried and degassed 800ml of toluene as solvent, nitrogen gas introduction for 15 minutes, addition of 14g (145.4mmol,2.0eq.) of sodium tert-butoxide, 1.3g (2% mol) of catalyst Pd2(dba)3And 5.9ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 24.5g of intermediate-5 with the yield of 76%.
Synthesis of Compound-71
[ reaction formula 6]
Figure GDA0002416056250000272
A dry 2L three-necked flask was charged with 37.6g (47mmol, 1.0eq.) of intermediate-4 and 20.9g (7mmol, 1.0eq.) of intermediate-5, then dried and degassed 600ml of toluene was added as solvent, nitrogen was passed through for 15 minutes, then 9g (94mmol,2.0eq.) of sodium tert-butoxide, 0.9g (2% mol) of catalyst Pd were added2(dba)3And 3.8ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 33.3g of compound-72 with the yield of 61%.
Nuclear magnetic resonance hydrogen and mass spectra of compound-71:
1H NMR(DMSO,300Hz):(ppm)＝8.64-8.47(d,1H),8.04-7.73(m,9H),7.68-7.44(m,19H),7.42-7.21(m,20H),7.19-7.05(m,2H),7.03-6.88(m,2H),1.78-1.43(s,6H)；
MS(FAB):1162(M+)。
example 2
Synthesis of Compound 75
Synthesis of intermediate-6
[ reaction formula 7]
Figure GDA0002416056250000281
19.3g (100mmol,1.0eq.) of 1-bromo-3, -difluorobenzene and 35.1g (210mmol,2.1eq.) of carbazole are put into a three-necked flask of 2L, dissolved in 900ml of DMF, heated to 170 ℃ overnight for 15 hours, cooled to room temperature after the reaction is finished, filtered, extracted by dichloromethane and water, washed 3 times with water, dried, spun off the solvent, beaten 2 times with ethanol, and recrystallized by toluene and ethanol to finally obtain 44.4g of intermediate-6 with the yield of 91%.
Synthesis of intermediate-7
[ reaction formula 8]
Figure GDA0002416056250000282
20.4g (100mmol,1.0eq.) of 5-phenyl-2-thiopheneboronic acid and 18.9g (110mmol,1.1eq.) of p-bromoaniline were charged into a 2L three-necked flask, dissolved in 800ml of toluene and 80ml of ethanol, purged with nitrogen for 15 minutes, and then 150ml of 2M containing 41.5g (300mmol,3.0eq.) of K2CO3To the aqueous solution of (1), and finally 2.3g of Pd (PPh) was added3)4(2 mol%). The temperature was raised to 100 ℃ and the reaction was terminated overnight. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 20.9g of intermediate-7 with the yield of 83%.
Synthesis of intermediate-8
[ reaction formula 9]
Figure GDA0002416056250000291
In a dry 2L three-necked flask, 20.9g (83mmol, 1.1eq.) of intermediate-8 and 36.8g (75.5mmol, 1.0eq.) of intermediate-7 were added, followed by additional drying and degassing1200ml of toluene as solvent, and introducing nitrogen for 15 minutes. Further, 14.5g (151mmol,2.0eq.) of sodium tert-butoxide and 1.4g (2% mol) of Pd as a catalyst were added2(dba)3And 6.1ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 37.2g of intermediate-8 with the yield of 75%.
Synthesis of intermediate-9
[ reaction formula 10]
Figure GDA0002416056250000292
37.2g (56.6mmol, 1.0eq.) of intermediate-8 and 22.4g (62.3mmol, 1.1eq.) of 4-bromo-4' -iodobiphenyl were placed in a dry 2L three-necked flask, 1200ml of toluene, dried and degassed, was added as solvent, nitrogen was passed through for 15 minutes, 10.9g (113.2mmol,2.0eq.) of sodium tert-butoxide, 1.0g (2% mol) of catalyst Pd were added2(dba)3And 4.6ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 36.2g of intermediate-9 with the yield of 72%.
Synthesis of intermediate-10
[ reaction formula 11]
Figure GDA0002416056250000301
In a dry 2L three-necked flask, 25.7g (100mmol,1.0eq.) of 2-bromophenanthrene and 27.6g (110mmol,1.1eq.) of intermediate-7 were placed, 1000ml of toluene which had been dried and degassed were added as a solvent, nitrogen was introduced for 15 minutes, 19.2g (200mmol,2.0eq.) of sodium tert-butoxide and 1.8g (2% mol.) of catalyst Pd were added2(dba)3And 8.1ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. Cooling to room temperature after the reaction is finished, adding active carbon for adsorption, performing suction filtration, removing the solvent by rotation, and using toluene and ethylRecrystallization of the alcohol gave 32.1g of intermediate-10 in 75% yield.
Synthesis of Compound-75
[ reaction formula 12]
Figure GDA0002416056250000302
A dry 2L three-necked flask was charged with 36.2g (40.7mmol, 1.0eq.) of intermediate-9 and 17.4g (40.7mmol, 1.0eq.) of intermediate-10, then 600ml of toluene dried and degassed was added as solvent, nitrogen was passed through for 15 minutes, then 7.8g (81.4mmol,2.0eq.) of sodium tert-butoxide, 0.7g (2% mol) of catalyst Pd were added2(dba)3And 3.3ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by spinning, and recrystallizing with toluene and ethanol to obtain 32.7g of compound-76 with the yield of 65%.
