CN115109039A - Carbazole derivative and application thereof in OLED - Google Patents

Carbazole derivative and application thereof in OLED Download PDF

Info

Publication number
CN115109039A
CN115109039A CN202210823591.7A CN202210823591A CN115109039A CN 115109039 A CN115109039 A CN 115109039A CN 202210823591 A CN202210823591 A CN 202210823591A CN 115109039 A CN115109039 A CN 115109039A
Authority
CN
China
Prior art keywords
substituted
unsubstituted
group
layer
aryl
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.)
Granted
Application number
CN202210823591.7A
Other languages
Chinese (zh)
Other versions
CN115109039B (en
Inventor
曹建华
谢佩
杨美跃
李留洋
王振宇
唐伟
姜坤
刘赛赛
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.)
Shanghai 800 Million Spacetime Advanced Material Co ltd
Original Assignee
Shanghai 800 Million Spacetime Advanced Material 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 Shanghai 800 Million Spacetime Advanced Material Co ltd filed Critical Shanghai 800 Million Spacetime Advanced Material Co ltd
Priority to CN202210823591.7A priority Critical patent/CN115109039B/en
Publication of CN115109039A publication Critical patent/CN115109039A/en
Priority to PCT/CN2023/107197 priority patent/WO2024012522A1/en
Application granted granted Critical
Publication of CN115109039B publication Critical patent/CN115109039B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • 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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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
    • 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
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • 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
    • H10K85/649—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
    • H10K85/657—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
    • C09K2211/1018—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
    • 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
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Indole Compounds (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to a carbazole derivative and application thereof in an Organic Light Emitting Diode (OLED). The carbazole derivative has a condensed carbazole structure and a high triplet state energy level, and increases the conjugation of a carbazole parent nucleus, thereby improving the thermal stability and the transport carrier of the materialThe capabilities of the streamer. The carbazole derivative is applied to an organic electroluminescent element, so that the driving voltage can be remarkably reduced, the luminous efficiency can be improved, and the service life can be prolonged. The structural formula of the carbazole derivative is shown as a formula (I).
Figure DDA0003745460600000011