Nuclear magnetic resonance hydrogen and mass spectra of compound-75:
1H NMR(DMSO,300Hz):(ppm)＝8.96-8.78(d,1H),8.73-8.63(d,1H),8.59-8.47(m,2H),8.26-8.13(m,2H),7.98-7.41(m,27H),7.39-7.26(m,14H),7.24-7.11(m,7H),7.03-6.87(m,4H)；
MS(FAB):1235(M+)。
example 3
Synthesis of Compound 81
Synthesis of intermediate-11
[ reaction formula 13]
Figure GDA0002416056250000311
23.8g (100mmol,1.0eq.) of 9, 9' -dimethylfluorene-4-boronic acid and 31.8g (110mmol,1.1eq.) of 2-bromo-5-iodothiophene were charged into a 2L three-necked flask, dissolved in 1100ml of toluene and 110ml of ethanol, purged with nitrogen for 15 minutes, and then 150ml of 2M solution containing 41.5g (300mmol,3.0eq.) of K2CO3To the aqueous solution of (1), and finally 2.3g of Pd (PPh) was added3)4(2 mol%). The temperature was raised to 100 ℃ and the reaction was terminated overnight. Adding active carbon for adsorption and pumpingFiltration, removal of the solvent by rotation, drying and recrystallization from toluene and ethanol gave 27.7g of intermediate-11 in 78% yield.
Synthesis of intermediate-12
[ reaction formula 14]
Figure GDA0002416056250000312
27.7g (78mmol,1.0eq.) of intermediate-11 and 11.7g (85.8mmol,1.1eq.) of p-aminobenzoic acid were charged in a 2L three-necked flask, dissolved in 800ml of toluene and 80ml of ethanol, purged with nitrogen for 15 minutes, and added with 117ml of 2M solution containing 32.3g (234mmol,3.0eq.) of K2CO3To the aqueous solution of (1.8 g) of Pd (PPh) was finally added3)4(2 mol%). The temperature was raised to 100 ℃ and the reaction was terminated overnight. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 23.5g of intermediate-12 with the yield of 82%.
Synthesis of intermediate-13
[ reaction formula 15]
Figure GDA0002416056250000321
23.5g (64mmol, 1.1eq.) of the product from step 2 and 15g (58.1mmol, 1.0eq.) of 2-bromophenanthrene were placed in a dry 2L three-necked flask, 800ml of toluene which had been dried and degassed were added as solvent, nitrogen was passed through for 15 minutes, 11.2g (116.2mmol,2.0eq.) of sodium tert-butoxide and 1.1g (2% mol.) of the catalyst Pd were added2(dba)3And 4.7ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 23.1g of intermediate-13 with the yield of 73%.
Synthesis of intermediate-14
[ reaction formula 16]
Figure GDA0002416056250000322
23.1g (42.4mmol,1.0eq.) of intermediate-13 and 16.7g (46.7mmol,1.1eq.) of 4-bromo-4' -iodobiphenyl were charged into a 2L three-necked flask, dissolved in 800ml of toluene and 80ml of ethanol, purged with nitrogen for 15 minutes, and 63.6ml of 2M containing 17.6g (127.2mmol,3.0eq.) of K was added2CO3To the aqueous solution of (1.0 g) of Pd (PPh) was finally added3)4(2 mol%). The temperature was raised to 100 ℃ and the reaction was terminated overnight. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 25.3g of intermediate-14 with the yield of 77%.
Synthesis of intermediate-15
[ reaction formula 17]
Figure GDA0002416056250000331
35.9g (100mmol,1.0eq.) of 1- (4-bromophenyl) -pyrene and 15.1g (110mmol,1.1eq.) of M-aminobenzoic acid were charged into a 2L three-necked flask, 1000ml of toluene and 100ml of ethanol were added for dissolution, nitrogen was introduced for 15 minutes, 150ml of 2M aqueous solution containing 41.5g (300mmol,3.0eq.) of K2CO3 was added, finally 2.3g of Pd (PPh3)4(2 mol%) was added, the temperature was raised to 100 ℃ and the reaction was terminated overnight, activated carbon adsorption, suction filtration, solvent removal, drying, recrystallization from toluene and ethanol were performed to give 29.7g of intermediate-15 with a yield of 80%.
Synthesis of intermediate-16
[ reaction formula 18]
Figure GDA0002416056250000332
A dry 2L three-necked flask was charged with 25.3g (32.7mmol, 1.0eq.) of intermediate-14 and 13.3g (35.9mmol, 1.1eq.) of intermediate-15, followed by addition of 800ml of toluene as solvent, which was dried and degassed, nitrogen gas purged for 15 minutes, addition of 6.3g (65.4mmol,2.0eq.) of sodium tert-butoxide, 0.6g (2% mol) of catalyst Pd2(dba)3And 6ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding active carbon for adsorption, performing suction filtration, removing the solvent by rotation, and usingRecrystallization from toluene and ethanol gave 24g of intermediate-16 in 69% yield.
Synthesis of intermediate-17
[ reaction formula 19]
Figure GDA0002416056250000333
20.4g (100mmol,1.0eq.) of 5-phenyl-2-thiopheneboronic acid and 31.1g (110mmol,1.1eq.) of p-bromoiodobenzene were charged into a 2L three-necked flask, dissolved in 1000ml of toluene and 100ml of ethanol, purged with nitrogen for 15 minutes, and then 150ml of 2M aqueous solution containing 41.5g (300mmol,3.0eq.) of K2CO3To the aqueous solution of (1), and finally 2.3g of Pd (PPh) was added3)4(2 mol%). The temperature was raised to 100 ℃ and the reaction was terminated overnight. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 19.6g of intermediate-17 with the yield of 78%.
Synthesis of Compound-81
[ reaction formula 20]
Figure GDA0002416056250000341
A dry 2L three-neck flask was charged with 24g (22.5mmol, 1.0eq.) of intermediate-16 and 5.7g (22.5mmol, 1.0eq.) of intermediate-17, then dried and degassed 600ml of toluene was added as solvent, nitrogen was passed through for 15 minutes, then 4.3g (45mmol,2.0eq.) of sodium tert-butoxide, 0.4g (2% mol.) of catalyst Pd2(dba)3And 1.8ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 18.1g of compound-81 with the yield of 62%.
Nuclear magnetic resonance hydrogen and mass spectra of compound-81:
1H NMR(DMSO,300Hz):(ppm)＝8.97-8.78(d,1H),8.73-8.64(d,1H),8.59-8.47(d,1H),8.37-8.24(d,1H),8.19-7.97(m,5H),7.94-7.11(m,47H),7.05-6.92(m,2H),1.79-1.43(s,6H)；
MS(FAB):1297(M+)。
example 4
Synthesis of Compound-101
Synthesis of intermediate-18
[ reaction formula 21]
Figure GDA0002416056250000351
17.2g (100mmol,1.0eq.) of p-bromoaniline and 22.4g (110mmol,1.1eq.) of 5-phenyl-2-thiopheneboronic acid were charged into a 2L three-necked flask, dissolved in 800ml of toluene and 80ml of ethanol, purged with nitrogen for 15 minutes, and then 150ml of 2M containing 41.5g (300mmol,3.0eq.) of K2CO3To the aqueous solution of (1), and finally 2.3g of Pd (PPh) was added3)4(2 mol%). The temperature was raised to 100 ℃ and the reaction was terminated overnight. Adding active carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing with toluene and ethanol to obtain 21.6g of intermediate-18 with the yield of 86%.
Synthesis of intermediate-19
[ reaction formula 22]
Figure GDA0002416056250000352
36g (100mmol,1.0eq.) of 9, 9' -spirobifluorene-2-boronic acid and 31.1g (110mmol,1.1eq.) of p-bromoiodobenzene were charged into a 3L three-necked flask, dissolved in 1400ml of toluene and 140ml of ethanol, purged with nitrogen for 15 minutes, and then 150ml of 2M solution containing 41.5g (300mmol,3.0eq.) of K2CO3To the aqueous solution of (1), and finally 2.3g of Pd (PPh) was added3)4(2 mol%). The temperature was raised to 100 ℃ and the reaction was terminated overnight. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 35.8g of intermediate-19, wherein the yield is 76%.
Synthesis of intermediate-20
[ reaction formula 23]
Figure GDA0002416056250000353
In a dry 2L three-neck flask21g (83.6mmol, 1.1eq.) of intermediate-18 and 35.8g (76mmol, 1.0eq.) of intermediate-19 were added, followed by 900ml of toluene, dried and degassed, as solvent, and nitrogen purged for 15 minutes. Further, 14.6g (152mmol,2.0eq.) of sodium tert-butoxide and 1.4g (2% mol) of Pd as a catalyst were added2(dba)3And 6.2ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 38g of intermediate-20 with the yield of 78%.
Synthesis of intermediate-21
[ reaction formula 24]
Figure GDA0002416056250000361
A dry 2L three-necked flask was charged with 38g (59.3mmol, 1.0eq.) of intermediate-20 and 23.4g (65.2mmol, 1.1eq.) of 4-bromo-4' -iodobiphenyl, followed by addition of 1200ml of dried and degassed toluene as solvent, nitrogen gas was passed through for 15 minutes, followed by addition of 11.4g (118.6mmol,2.0eq.) of sodium tert-butoxide, 1.1g (2% mol) of catalyst Pd2(dba)3And 4.8ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 36.8g of intermediate-21 with the yield of 71%.
Synthesis of intermediate-22
[ reaction formula 25]
Figure GDA0002416056250000362
17.2g (100mmol,1.0eq.) of p-bromoaniline and 22.4g (110mmol,1.1eq.) of 5-phenyl-2-thiopheneboronic acid were charged into a 2L three-necked flask, dissolved in 800ml of toluene and 80ml of ethanol, purged with nitrogen for 15 minutes, and then 150ml of 2M containing 41.5g (300mmol,3.0eq.) of K2CO3To the aqueous solution of (1), and finally 2.3g of Pd (PPh) was added3)4(2 mol%). The temperature was raised to 100 ℃ and the reaction was terminated overnight. Adding active carbonAdsorption, suction filtration, solvent removal, drying, recrystallization from toluene and ethanol gave 21.6g of intermediate-22 in 86% yield.
Synthesis of intermediate-23
[ reaction formula 26]
Figure GDA0002416056250000371
A dry 2L three-necked flask was charged with 36.8g (42.1mmol, 1.0eq.) of intermediate-21 and 11.6g (46.3mmol, 1.1eq.) of intermediate-22, followed by addition of 800ml of toluene as solvent, which was dried and degassed, nitrogen purged for 15 minutes, addition of 8.1g (84.2mmol,2.0eq.) of sodium tert-butoxide, 0.8g (2% mol) of catalyst Pd2(dba)3And 3.4ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 30.3g of intermediate-23 with the yield of 69%.