Description

Carbazole derivative and application thereof in OLED
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a carbazole derivative and application thereof in an organic light-emitting diode (OLED).
Background
In general, the organic light emitting phenomenon refers to a phenomenon in which light is emitted when electric energy is applied to an organic substance. That is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer; when the injected holes and electrons meet, excitons are formed, and when the excitons transition to a ground state, light and heat are emitted.
In recent years, organic electroluminescent display technology has become mature, some products have entered the market, but in the process of industrialization, many problems still need to be solved. In particular, various organic materials used for manufacturing elements have many problems which are not solved, such as carrier injection and transmission performance, electroluminescent performance of the materials, service life, color purity, matching between various materials and between various electrodes, and the like; especially, the luminous efficiency and the service life of the light-emitting element are not practical, which greatly limits the development of the OLED technology. The metal complex phosphorescent material utilizing triplet state luminescence has high luminescence efficiency, and green and red materials thereof meet the use requirements, but the metal complex phosphorescent material requires a phosphorescent material or a hole material with high triplet state energy level to be matched with the metal complex phosphorescent material. Therefore, the development of phosphorescent materials or hole materials having a high triplet energy level is an urgent need for the development of current OLEDs.
Under the current technological development, improvements are also needed, both for fluorescent materials and for phosphorescent materials, in particular in terms of operating voltage, efficiency and lifetime for use in organic electroluminescent elements and thermal stability during sublimation.
In view of this, the invention is particularly proposed.
Disclosure of Invention
In order to overcome the above-described problems of the conventional techniques and to further improve the characteristics of the organic electroluminescent element, development of a more stable and effective substance which can be used as a phosphorescent material or a hole-forming material in the organic electroluminescent element is continuously required.
The invention provides a carbazole derivative, which can improve the thermal stability of materials and the capability of transporting carriers, and an organic electroluminescent element prepared by using the carbazole derivative can obviously reduce the driving voltage, improve the luminous efficiency and prolong the service life.
The structural formula of the carbazole derivative is shown as the formula (I):
Figure BDA0003745460580000011
wherein, the first and the second end of the pipe are connected with each other,
L 1 selected from single bond, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 A heteroarylene group;
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 the same or different compounds are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl radical, C 1 -C 40 Alkoxy radical, C 2 -C 40 Alkenyl radical, C 1 -C 40 Alkylthio radical, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl, C 1 -C 40 Alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 Silyl, substituted or unsubstituted boron group, substituted or unsubstituted amine group, substituted or unsubstituted aryl phosphine group, substituted or unsubstituted phosphine oxide group, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
n represents an integer of 0 to 5;
Ar 1 selected from substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups.
Preferably, said R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylene, carbazole, dibenzofuran, or dibenzothiophene.
Preferably, Ar is 1 A group selected from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,
Figure BDA0003745460580000022
Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, idobenzene, terphenyl, quaterphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-indenocarbazole, cis-or trans-indolocarbazole, triindene, isotridenzene, spirotriindene, spiroisotridenzene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, perylene, and perylene,Benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo [5,6 ]]Quinoline, benzo [6,7 ]]Quinoline, benzo [7,8 ]]Quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxaloimidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroixazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diaza-thracene, 2, 7-diaza, 2, 3-diaza-pyrene, 1, 6-diaza-pyrene, 1, 8-diaza-pyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescent red ring, naphthyridine, azacarbazole, benzocarbazine, carboline, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, tetrazole, 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3, 5-tetrazine, purine, pteridine, indolizine, quinazoline and benzothiadiazole, or a group derived from a combination of these systems.
Preferably, said n is selected from 0, 1 or 2.
Preferably, Ar is 1 Selected from the group consisting of groups represented by II-1 to II-17:
Figure BDA0003745460580000021
wherein the content of the first and second substances,
Z 1 、Z 2 each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxy or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 represents O, S, CR 'R "or NAr';
r 'and R' are each independently selected from hydrogen, deuterium, C 1 ～C 40 Alkyl of (C) 1 ～C 40 With heteroalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl, 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 so formed; preferably, R', R "are methyl, phenyl or fluorenyl;
ar' is selected from C 1 ～C 40 Alkyl of (C) 1 ～C 40 Heteroalkyl of (a), C 3 ～C 40 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 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl, biphenyl or naphthyl.
Preferably, said L 1 Selected from the group consisting of the following groups III-1 to III-15:
Figure BDA0003745460580000031
wherein the content of the first and second substances,