Synthesis of Compound-101
[ reaction formula 27]
Figure GDA0002416056250000372
30.3g (29mmol, 1.0eq.) of intermediate-23 and 6.8g (29mmol, 1.0eq.) of 4-bromobiphenyl were placed in a dry 2L three-necked flask, 800ml of toluene which had been dried and degassed were added as solvent, nitrogen was passed through for 15 minutes, 5.6g (58mmol,2.0eq.) of sodium tert-butoxide and 0.5g (2% mol.) of catalyst Pd were added2(dba)3And 2.3ml (4% mol) of P (t-bu)3In toluene (m/v, 10%). The temperature was raised to 90 ℃ and the reaction was carried out for 1.5 hours. After the reaction is finished, cooling to room temperature, adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, and recrystallizing with toluene and ethanol to obtain 20.8g of compound-101 with the yield of 60%.
Nuclear magnetic resonance hydrogen spectrum of compound-101:
1H NMR(DMSO,300Hz):(ppm)＝8.17-8.03(d,1H),7.97-7.75(m,11H),7.65-7.16(m,42H),7.05-6.93(m,4H)；
MS(FAB):1195(M+)。
further, other compounds encompassed by the general structures of the present invention, particularly compounds 1-120, can also be prepared by reference to the methods of formulas 1-27 above.
Application example 1
An organic electroluminescent device using ITO as the anode substrate material of the reflecting layer and N2Plasma or UV-Ozone is used for surface treatment. Depositing a hole injection layer over the anode substrate
Figure GDA0002416056250000381
HAT-CN of thickness. Vacuum vapor deposition of the compound 5 selected above the hole injection layer
Figure GDA0002416056250000382
A hole transport layer is formed. Vacuum evaporation of TCTA on the hole transport layer
Figure GDA0002416056250000383
The electron blocking layer is formed by evaporating blue EM L9, 10-Bis (2-naphthyl) Anthracenes (ADN) as a light emitting layer, and is formed by doping about 5% of 2,5,8, 11-tetrabutyl perylene with dopant
Figure GDA0002416056250000384
Mixing anthracene derivative and L iq at a ratio of 1:1, and evaporating to obtain a mixture
Figure GDA0002416056250000385
To the electron transport layer, vapor depositing on the electron transport layer
Figure GDA0002416056250000386
L iq as electron injection layer, and finally evaporating at cathode
Figure GDA0002416056250000387
Thickness of silver. In addition, the surface of the cathode is sealed by a water absorbing material containing a UV curable adhesive to protect the organic electroluminescent deviceIs not affected by oxygen or moisture in the atmosphere.
The structural formula of the compound involved in the application example is as follows:
Figure GDA0002416056250000388
application examples 2 to 12
The organic electroluminescent devices of application examples 1 to 12 were produced by using compounds 8, 19, 32, 41, 45, 56, 71, 81, 95, 101 and 114 as the hole transport layer (HT L) material, respectively, and the rest of the materials were the same as those of application example 1.
Comparative example 1
The difference from application example 1 is that NPD was used as a hole transport layer material in place of the organic electroluminescent compound of the present invention, and the rest was the same as application example 1.
The organic electroluminescent devices prepared in application examples 1 to 12 and application example 1 were subjected to performance tests under the condition of a current density of 10mA/cm2, and the results are shown in the following table.
Table 1 device performance test results for different experimental groups:
Figure GDA0002416056250000391
as can be seen from the experimental results shown in table 1, the organic electroluminescent devices of application examples 1 to 12 of the present invention have significantly improved luminous efficiency performance as compared with the conventional organic electroluminescent device described in comparative example 1.
Further, it is understood from the above experimental results that when the organic compound of the present invention is used as a hole transporting substance, it is confirmed that the driving voltage of the organic electroluminescent device is significantly reduced, the organic compound of the present invention can provide the device with the effects of reducing the electric power driving and reducing the electric power consumption, and further, the life of the organic electroluminescent device is improved by the lower electric power driving.
While particular application examples have been illustrated and described, it should be appreciated that many other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (7)

1. An organic electroluminescent compound, characterized in that the organic electroluminescent compound is any one of the following compounds:
Figure FDA0002416056240000011
Figure FDA0002416056240000021
Figure FDA0002416056240000031
Figure FDA0002416056240000041
Figure FDA0002416056240000051
Figure FDA0002416056240000061
Figure FDA0002416056240000071
Figure FDA0002416056240000081
Figure FDA0002416056240000091
2. an organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
3. The organic electroluminescent device according to claim 2, characterized in that the organic electroluminescent device comprises:
a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially stacked;
wherein, an electron blocking layer is optionally arranged between the anode and the luminescent layer;
a hole blocking layer is optionally arranged between the cathode and the light-emitting layer;
the cathode surface is optionally also provided with a cover layer.
4. The organic electroluminescent device according to claim 3, wherein at least one of the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer, the light emitting layer, and the cover layer comprises the organic electroluminescent compound according to claim 1.
5. An organic electroluminescent display device comprising the organic electroluminescent device according to any one of claims 2 to 4.
6. Use of the organic electroluminescent compound according to claim 1 for the preparation of organic electroluminescent devices.
7. Use of the organic electroluminescent compound according to claim 1 for the preparation of organic electroluminescent display devices.
CN201711430623.2A 2017-12-26 2017-12-26 Novel organic electroluminescent compound and organic electroluminescent device comprising same Active CN108101898B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711430623.2A CN108101898B (en) 2017-12-26 2017-12-26 Novel organic electroluminescent compound and organic electroluminescent device comprising same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711430623.2A CN108101898B (en) 2017-12-26 2017-12-26 Novel organic electroluminescent compound and organic electroluminescent device comprising same