Z 11 、Z 12 each independently selected from the group consisting of hydrogen, deuterium, hydrogen, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxy or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
Z 13 represents substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 One or more of a heterocyclic aryl group;
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;
T 3 represents O or S;
it is emphasized that, in the present invention,
Figure BDA0003745460580000032
represents Ar 1 And L 1 Or a connecting bond of N; "-" and "-" indicate a connecting bond.
It is emphasized that, in the present invention, the term "substituted or unsubstituted" means a compound selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, and C 1 -C 60 Alkyl radical, C 2 -C 60 Alkenyl radical, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy radical, C 3 -C 60 Cycloalkyl radical, C 3 -C 60 Cycloalkenyl radical, C 6 -C 60 Aryl radical, C 6 -C 60 Aryloxy radical, C 6 -C 60 An arylthioether group and C 2 -C 60 The heterocyclic aryl group may be substituted or unsubstituted with 1 or more substituents, or may be substituted or unsubstituted with substituents formed by connecting 2 or more substituents among the above-exemplified substituents.
Preferably, the carbazole derivative is selected from compounds represented by the following formula M470-M622:
Figure BDA0003745460580000033
Figure BDA0003745460580000041
Figure BDA0003745460580000051
Figure BDA0003745460580000061
Figure BDA0003745460580000071
Figure BDA0003745460580000081
Figure BDA0003745460580000091
wherein, G is selected from O, S or one of the following structures:
Figure BDA0003745460580000092
Figure BDA0003745460580000101
based on the same technical concept, the invention further provides a preparation method of the carbazole derivative, as shown in scheme 1.
Scheme 1:
Figure BDA0003745460580000102
in scheme 1, the symbols used are as defined in formula (I), and Y is 1 、Y 2 、Y 3 、Y 4 Each independently selected from Cl, Br, I or OTf;
the raw materials for synthesizing the compound shown in the formula (I) can be purchased from commercial sources, the method principle, the operation process, the conventional post treatment, the column purification, the recrystallization purification and other means are well known by the synthesis personnel in the field, and the synthesis process can be completely realized to obtain the target product.
In particular, the compounds of formula (I) are represented by the formula 3-R 1 Substituted-5-halogenated carbazoles I-0 and R 2 Carrying out substitution reaction on the radical acetylene to prepare an intermediate I-1; carrying out a ring closure reaction on the intermediate I-1 to prepare an intermediate I-2; carrying out halogenation reaction on the carbazole intermediate I-2 to obtain I-3; carrying out coupling reaction on a dihalogenated intermediate I-3 and substituted 1-naphthalene boric acid to prepare a condensed carbazole parent nucleus I-4; intermediate I-4 with Ar 1 -(L 1 )n-Y 4 Carrying out a coupling reaction to prepare the compound of formula (I). Intermediate Ar 1 -(L 1 )n-Y 4 Prepared by palladium-catalyzed or base-catalyzed coupling reactions.
As palladium catalysts which may be used in the palladium-catalyzed coupling reaction, there may be selected: pd (P- t Bu 3 ) 2 、Pd(PPh 3 ) 4 、Pd 2 (dba) 3 、Pd 2 (dba) 3 CHCl 3 、PdCl 2 (PPh 3 ) 2 、PdCl 2 (CH 3 CN) 2 、Pd(OAc) 2 、Pd(acac) 2 、Pd/C、PdCl 2 、[Pd(allyl)Cl] 2 Any one of them, or a mixture of two or more of them.
In addition, the base used in the palladium-catalyzed coupling reaction or base-catalyzed coupling reaction may be selected from: sodium tert-butoxide, potassium tert-butoxide, sodium hydride, lithium hydride, sodium tert-amylate, sodium ethoxide, sodium methoxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium, potassium hydride, triethylamine, cesium fluoride, and the like, or a mixture of two or more thereof.
The coupling reaction may be carried out in an organic solvent, wherein the organic solvent may be selected from: ether solvents such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, or anisole, aromatic hydrocarbon solvents such as benzene, toluene, or xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane, and one or a mixture of two or more thereof may be used.
The invention also provides an organic electroluminescent material, the raw material of which comprises the carbazole derivative; and the organic electroluminescent material containing the carbazole derivative has the carrier transport capacity.
The invention also provides application of the organic electroluminescent material in preparation of organic electroluminescent elements.
The present invention also provides an organic electroluminescent element comprising: the organic light-emitting diode comprises a first electrode, a second electrode, a capping layer and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the carbazole derivative described above.
The organic electroluminescent element includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example comprising 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 generation layers. An intermediate layer having, for example, exciton blocking function can likewise be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not be present. The organic electroluminescent device described herein may include one light emitting layer, or it may include a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred are systems with three light-emitting layers, wherein the three layers can exhibit blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises, according to the invention, the carbazole derivative described in the invention.
Further, the organic electroluminescent element according to the 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 electron blocking layer or hole transport layer or the anode and/or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or the cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole-injecting and hole-transporting layer and in the electron-injecting and electron-transporting layer, all materials can be used in the manner conventionally 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 light-emitting layer according to the invention without inventive effort.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process in which the temperature in a vacuum sublimation apparatus is below 10 -5 Pa, preferably less than 10 -6 Pa is applied by vapor deposition. However, the initial pressure may also be even lower, e.g. below 10 -7 Pa。
Preference is likewise given to organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where 10 -5 The material is applied under a pressure between Pa and 1 Pa. A particular example of such a process is an organic vapour jet printing process wherein the material is jettedThe mouth is applied directly and is therefore structured.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet printing or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution of a compound of formula (I). These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition. These methods are generally known to those skilled in the art, and they can be applied to an organic electroluminescent element comprising the compound according to the present invention without inventive labor.
The invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, at least one layer being applied by means of a sublimation method, and/or at least one layer being applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or at least one layer being applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to a carbazole derivative comprising at least one of the above-indicated carbazole derivatives of the present invention. The same preferences as indicated above for the organic electroluminescent elements apply to the compounds according to the invention. In particular, the compounds may furthermore preferably comprise further compounds. The processing of the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires the preparation of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchylone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, methyl benzoate, p-xylene, methyl benzoate, mesitylene, and mixtures thereof, Cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, or a mixture of these solvents.
Preferably, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
The invention also provides a consumer product comprising the organic electroluminescent element.
In addition, the starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange therebetween and any value between the endpoints or any subrange therebetween.
The invention has the beneficial effects that:
the carbazole derivative (shown in formula (I)) has a high triplet state energy level, increases the conjugation of a carbazole parent nucleus, improves the thermal stability of the material and the capability of transporting carriers, and can obviously reduce the driving voltage, improve the luminous efficiency and prolong the service life when the carbazole derivative is applied to an organic electroluminescent element.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic diagram of an organic light emitting device 100. 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 described layers.
Fig. 2 is a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device comprises a substrate 201, an anode 202, a hole injection 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 213. The device 200 may be prepared by sequentially depositing the described layers. Since the most common OLED devices have one light emitting layer, while device 200 has a first light emitting layer and a second light emitting layer, the light emitting peak shapes of the first light emitting layer and the second light emitting layer 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 device 100.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The experimental raw materials and the related equipments used in the following examples are commercially available unless otherwise specified, and the percentages are by mass unless otherwise specified.
The following examples are provided for testing the performance of OLED materials and devices using the following test apparatus and method:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C.
Example 1
A method for preparing compound M473, comprising the steps of:
the first step is as follows: preparation of intermediate Int-1
Figure BDA0003745460580000121
20.0mmol of 5-bromo-3-chlorocarbazole (reactant 1) was dissolved in 40mL of toluene and 20mL of triethylamine, and under the protection of nitrogen, 22.0mmol of trimethylsilylacetylene (reactant 2), 4.0mmol of cuprous iodide, and 2.0mmol of PdCl were added 2 (PPh 3 ) 2 Heating reflux reaction is carried out for 24 hours, the temperature is reduced to room temperature, decompression concentration is carried out to dryness, and residues are separated and purified by a silica gel column to obtain a compound Int-1, a white solid, and the yield is 42%.
The second step: preparation of intermediate Int-2
Figure BDA0003745460580000122
Under the protection of nitrogen, 20.0mmol of Int-1 is dissolved in 80mL of nitromethane and 20mL of THF, 60.0mmol of copper bromide and 10.0mmol of anhydrous potassium phosphate are added, the mixture is stirred at room temperature for 12 hours, 20mL of concentrated hydrochloric acid and 20mL of dichloromethane are added, the mixture is stirred for 1 hour, an organic phase is separated, the organic phase is dried, filtered, concentrated under reduced pressure to dryness, and a residue is separated and purified by a silica gel column to obtain the compound Int-2, namely a white solid with the yield of 84%.
Preparation of Compound B-1
Figure BDA0003745460580000131
Referring to the above-mentioned similar synthetic method, compound B-1 is prepared by replacing only trimethylsilylacetylene in the first step with aryl acetylene or alkyl acetylene or the like substituted acetylene, for example, phenyl acetylene.
Preparation of Compound B-2
Figure BDA0003745460580000132
Referring to the above-mentioned similar synthetic method, compound B-2 was prepared by replacing only trimethylsilylacetylene in the first step with 3-pyridylacetylene.
The third step: preparation of intermediate Int-3
Figure BDA0003745460580000133
Under nitrogen protection, 10.0mmol of Int-2 was dissolved in 40mL of toluene, 20mL of ethanol and 20mL of water, and 12.0mmol of 1-naphthalene boronic acid, 25.0mmol of anhydrous sodium carbonate and 1.0mmol of Pd (PPh) were added 3 ) 4 Heating, refluxing and stirring for reaction for 12 hours, adding 60mL of ethyl acetate and 20mL of water, separating an organic phase, extracting a water phase by using ethyl acetate, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain yellow solid Int-3 with the yield of 83%.
The fourth step: preparation of intermediate Int-4
Figure BDA0003745460580000134
Under the protection of nitrogen, dissolving 20.0mmol of Int-3 in 200mL of dry THF, adding 0.1mol of metal potassium, heating, refluxing, stirring and reacting for 20 hours, cooling to room temperature, adding 20mL of tert-butyl alcohol, pouring out reaction liquid to remove excessive potassium, adding iodine in batches under stirring until the solution is purple, adding 50mL of saturated sodium thiosulfate aqueous solution, extracting with EA, drying an organic phase, filtering, concentrating under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain yellow solid Int-4, wherein the yield is as follows: and 64 percent.
The fifth step: preparation of intermediate Int-5
Figure BDA0003745460580000135
Under the protection of nitrogen, 10.0mmol of intermediate Int-4 is dissolved in 40mL of dry DMF, the temperature is reduced to 0 ℃, 12.0mmol of 65% sodium hydride solid is added in batches, the mixture is stirred and reacted for 30 minutes, 11.0mmol of 2-chloro-4-biphenyl-6-phenyl-1, 3, 5-triazine (reactant 3) is added, the mixture is heated to room temperature and stirred and reacted for 12 hours, the reaction solution is poured into 150mL of ice water, the mixture is filtered, a filter cake is washed by water and ethanol, and the mixture is separated and purified by a silica gel column to obtain yellow solid Int-5 with the yield of 79%.
And a sixth step: preparation of Compound M473
Figure BDA0003745460580000141
10.0mmol of intermediate Int-5 was dissolved in 60mL of THF and 10mL of triethylamine, 0.5g of 10% palladium on carbon was added, hydrogen was introduced to 0.1MPa, the reaction was stirred at room temperature for 12 hours, filtered, the cake was washed with THF, the filtrate was concentrated under reduced pressure to dryness, separated and purified by a silica gel column, and recrystallized from toluene/THF to give M473 as a yellow solid in 98% yield, MS (MALDI-TOF): 623.2243[ M + H ] M/z] + ； 1 HNMR(δ、CDCl 3 )：8.56(1H,s)；8.35～8.32(2H,m)；8.21～8.13(3H,m)；7.95～7.89(3H,m)；7.75～7.72(2H,m)；7.65～7.63(2H,m)；7.51～7.42(8H,m)；7.40～7.36(3H,m)；7.27～7.24(2H,m)。
With reference to the above synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
Figure BDA0003745460580000142
Figure BDA0003745460580000151
Figure BDA0003745460580000161
Figure BDA0003745460580000171
Example 2
A process for the preparation of compound M522 comprising the steps of:
the first step is as follows: preparation of intermediate Int-6
Figure BDA0003745460580000172
Under the protection of nitrogen, 20.0mmol of Int-4 (reactant 1), 22.0mmol of phenylboronic acid (reactant 2), 45.0mmol of anhydrous potassium carbonate, 0.01mmol of Pd0132, 40mL of toluene, 20mL of ethanol and 20mL of water are mixed, heated to reflux, stirred and reacted for 12 hours, cooled to room temperature, 50mL of water is added, EA is used for extraction, an organic phase is dried, filtered, concentrated under reduced pressure and dried, and silica gel column separation and purification are carried out to obtain yellow solid Int-6, wherein the yield is as follows: 87 percent.
With reference to the analogous synthetic procedures described above, the following compounds were prepared:
Figure BDA0003745460580000173
the second step is that: preparation of Compound M522
Figure BDA0003745460580000181
10.0mmol of intermediate Int-6 are dissolved in 40mL of dry DMSO under nitrogen, 12.0mmol of a 65% sodium hydride solid is added, the mixture is stirred and reacted for 30 minutes, 12.0mmol of 2-chloro-4-naphthyl-6-phenyl-1, 3, 5-triazine (reactant 3) is added, the mixture is heated to 45 ℃ and stirred and reacted for 12 hours, the temperature is reduced to room temperature, the reaction solution is poured into 150mL of ice water, filtered, the filter cake is washed with water and ethanol, the separation and purification are carried out by a silica gel column, and the mixture is recrystallized from toluene/THF to obtain a yellow solid M522, yield 87%, MS (MALDI-TOF): 673.2406[ M + H ] M/z] + ； 1 HNMR(δ、CDCl 3 )：8.93(1H,s)；8.58～8.52(5H,m)；8.48～8.41(2H,m)；8.15～8.11(2H,m)；8.04～8.02(1H,d)；7.86～7.75(7H,m)；7.62～7.51(4H,m)；7.45～7.35(6H,m)。
With reference to the above synthetic method, the following compounds shown in table 2 were prepared:
TABLE 2
Figure BDA0003745460580000182
Figure BDA0003745460580000191
Figure BDA0003745460580000201
Figure BDA0003745460580000211
Example 3
A process for the preparation of compound M573, comprising the steps of:
the first step is as follows: preparation of intermediate Int-7
Figure BDA0003745460580000212
10.0mmol of intermediate Int-4 (reaction 1) was dissolved in 40mL of THF and 10mL of triethylamine, 0.2g of 10% palladium/carbon was added, hydrogen was introduced to 0.1MPa, the reaction was stirred at room temperature for 12 hours, filtered, the cake was washed with THF, the filtrate was concentrated under reduced pressure to dryness, separated and purified by a silica gel column, and recrystallized from toluene/THF to obtain compound Int-7 with a yield of 100%.
The second step is that: preparation of Compound M573
Figure BDA0003745460580000213
Under the protection of nitrogen, 10.0mmol of intermediate Int-7 is dissolved in 50mL of dry xylene, and 12.0mmol of 2- ([1,1' -biphenyl) is added]-3-yl) -4- (2-bromophenyl) -6-phenyl-1, 3, 5-triazine (reaction 2), 15.0mmol sodium tert-butoxide, 0.1mmol Pd 2 (dba) 3 And 0.2mmol of XPhos, heated to 110 ℃, stirred to react for 12 hours, cooled to room temperature, added with 50mL of water, filtered, washed with water and ethanol, separated and purified by a silica gel column, and recrystallized from dichloromethane/THF to obtain M573 as a yellow solid with a yield of 87%, MS (MALDI-TOF): 699.2562[ M + H ] M/z] + ； 1 HNMR(δ、CDCl 3 )：9.12(1H,s)；8.36～8.32(3H,m)；8.21～8.14(3H,m)；7.99～7.97(1H,m)；7.94～7.89(3H,m)；7.81～7.72(4H,m)；7.66～7.59(3H,m)；7.49～7.36(9H,m)；7.34～7.29(3H,m)。
With reference to the above synthetic method, the following compounds shown in table 4 were prepared:
TABLE 4
Figure BDA0003745460580000214
Figure BDA0003745460580000221
Figure BDA0003745460580000231
Figure BDA0003745460580000241
In the above examples 1 to 3, — G — is selected from — _ O —, — _ S —, or one of the following structures:
Figure BDA0003745460580000251
example 4
An OLED element, as shown in fig. 1, the OLED element of this embodiment is a top emission light element, and includes a substrate 101, an anode layer 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode layer 102, a hole transport layer 104 disposed on the hole injection layer 103, an electron blocking layer 105 disposed on the hole transport layer 104, an organic light emitting layer 106 disposed on the electron blocking layer 105, an electron transport layer 107 disposed on the organic light emitting layer 106, an electron injection layer 108 disposed on the electron transport layer 107, a cathode layer 109 disposed on the electron injection layer 108, and a capping layer 110 disposed on the cathode 109, and the method for manufacturing the OLED element includes 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, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to 1 × 10 -5 ～9×10 -3 Pa, depositing silver on the ITO film as anode layer to obtain a deposited film with a thickness of
Figure BDA0003745460580000253
Continuing to respectively evaporate compounds HI01 and HI101 as hole injection layers, wherein HI101 is 3% of HI01 by mass, and the thickness of the evaporated film is
Figure BDA0003745460580000254
3) The compound HTM102 is continuously deposited on the hole injection layer to form a hole transport layer, and the thickness of the deposited layer is
Figure BDA0003745460580000255
4) Continuously depositing a compound EBL on the hole injection layer to form an electron blocking layer with a thickness of
Figure BDA0003745460580000256
5) The compound of the invention with formula (I) as a host material and RD012 as a doping material are continuously evaporated on the electron blocking layer, RD012 is 3% of the mass of formula (I), the organic luminescent layer of the element is formed, and the thickness of the organic luminescent layer obtained by evaporation is the film thickness
Figure BDA0003745460580000257
6) Continuously evaporating a layer of LiQ and ET010 on the organic light-emitting layer to be used as an electron transport layer of the element, wherein the ET010 accounts for 50 percent of the mass of the LiQ, and the thickness of the evaporated film is
Figure BDA0003745460580000259
7) Continuously evaporating a layer of LiF on the electron transport layer to form an electron injection layer, wherein the thickness of the evaporated film is
Figure BDA00037454605800002510
8) Depositing a transparent cathode layer with Mg and Ag as elements on the electron injection layer at a mass ratio of 1:10 and a thickness of the deposited film
Figure BDA00037454605800002511
9) In the transparent stateA CPL layer as an element is formed by vapor deposition of an NPD layer on the cathode layer with a thickness of
Figure BDA00037454605800002512
The OLED element provided by the invention is obtained.
The compound used in example 4 above has the following structure:
Figure BDA0003745460580000252
example 5
An organic electroluminescent device 200 is shown in fig. 2 and comprises a substrate 201, an anode 202, a hole injection 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 213.
Comparative example 1
Following the same procedure as in example 4, the compound (formula I) in step 5) was replaced with HS01 to give comparative element 1;
Figure BDA0003745460580000261
comparative example 2
Following the same procedure as in example 4, the compound (formula I) in step 5) was replaced with HS02 to give comparative element 2;
Figure BDA0003745460580000262
the organic electroluminescent element prepared by the above process was subjected to the following performance tests:
the driving voltage and current efficiency of the organic electroluminescent element prepared in example 4 and comparative examples 1 and 2 and the lifetime of the element were measured using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and the organic phase was measuredThe brightness of the electroluminescent element reaches 1000cd/m 2 The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the LT 90% lifetime test is as follows: using a luminance meter at 1000cd/m 2 The luminance decay of the organic electroluminescent element was measured to 900cd/m while maintaining a constant current at luminance 2 Time in hours. The data listed in table 5 are relative data compared to comparative element 1.
TABLE 5
Figure BDA0003745460580000263
Figure BDA0003745460580000271
Figure BDA0003745460580000281
Figure BDA0003745460580000291
Wherein Ph represents a phenyl group; PhPhPh represents biphenyl; nap represents a naphthyl group; FR represents a 9, 9-fluorenyl group.
As can be seen from table 5, the driving voltage of the device prepared by the compound of the present invention is lower than that of HS01 under the same brightness, the current efficiency is improved significantly, which is up to 1.2 times that of the comparative device, and the LT 90% lifetime of the device is greatly improved.
The compound HS01 in comparative example 1 is different from the compound of the present invention in that the plane conjugation ability of benzocarbazole is weak, the transport of holes and electrons is unbalanced, the ability to accept holes is stronger than the ability to accept electrons, and this imbalance of transport affects the formation of excitons in the light-emitting layer, resulting in high voltage, low efficiency, and reduced lifetime. The compound of the invention is condensed with naphthalene ring on the basis of benzocarbazole, and increases the plane conjugation of parent nucleus, so that the compound has excellent performances on molecular film formation and charge transmission, the charge transmission in the element is more balanced, and the element performance is improved.
Compared with the compound of the present invention, the compound HS02 in comparative example 2 is distinguished in that HS02 is naphthocarbazole, although the planar conjugation ability is enhanced, the planar conjugation ability is weak compared with the fused carbazole compound of the present invention, and the incorporation of naphthalene ring forms a large conjugated fused ring planar structure, so that the compound has excellent performance in molecular film formation and charge transport, the charge transport in the element is more balanced, and the element performance, especially LT 90% lifetime is much longer than that of the comparative element, and thus the carbazole derivative of the present invention is an organic electroluminescent material with excellent performance.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A carbazole derivative having a structural formula represented by formula (I):
Figure FDA0003745460570000011
wherein the content of the first and second substances,
L 1 selected from single bond, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 A heteroarylene group;
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 the same or different compounds are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl radical, C 1 -C 40 Alkoxy radical, C 2 -C 40 Alkenyl radical, C 1 -C 40 Alkylthio radical, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 1 -C 40 Alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 Silyl, substituted or unsubstituted boron group, substituted or unsubstituted amine group, substituted or unsubstituted aryl phosphine group, substituted or unsubstituted phosphine oxide group, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
n represents an integer of 0 to 5;
Ar 1 selected from substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups.
2. The carbazole derivative according to claim 1, wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylene, carbazole, dibenzofuran, or dibenzothiophene;
n is 0, 1 or 2;
Ar 1 a group selected from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,
Figure FDA0003745460570000012
Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, idobenzene, terphenyl, quaterphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluoreneCarbazole, cis-or trans-indolocarbazoles, triindenes, isotridecylines, spirotriindenes, spiroisotridecylines, furans, benzofurans, isobenzofurans, dibenzofurans, thiophenes, benzothiophenes, isobenzothiophenes, dibenzothiophenes, pyrroles, indoles, isoindoles, carbazoles, pyridines, quinolines, isoquinolines, acridines, phenanthridines, benzo [5,6 ] indenes]Quinoline, benzo [6,7 ]]Quinoline, benzo [7,8 ]]Quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxaloimidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroixazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diazahenanthrene, 2, 7-diazapyrene, 2, 3-diazapyrene, 1, 6-diazapyrene, 1, 8-diazapyrene, 4,5,9, 10-tetraazapyrene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescentrene, naphthyridine, azacarbazole, benzocarbazine, carboline, phenanthroline, 1,2, 3-triazole, perylene, 1,2, 4-triazole, benzotriazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, tetrazole, 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3, 5-tetrazine, purine, pteridine, indolizine, quinazoline, and benzothiadiazole, or a group derived from a combination of these systems.
3. The carbazole derivative according to claim 1, wherein Ar is 1 Selected from the group consisting of groups represented by II-1 to II-17:
Figure FDA0003745460570000021
wherein the content of the first and second substances,
Z 1 、Z 2 each independently selected from hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxy or carboxylate thereof,Sulfonic acid group or sulfonate, phosphoric acid group or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 o, S, CR 'R "or NAr';
r 'and R' are each independently selected from hydrogen, deuterium, C 1 ～C 40 Alkyl of (C) 1 ～C 40 With heteroalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl, 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 so formed; preferably, R', R "are methyl, phenyl or fluorenyl;
ar' is selected from C 1 ～C 40 Alkyl of (C) 1 ～C 40 Heteroalkyl of (a), C 3 ～C 40 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 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl, biphenyl or naphthyl.
4. Carbazole derivative according to claim 1, characterized in thatSaid L is 1 Selected from the group consisting of the following groups III-1 to III-15:
Figure FDA0003745460570000031
Figure FDA0003745460570000041
wherein the content of the first and second substances,
Z 11 、Z 12 each independently selected from the group consisting of hydrogen, deuterohydrogen, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxy or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
Z 13 represents substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 One or more of a heterocyclic aryl group;
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;
T 3 represents O or S.
5. The carbazole derivative according to any one of claims 1 to 4, wherein the carbazole derivative is selected from compounds represented by the following formulae M470-M622:
Figure FDA0003745460570000042
Figure FDA0003745460570000051
Figure FDA0003745460570000061
Figure FDA0003745460570000071
Figure FDA0003745460570000081
Figure FDA0003745460570000091
Figure FDA0003745460570000101
wherein G-is selected from O-, S-or one of the following structures:
Figure FDA0003745460570000102
Figure FDA0003745460570000111
6. an organic electroluminescent material, characterized in that a raw material of the organic electroluminescent material comprises the carbazole derivative as recited in any one of claims 1 to 5.
7. Use of the organic electroluminescent material according to claim 6 for the production of organic electroluminescent elements.
8. An organic electroluminescence element, characterized in that the organic electroluminescence element comprises: the organic light-emitting diode comprises a first electrode, a second electrode, a capping layer and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the carbazole derivative as recited in any one of claims 1 to 5.
9. The organic electroluminescent element according to claim 8, wherein the organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
10. A consumer product, characterized in that it comprises an organic electroluminescent element according to claim 8 or 9.
CN202210823591.7A 2022-07-14 2022-07-14 Carbazole derivative and application thereof in OLED Active CN115109039B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202210823591.7A CN115109039B (en) 2022-07-14 2022-07-14 Carbazole derivative and application thereof in OLED
PCT/CN2023/107197 WO2024012522A1 (en) 2022-07-14 2023-07-13 Carbazole derivative and use thereof in oled

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210823591.7A CN115109039B (en) 2022-07-14 2022-07-14 Carbazole derivative and application thereof in OLED

Publications (2)

Publication Number Publication Date
CN115109039A true CN115109039A (en) 2022-09-27
CN115109039B CN115109039B (en) 2024-02-02

Family

ID=83331428

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210823591.7A Active CN115109039B (en) 2022-07-14 2022-07-14 Carbazole derivative and application thereof in OLED

Country Status (2)

Country Link
CN (1) CN115109039B (en)
WO (1) WO2024012522A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116621836A (en) * 2023-05-23 2023-08-22 北京八亿时空液晶科技股份有限公司 Carbazole derivative and application thereof
WO2024012522A1 (en) * 2022-07-14 2024-01-18 上海八亿时空先进材料有限公司 Carbazole derivative and use thereof in oled
WO2024012469A1 (en) * 2022-07-14 2024-01-18 上海八亿时空先进材料有限公司 Carbazole derivative and use thereof in organic light-emitting element
EP4372067A1 (en) * 2022-11-15 2024-05-22 Canon Kabushiki Kaisha Organometallic complex and organic light-emitting element

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110437241A (en) * 2019-07-03 2019-11-12 浙江华显光电科技有限公司 A kind of red phosphorescent host compound and the organic luminescent device using the compound
CN114591328A (en) * 2022-02-28 2022-06-07 上海八亿时空先进材料有限公司 Carbazole derivative and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101603388B1 (en) * 2013-12-05 2016-03-14 주식회사 두산 Organic compounds and organic electro luminescence device comprising the same
KR101667447B1 (en) * 2013-12-17 2016-10-18 주식회사 두산 Organic compounds and organic electro luminescence device comprising the same
KR20160076302A (en) * 2014-12-22 2016-06-30 삼성디스플레이 주식회사 Condensed-cyclic compound and organic light emitting diode comprising the same
CN106866498A (en) * 2017-02-23 2017-06-20 南京高光半导体材料有限公司 Organic compound, organic electroluminescence device and its application
CN111704605B (en) * 2020-06-28 2023-09-22 宁波卢米蓝新材料有限公司 Carbazole derivative and preparation method and application thereof
CN113354624A (en) * 2021-07-10 2021-09-07 浙江华显光电科技有限公司 Organic compound and organic light-emitting device using same
CN115109039B (en) * 2022-07-14 2024-02-02 上海八亿时空先进材料有限公司 Carbazole derivative and application thereof in OLED

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110437241A (en) * 2019-07-03 2019-11-12 浙江华显光电科技有限公司 A kind of red phosphorescent host compound and the organic luminescent device using the compound
CN114591328A (en) * 2022-02-28 2022-06-07 上海八亿时空先进材料有限公司 Carbazole derivative and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PEADEN, PAUL A.: "High-performance liquid chromatographic separation of high-molecular-weight polycyclic aromatic compounds in carbon black", ANALYTICAL CHEMISTRY, vol. 52, no. 14, pages 2268 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024012522A1 (en) * 2022-07-14 2024-01-18 上海八亿时空先进材料有限公司 Carbazole derivative and use thereof in oled
WO2024012469A1 (en) * 2022-07-14 2024-01-18 上海八亿时空先进材料有限公司 Carbazole derivative and use thereof in organic light-emitting element
EP4372067A1 (en) * 2022-11-15 2024-05-22 Canon Kabushiki Kaisha Organometallic complex and organic light-emitting element
CN116621836A (en) * 2023-05-23 2023-08-22 北京八亿时空液晶科技股份有限公司 Carbazole derivative and application thereof

Also Published As

Publication number Publication date
WO2024012522A1 (en) 2024-01-18
CN115109039B (en) 2024-02-02

Similar Documents

Publication Publication Date Title
CN115109039B (en) Carbazole derivative and application thereof in OLED
CN115073461B (en) Carbazole derivative and application thereof in organic light-emitting element
CN115093414B (en) Carbazole derivative and organic light-emitting element comprising same
CN114181095B (en) Arylamine compound and organic electroluminescent element containing the same
WO2023236955A1 (en) Polysubstituted carbazole derivative and use thereof
CN114957226B (en) Phenanthridine derivative and application thereof
WO2023151394A1 (en) Fluorene derivative and use thereof
CN114890996B (en) Heterocyclic compound and organic light-emitting element comprising same
CN115304497B (en) Fluorene derivative containing homotriptycene and application thereof
CN115322177A (en) Fluorene derivative and application thereof
CN115124433A (en) Spirobifluorene derivative and application thereof
WO2023241569A1 (en) Aza-adamantane compound and organic electroluminescent element
CN114605411B (en) Acridine derivative and application thereof
CN114605314B (en) Indene derivative and application thereof
CN115073306A (en) Acenaphthene derivative and organic electroluminescent element containing same
CN114437095B (en) Heterocyclic compound, organic electroluminescent material and device
CN114907394A (en) Silafluorene derivative and organic electroluminescent element containing same
CN116354833A (en) High triptycene derivative and application thereof
CN114456167A (en) Azafluoranthene derivative and application thereof
CN114456076B (en) Fluorene derivative and organic electroluminescent element comprising same
CN112812023A (en) Organic compound, material for organic electroluminescent element, and organic electroluminescent element
CN115322104B (en) Fluorene derivative and organic light-emitting element comprising same
CN115724749B (en) Fluorene derivative and organic light-emitting element comprising same
CN114890959A (en) Fluoranthene derivative and application thereof
CN115108921A (en) Acenaphthene derivative and application thereof

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