Publications (2)

Publication Number Publication Date
CN108101898A CN108101898A (en) 2018-06-01
CN108101898B true CN108101898B (en) 2020-07-14

Family

ID=62213180

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711430623.2A Active CN108101898B (en) 2017-12-26 2017-12-26 Novel organic electroluminescent compound and organic electroluminescent device comprising same

Country Status (1)

Country Link
CN (1) CN108101898B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3812367A4 (en) * 2018-06-25 2022-03-23 Hodogaya Chemical Co., Ltd. Compound having triarylamine structure and electroluminescence device
JP2022053547A (en) * 2018-12-03 2022-04-06 出光興産株式会社 Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device
CN110950874A (en) * 2019-12-24 2020-04-03 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound, preparation method thereof and organic electroluminescent device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101473464A (en) * 2006-06-22 2009-07-01 出光兴产株式会社 Organic electroluminescent element using heterocyclic aromatic amine derivative
CN101506191A (en) * 2006-08-23 2009-08-12 出光兴产株式会社 Aromatic amine derivative and organic electroluminescent element using same
CN101687837A (en) * 2007-08-06 2010-03-31 出光兴产株式会社 Aromatic amine derivative and organic electroluminescent element using the same
CN102334210A (en) * 2009-02-27 2012-01-25 出光兴产株式会社 Organic electroluminescent element
CN104513660A (en) * 2013-09-30 2015-04-15 北京鼎材科技有限公司 Organic luminescence material and applications thereof
CN104673276A (en) * 2014-12-31 2015-06-03 北京鼎材科技有限公司 Organic luminescent material and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013191649A (en) * 2012-03-13 2013-09-26 Idemitsu Kosan Co Ltd Organic electroluminescent element

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101473464A (en) * 2006-06-22 2009-07-01 出光兴产株式会社 Organic electroluminescent element using heterocyclic aromatic amine derivative
CN101506191A (en) * 2006-08-23 2009-08-12 出光兴产株式会社 Aromatic amine derivative and organic electroluminescent element using same
CN101687837A (en) * 2007-08-06 2010-03-31 出光兴产株式会社 Aromatic amine derivative and organic electroluminescent element using the same
CN102334210A (en) * 2009-02-27 2012-01-25 出光兴产株式会社 Organic electroluminescent element
CN104513660A (en) * 2013-09-30 2015-04-15 北京鼎材科技有限公司 Organic luminescence material and applications thereof
CN104673276A (en) * 2014-12-31 2015-06-03 北京鼎材科技有限公司 Organic luminescent material and application thereof

Also Published As

Publication number Publication date
CN108101898A (en) 2018-06-01

Similar Documents

Publication Publication Date Title
CN107936957B (en) Organic electroluminescent compound, organic electroluminescent device and application thereof
CN106518603B (en) Organic material and organic electroluminescent module using the same
Wu et al. High efficiency non-dopant blue organic light-emitting diodes based on anthracene-based fluorophores with molecular design of charge transport and red-shifted emission proof
TWI607985B (en) Organic material and organic electroluminescent device using the same
WO2011024451A1 (en) Organic electroluminescent element and compound having carbazole ring structure
CN109796435B (en) Organic photoelectric material and organic electroluminescent device including the same
CN108101897B (en) Novel organic electroluminescent compound and organic electroluminescent device containing same
JP2013526014A (en) Novel organic electroluminescent compound and organic electroluminescent device using the same
KR20110116635A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR101559430B1 (en) Organic light compound and organic light device using the same
JP2000021572A (en) Organic electroluminescance element
CN107652307B (en) Organic electroluminescent material and application thereof
Lin et al. Highly efficient deep-blue organic electroluminescent devices doped with hexaphenylanthracene fluorophores
CN108101898B (en) Novel organic electroluminescent compound and organic electroluminescent device comprising same
KR20120020818A (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
TWI641598B (en) Compound and organic electronic device using the same
CN115557920A (en) Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
JP2007023041A (en) Synthetic method
KR101779915B1 (en) Fused arylamine compound and organic electroluminescent devices comprising the same
WO2015085728A1 (en) Indoloacridine-containing derivative, preparation method and use thereof, and organic light-emitting device
WO2015085729A1 (en) Bicarbazole derivative, preparation method and use thereof, and organic light-emitting device
CN109897040B (en) Organic compound and organic electroluminescent device containing same
US9938287B1 (en) Blue fluorescence dopant compound and organic electroluminescent device using the same
TW201706235A (en) Organic material and organic electroluminescence device using the same
CN115611835B (en) Organic compound and organic electroluminescent device comprising the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant