CN113651785A - Heterocyclic compound and organic light-emitting device thereof - Google Patents

Heterocyclic compound and organic light-emitting device thereof Download PDF

Info

Publication number
CN113651785A
CN113651785A CN202111095320.6A CN202111095320A CN113651785A CN 113651785 A CN113651785 A CN 113651785A CN 202111095320 A CN202111095320 A CN 202111095320A CN 113651785 A CN113651785 A CN 113651785A
Authority
CN
China
Prior art keywords
substituted
unsubstituted
layer
group
deuterated
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
CN202111095320.6A
Other languages
Chinese (zh)
Other versions
CN113651785B (en
Inventor
孙敬
韩春雪
王海丹
李梦茹
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.)
Changchun Hyperions Technology Co Ltd
Original Assignee
Changchun Hyperions Technology 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 Changchun Hyperions Technology Co Ltd filed Critical Changchun Hyperions Technology Co Ltd
Priority to CN202111095320.6A priority Critical patent/CN113651785B/en
Publication of CN113651785A publication Critical patent/CN113651785A/en
Application granted granted Critical
Publication of CN113651785B publication Critical patent/CN113651785B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C07B59/002—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • 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
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • 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
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • 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
    • C07D405/02—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 two hetero rings
    • C07D405/12—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 two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • 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
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • 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
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. 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
    • 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
    • H10K85/631—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
    • H10K85/654—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
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/05—Isotopically modified compounds, e.g. labelled
    • 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
    • C09K2211/1022—Heterocyclic 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • 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
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • 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)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides a heterocyclic compound and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The compound takes triarylamine as a center, introduces a dibenzo five-membered ring group connected to the 9-position of fluorenyl, introduces a cycloalkyl (adamantane/norbornane or derivatives thereof) with a stereo configuration or an N-heterocycloalkyl with electron-pushing capability, and introduces two specific groups, so that the material has proper hole mobility, thereby improving the luminous efficiency and the service life of an organic light-emitting device and reducing the driving voltage of the device. The heterocyclic compound provided by the invention is used as a covering layer material to be applied to an organic light-emitting device, so that the light-emitting efficiency of the organic light-emitting device can be improved, and the service life of the device can be prolonged. The heterocyclic compound has good physical and thermal stability, and can be widely applied to the fields of panel display, lighting sources, organic solar cells, organic photoreceptors or organic thin film transistors and the like.

Description

Heterocyclic compound and organic light-emitting device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a heterocyclic compound and an organic light-emitting device thereof.
Background
The organic electroluminescence refers to a phenomenon that an organic semiconductor material emits light by carrier injection, transport and recombination to form excitons and exciton decay under the drive of an electric field. Displays produced according to this principle of light emission are OLEDs. Compared with the conventional display technology, OLEDs have the following characteristics: (1) the material selection range is wide, and the light emitting of any color from red light to blue light can be realized; (2) the energy consumption is low, the driving voltage is low (generally only 3-12V direct current voltage is needed); (3) the luminous brightness is high, the viewing angle is wide, and the response speed is high; (4) the light-emitting diode is ultrathin, light in weight and capable of emitting light in a fully-cured active mode; (5) the display device can be manufactured on a flexible substrate, and the device can be bent and folded, and can also realize transparent display; (6) the working temperature range is wide; (7) the molding process is relatively simple, and complicated images can be formed and mass-produced in a large area by a spin coating technique, an inkjet printing technique, or the like. OLEDs are considered to be the mainstream of next-generation display technologies, and have attracted wide attention from both academic and industrial circles at home and abroad.
At present, the organic light emitting device mainly adopts a sandwich-type layered structure, and can be divided into: bottom emitting organic light emitting devices, top emitting organic light emitting devices. Bottom-emitting organic light emitting device structures typically include a transparent ITO anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode, and the like. Top-emitting organic light emitting device structures typically include an opaque ITO anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode, a capping layer, and the like. The hole/electron injection layer is mainly used for reducing an injection barrier between the electrode and the corresponding carrier transport layer to improve the injection efficiency of carriers and reduce the driving voltage of the device, and the hole/electron transport layer is used for the migration of the corresponding carriers in the device and is mainly used for improving the mobility of the carriers in the device and reducing the driving voltage of the device, so that the luminous efficiency is improved; the luminescent layer can be composed of a single substance or a host material and a guest doping material; the covering layer is mainly applied to a top-emission organic light-emitting device, is positioned on one side of the cathode, which is far away from the anode, and generally adopts an organic electroluminescent material with a larger refractive index, so that the total reflection of light inside the device is reduced, and the light-emitting efficiency of the device is improved.
In recent years, with continuous progress of industrial technologies, the luminous efficiency and the service life of an organic light emitting device have been advanced sufficiently, but unbalanced carrier injection inside the device and low light extraction efficiency are main problems in the industry, so that the development of a material capable of promoting carrier injection balance and improving light extraction efficiency is an urgent problem to be solved.
Disclosure of Invention
The present invention aims to provide a heterocyclic compound and an organic light emitting device thereof, which are prepared by using the heterocyclic compound, based on the prior art and aiming at industrialization, and the organic light emitting device prepared by using the heterocyclic compound is applied to a hole transport layer or an auxiliary hole transport layer (a second hole transport layer) to develop an organic light emitting device with low driving voltage, high light emitting efficiency and long service life, or is applied to a cover layer to improve the light emitting efficiency and the service life of the organic light emitting device, and the molecular structure formula of the heterocyclic compound is shown as formula i:
Figure BDA0003268998140000011
wherein X is selected from O or S;
ar is1One selected from the following groups:
Figure BDA0003268998140000021
the R is0One or adjacent R selected from hydrogen, deuterium, halogen atoms, cyano, C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl0Can be connected into a ring;
ar is selected from one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;
k is1Selected from 0,1 or 2;
k is2Selected from 0,1, 2,3 or 4;
k is3Selected from 0,1, 2,3, 4,5 or 6;
k is4Selected from 0,1, 2,3, 4,5, 6,7 or 8;
k is5Selected from 0,1, 2,3, 4,5, 6,7, 8,9 or 10;
k is6Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11;
k is7Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10,11 or 12;
k is8Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10,11, 12, 13 or 14;
k is9Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10,11, 12, 13, 14 or 15;
ar is2One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C25 heteroaryl;
the R is selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;
said L0、L1、L2、LaIndependently selected from a single bond, substituted or unsubstituted arylene of C6-C25, substituted or unsubstituted heteroarylene of C2-C20;
the R is1、R2、R3、R4The same or different from each other, and each is independently selected from one of hydrogen, deuterium, a halogen atom, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, or adjacent R1Adjacent R2Adjacent R3Adjacent R4Can be connected into a ring structure;
a is selected from 0,1, 2,3 or 4;
b is selected from 0,1, 2,3 or 4;
c is selected from 0,1, 2 or 3;
d is selected from 0,1, 2 or 3.
The invention also provides an organic light-emitting device which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or positioned outside more than one of the anode and the cathode, and the organic layer contains any one or the combination of at least two of the heterocyclic compounds.
The invention has the beneficial effects that:
the invention provides a heterocyclic compound and an organic light-emitting device thereof, the compound takes triarylamine as a center, a 9-position of fluorenyl is connected with a dibenzo five-membered ring as a substituent group on the triarylamine, the introduction of the substituent group can reduce the conjugation degree of the compound so as to reduce the hole mobility, the other substituent group is cycloalkyl (adamantane/norbornane or derivatives thereof) with a three-dimensional configuration or N-heterocycloalkyl (three-membered ring to eight-membered ring) with electron-pushing capability, compared with aromatic groups, the heterocyclic compound has stronger electron-pushing capability and further enhances the electron-donating capability of the compound, and the introduction of two specific groups ensures that the compound has proper hole mobility, the compound has excellent hole transmission performance, is a good hole transmission material, can improve the light-emitting efficiency of the organic light-emitting device and prolong the service life of the device, and the driving voltage of the device can be reduced.
The heterocyclic compound can also be used as a covering layer material to be applied to an organic light-emitting device, can effectively solve the problem of total emission of an interface of an ITO film and a glass substrate and an interface of the glass substrate and air, reduces total reflection loss and waveguide loss in the OLED device, and improves light extraction efficiency, thereby improving the light-emitting efficiency of the organic light-emitting device. In addition, the heterocyclic compound provided by the invention can improve the molecular weight of the material, reduce the molecular symmetry, improve the glass transition temperature and the evaporation temperature of the material, control the crystallinity of the material, has good physical and thermal stability and can prolong the service life of the organic light-emitting device on the premise of avoiding an over-strong pi-pi stacking effect.
Detailed Description
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.
Halogen as referred to herein means fluorine, chlorine, bromine and iodine.
The alkyl group in the present invention refers to a hydrocarbon group obtained by dropping one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group or a branched-chain alkyl group, and preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight chain alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but is not limited thereto; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, the isomeric form of n-pentyl, the isomeric form of n-hexyl, the isomeric form of n-heptyl, the isomeric form of n-octyl, the isomeric form of n-nonyl, the isomeric form of n-decyl, and the like. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
The cycloalkyl group in the present invention means a hydrocarbon group obtained by subtracting one hydrogen atom from a cycloalkane molecule, and preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms, and examples thereof may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, and the like. The cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group or a norbornyl group.
The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic compound molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl group means an aryl group having only one aromatic ring in the molecule, for example, phenyl group and the like, but is not limited thereto; the polycyclic aromatic group means an aromatic group having two or more independent aromatic rings in the molecule, for example, biphenyl group, terphenyl group and the like, but is not limited thereto; the fused ring aryl group refers to an aryl group in which two or more aromatic rings are contained in a molecule and are fused together by sharing two adjacent carbon atoms, and examples thereof include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, spirobifluorenyl, and the like. The above aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthryl group (preferably a 2-anthryl group), a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylene group, or a spirobifluorenyl group.
The heteroaryl group in the present invention refers to a general term of a group obtained by replacing one or more aromatic nucleus carbon atoms in an aryl group with a heteroatom, including but not limited to oxygen, sulfur, nitrogen or phosphorus atom, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, the attachment site of the heteroaryl group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group. The monocyclic heteroaryl group includes pyridyl, pyrimidyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl and the like, but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, phenylpyridyl, and the like, but is not limited thereto; the fused ring heteroaryl group includes quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl and the like, but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a dibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group or a phenoxathiyl group.
The alkenyl group in the present invention means a monovalent group obtained by removing one hydrogen atom from an olefin molecule, and includes a monoalkenyl group, a dienyl group, a polyalkenyl group, and the like. Preferably from 2 to 60 carbon atoms, more preferably from 2 to 30 carbon atoms, particularly preferably from 2 to 15 carbon atoms, most preferably from 2 to 6 carbon atoms. Examples of the alkenyl group include vinyl, butadienyl and the like, but are not limited thereto. The alkenyl group is preferably a vinyl group.
The cycloalkenyl group in the present invention means a monovalent group obtained by removing one hydrogen atom from a cycloolefin molecule, and is a cyclic hydrocarbon group having an intra-cyclic carbon-carbon double bond, and includes cyclic monoolefin, cyclic polyene and the like. Preferably from 2 to 60 carbon atoms, more preferably from 2 to 30 carbon atoms, particularly preferably from 2 to 15 carbon atoms, most preferably from 2 to 6 carbon atoms. Examples of the alkenyl group include cyclopropene, cyclobutene, cyclopentene and cyclohexene, cyclobutadiene, cyclopentadiene and the like, but are not limited thereto.
The arylene group in the present invention refers to a general term of divalent groups remaining after two hydrogen atoms are removed from the aromatic core carbon of the aromatic compound molecule, and may be monocyclic arylene group, polycyclic arylene group or condensed ring arylene group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic arylene group includes phenylene group and the like, but is not limited thereto; the polycyclic arylene group includes, but is not limited to, biphenylene, terphenylene, and the like; the condensed ring arylene group includes naphthylene, anthrylene, phenanthrylene, fluorenylene, pyrenylene, triphenylene, fluoranthenylene, phenylfluorenylene, and the like, but is not limited thereto. The arylene group is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a fluorenylene group, or a phenylfluorenylene group.
Heteroarylene as used herein refers to the generic term for groups in which one or more of the aromatic core carbons in the arylene group is replaced with a heteroatom, including, but not limited to, oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, the linking site of the heteroarylene group may be located on a ring-forming carbon atom or on a ring-forming nitrogen atom, and the heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a fused ring heteroarylene group. The monocyclic heteroarylene group includes a pyridylene group, a pyrimidylene group, a triazinylene group, a furanylene group, a thiophenylene group and the like, but is not limited thereto; the polycyclic heteroarylene group includes bipyridyl idene, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroarylene group includes, but is not limited to, a quinolylene group, an isoquinolylene group, an indolyl group, a benzothiophene group, a benzofuranylene group, a benzoxazolyl group, a benzimidazolylene group, a benzothiazolyl group, a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolyl group, a benzocarbazolyl group, an acridinylene group, a 9, 10-dihydroacridine group, a phenoxazinyl group, a phenothiazinylene group, a phenoxathiin group and the like. The heteroaryl group is preferably a pyridylene group, pyrimidylene group, thienylene group, furylene group, benzothienylene group, benzofuranylene group, benzoxazolyl group, benzimidazolylene group, benzothiazolyl group, dibenzofuranylene group, dibenzothiophenylene group, dibenzofuranylene group, carbazolyl group, acridinylene group, phenoxazinyl group, phenothiazinylene group, phenoxathiin group.
The term "substituted …" as used herein, such as substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted cycloalkenyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, and the like, means mono-or poly-substituted with groups independently selected from, but not limited to, deuterium, halogen, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, substituted or unsubstituted amine, and the like, preferably with groups selected from deuterium, methyl, ethyl, isopropyl, t-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylene, pyrenyl, benzyl, tolyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9-diphenylfluorenyl, 9-phenylfluorenyl, and the like, Groups of dianilino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzofuryl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuryl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl are mono-or polysubstituted. In addition, the above substituents may be substituted with one or more substituents selected from deuterium, a halogen atom, cyano, alkyl, cycloalkyl, and aryl.
The term "ring" as used herein, unless otherwise specified, refers to a fused ring consisting of an aromatic ring having 6 to 60 carbon atoms, preferably 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms, or a heterocyclic ring having 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, or a combination thereof, which contains a saturated or unsaturated ring.
In this specification, when a substituent is not fixed in position on a ring, it means that it can be attached to any of the respective optional sites of the ring. For example,
Figure BDA0003268998140000061
can represent
Figure BDA0003268998140000062
And so on.
The bonding to form a cyclic structure according to the present invention means that the two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:
Figure BDA0003268998140000063
in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a condensed ring, such as benzene, naphthalene, fluorene, cyclopentene, cyclopentane, cyclohexane acene, pyridine, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but not limited thereto.
The invention provides a heterocyclic compound, the molecular structural general formula of which is shown as formula I:
Figure BDA0003268998140000064
wherein X is selected from O or S;
ar is1One selected from the following groups:
Figure BDA0003268998140000065
the R is0One or adjacent R selected from hydrogen, deuterium, halogen atoms, cyano, C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl0Can be connected into a ring;
ar is selected from one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;
k is1Selected from 0,1 or 2;
k is2Selected from 0,1, 2,3 or 4;
k is3Selected from 0,1, 2,3, 4,5 or 6;
k is4Selected from 0,1, 2,3, 4,5, 6,7 or 8;
k is5Selected from 0,1, 2,3, 4,5, 6,7, 8,9 or 10;
k is6Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11;
k is7Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10,11 or 12;
k is8Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10,11, 12, 13 or 14;
k is9Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10,11, 12, 13, 14 or 15;
ar is2One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C25 heteroaryl;
the R is selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;
said L0、L1、L2、LaIndependently selected from a single bond, substituted or unsubstituted arylene of C6-C25, substituted or unsubstituted heteroarylene of C2-C20;
the R is1、R2、R3、R4The same or different from each other, and each is independently selected from one of hydrogen, deuterium, a halogen atom, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, or adjacent R1Adjacent R2Adjacent R3Adjacent R4Can be connected into a ring structure;
a is selected from 0,1, 2,3 or 4;
b is selected from 0,1, 2,3 or 4;
c is selected from 0,1, 2 or 3;
d is selected from 0,1, 2 or 3.
Preferably, the "substituted …" in the "substituted or unsubstituted …" is substituted with one or more substituents independently selected from the group consisting of deuterium, cyano, substituted or unsubstituted C1 to C15 alkyl, substituted or unsubstituted C3 to C15 cycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 cycloalkenyl, substituted or unsubstituted C6 to C25 aryl, and substituted or unsubstituted C2 to C20 heteroaryl.
Preferably, said R is0One or more selected from hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl, or adjacent R0May be linked to a benzene ring or a naphthalene ring, and in the case of being substituted with a plurality of substituents, the plurality of substituents may be the same as or different from each other;
ar is selected from one of deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl and naphthyl.
More preferably, Ar is1One selected from the following groups:
Figure BDA0003268998140000081
Figure BDA0003268998140000091
preferably, Ar is2Any one selected from the following groups:
Figure BDA0003268998140000092
Figure BDA0003268998140000101
the R is12One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl;
the R is13One of deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or adjacent R13Can be connected into a ring structure;
wherein said R13Can also be substituted by R23Substituted, R23One or more substituents selected from the group consisting of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl, and, in the case of substitution with a plurality of substituents, the plurality of substituents may be the same or different from each other;
at least one X is selected from N, and the rest X is selected from CR13；
A' is 0,1 or 2; a is a0Is 0,1, 2 or 3; a is a1Is 0,1, 2,3 or 4; a is a2Is 0,1, 2,3, 4 or 5; a is a3Is 0,1, 2,3, 4,5, 6 or 7; a is a4Is 0,1, 2,3, 4,5, 6,7 or 8; a is a5Is 0,1, 2,3, 4,5, 6,7, 8 or 9.
Preferably, Ar is2Any one selected from the following groups:
Figure BDA0003268998140000111
Figure BDA0003268998140000121
Figure BDA0003268998140000131
preferably, R is selected from one of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, and dibenzofuranyl.
Further preferably, R is selected from hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl or one of the following groups:
Figure BDA0003268998140000132
preferably, said R is1、R2、R3、R4Are the same or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, a halogen atom, cyano group, methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclopentyl group, cyclobutyl group, adamantyl group, norbornyl group, phenyl group, tolyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, triphenylene group, phenyl-naphthyl group, acridinyl group, spirobifluorenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, carbazolyl group, 9-phenylcarbazolyl group, pyrenyl group, indolyl group, acridinyl group, pyridyl group, furyl group, thienyl group, benzothienyl group, benzofuryl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl groupOne of dibenzothienyl, dibenzofuranyl, phenothiazinyl, phenoxazinyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl, deuterated terphenyl, deuterated anthracenyl, deuterated phenanthrenyl, deuterated triphenylenyl, deuterated phenyl-naphthyl, deuterated phenyl-deuterated naphthyl, deuterated dibenzothienyl, deuterated dibenzofuranyl, deuterated 9, 9-dimethylfluorenyl, deuterated 9, 9-diphenylfluorenyl and deuterated spirobifluorenyl, or adjacent R1Adjacent R2Adjacent R3Adjacent R4Can be connected into a ring structure.
Preferably, said R is1、R2、R3、R4The same or different from each other, and each is independently selected from hydrogen, deuterium, a halogen atom, a cyano group, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a cyclohexyl group, a cyclopentyl group, a cyclobutyl group, an adamantyl group, a norbornyl group or one of the following substituents:
Figure BDA0003268998140000133
Figure BDA0003268998140000141
or adjacent R1Adjacent R2Adjacent R3Adjacent R4Can be connected into benzene ring or naphthalene ring.
More preferably, R is1、R2、R3、R4The same or different from each other, and each is independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, or one of the following substituents:
Figure BDA0003268998140000142
preferably, said L0、L1、L2、LaIndependently selected from a single bond or one of the following groups:
Figure BDA0003268998140000143
wherein R isaOne or more selected from deuterium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, and pentadeuterated phenyl, and in the case of substitution with a plurality of substituents, the plurality of substituents may be the same or different from each other;
m is 0,1 or 2; n is 0,1, 2 or 3; p is 0,1, 2,3 or 4; q is 0,1, 2,3, 4 or 5; and r is 0,1, 2,3, 4,5 or 6.
Preferably, said L0、L1、L2、LaIndependently selected from a single bond or one of the following groups:
Figure BDA0003268998140000144
more preferably, said L0、L1、L2、LaIndependently selected from a single bond or one of the following groups:
Figure BDA0003268998140000151
most preferably, the heterocyclic compound is selected from any one of the chemical structures shown below:
Figure BDA0003268998140000161
Figure BDA0003268998140000171
Figure BDA0003268998140000181
Figure BDA0003268998140000191
Figure BDA0003268998140000201
Figure BDA0003268998140000211
Figure BDA0003268998140000221
Figure BDA0003268998140000231
Figure BDA0003268998140000241
Figure BDA0003268998140000251
Figure BDA0003268998140000261
Figure BDA0003268998140000271
Figure BDA0003268998140000281
the heterocyclic compounds of formula I of the present invention can be prepared by coupling reactions conventional in the art, for example, by the following synthetic routes, but the present invention is not limited thereto:
Figure BDA0003268998140000291
the preparation method of the heterocyclic compound shown in the formula I comprises the following steps of firstly preparing an intermediate A, namely, under the nitrogen atmosphere, carrying out a Buchwald reaction on an amine compound a and a halogen compound b to obtain the intermediate A; then preparing an intermediate M, namely, carrying out lithiation reaction on a double-halogen compound c in an n-butyllithium environment to obtain a lithium compound, and simultaneously reacting the lithium compound with a compound d to obtain the intermediate M; the intermediate M and the intermediate A are subjected to a Buchwald reaction and react under a corresponding catalyst, an organic base, a ligand, a solution and a corresponding temperature to obtain the compound shown in the formula I, wherein B0、B1、B2Represents Cl, Br or I.
Alternatively, intermediate M can be converted to another intermediate M by Suzuki reaction, and then subjected to Buhward reaction with intermediate A and reacted with corresponding catalyst, organic base, ligand, solution and corresponding temperature to obtain the compound of formula I, wherein B0、B1、B2Represents Cl, Br or I.
The present invention is not particularly limited in terms of the source of the raw materials used in the above-mentioned various reactions, and can be obtained using commercially available raw materials or by a preparation method known to those skilled in the art. The present invention is not particularly limited to the above-mentioned reaction, and a conventional reaction known to those skilled in the art may be used. The compound provided by the invention has the advantages of few synthesis steps and simple method, and is beneficial to industrial production.
The invention also provides an organic light-emitting device which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or positioned outside more than one of the anode and the cathode, and the organic layer contains any one or the combination of at least two of the heterocyclic compounds.
Preferably, the organic layer includes a hole transport layer containing any one or a combination of at least two of the heterocyclic compounds according to the present invention.
Preferably, the hole transport layer includes a first hole transport layer and a second hole transport layer, and the first hole transport layer and/or the second hole transport layer contains any one or a combination of at least two of the heterocyclic compounds described in the present invention.
Preferably, the organic layer includes a capping layer containing any one or a combination of at least two of the heterocyclic compounds of the present invention.
Preferably, the cover layer according to the present invention may have a single-layer structure, a two-layer structure or a multi-layer structure, and the cover layer material according to the present invention may have at least one selected from the heterocyclic compounds according to the present invention, or may contain a conventional cover layer material known to those skilled in the art.
Preferably, the organic light emitting device of the present invention is selected from the following structures, but is not limited thereto:
(1) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;
(2) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode;
(3) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/hole blocking layer/cathode;
(4) anode/hole transport layer/light emitting layer/electron transport layer/cathode;
(5) anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(6) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode;
(7) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(8) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/cathode;
(9) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(10) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;
(11) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(12) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;
(13) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(14) anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode;
(15) anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
(16) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode;
(17) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
(18) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode/capping layer;
(19) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;
(20) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(21) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;
(22) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(23) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode/capping layer;
(24) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
(25) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;
(26) anode/hole injection layer/hole buffer layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
(27) anode/hole injection layer/hole buffer layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;
(28) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode;
(29) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron injection layer/cathode;
(30) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;
(31) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/cathode;
(32) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron injection layer/cathode;
(33) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/cathode/capping layer;
(34) anode/hole injection layer/hole transport layer/light emitting layer/cathode/capping layer;
(35) anode/hole injection layer/hole transport layer/light emitting layer/cathode;
(36) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/cathode;
(37) anode/hole injection layer/first hole transport layer/second hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode/capping layer;
(38) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;
(39) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode;
(40) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode;
(41) an anode/a first hole transport layer/a second hole transport layer/a light emitting layer/an electron transport layer/a cathode;
(42) an anode/a first hole transport layer/a second hole transport layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;
(43) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/cathode;
(44) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(45) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/cathode;
(46) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode;
(47) an anode/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/a cathode;
(48) an anode/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;
(49) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/a cathode;
(50) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;
(51) an anode/a first hole transport layer/a second hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/a cathode;
(52) an anode/a first hole transport layer/a second hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;
(53) anode/hole injection layer/first hole transport layer/second hole transport layer/luminescent layer/hole blocking layer/electron transport layer/cathode;
(54) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;
(55) anode/hole injection layer/first hole transport layer/second hole transport layer/luminescent layer/hole blocking layer/electron transport layer/cathode/capping layer;
(56) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/a cathode;
(57) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;
(58) an anode/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/a cathode;
(59) an anode/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;
(60) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/cathode/capping layer;
(61) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;
(62) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode/a capping layer;
(63) an anode/a hole injection layer/a hole buffer layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;
(64) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;
(65) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode;
(66) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/electron injection layer/cathode;
(67) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;
(68) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/a cathode;
(69) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron injection layer/a cathode;
(70) anode/hole injection layer/first hole transport layer/second hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/cathode/capping layer;
(71) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/cathode/capping layer;
(72) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/cathode;
(73) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/light emitting layer/cathode;
(74) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer.
However, the structure of the organic light emitting device is not limited thereto. The organic light-emitting device can be selected and combined according to the parameter requirements of the device and the characteristics of materials, and part of organic layers can be added or omitted. For example, an electron buffer layer can be added between the electron transport layer and the electron injection layer; the organic layer having the same function may be formed in a stacked structure of two or more layers, for example, the electron transport layer may have a first electron transport layer and a second electron transport layer.
The light emitting device of the present invention is generally formed on a substrate. The substrate may be any substrate as long as it does not change when forming an electrode or an organic layer, for example, a substrate of glass, plastic, a polymer film, silicon, or the like. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.
The anode material is preferably a material having a large work function so that holes are smoothly injected into the organic material layer, and a conductive metal oxide film, a translucent metal thin film, or the like is often used. For example, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from small molecular materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and polymer materials such as poly-p-phenylene derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polyvinylcarbazole and its derivatives, polysilane and its derivatives, in addition to the heterocyclic compound of the present invention, but is not limited thereto. Preferably, the hole transport layer of the present invention is selected from the group consisting of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (abbreviated as NPB), N '-di (naphthalene-1-yl) -N, N' -di (phenyl) -2,2 '-dimethylbenzidine (abbreviated as. alpha. -NPD), N' -diphenyl-N, N '-di (3-methylphenyl) -1,1' -biphenyl-4, 4 '-diamine (abbreviated as TPD), 4' -cyclohexyldi [ N, N-di (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetra (diphenylamino) -9, 9-spirobifluorene (abbreviated as spirobifluorene-TAD) and the like can be a single structure formed by a single substance, can also be a single-layer structure or a multi-layer structure formed by different substances, and more preferably, the hole transport layer is any one or the combination of at least two of the heterocyclic compounds. The material of the hole transport region may comprise a first hole transport layer material and/or a second hole transport layer material.
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. The hole injection material of the present invention may be a metal oxide such as molybdenum oxide, silver oxide, vanadium oxide, tungsten oxide, ruthenium oxide, nickel oxide, copper oxide, or titanium oxide, or a low molecular weight organic compound such as a phthalocyanine-based compound or a polycyano group-containing conjugated organic material, but is not limited thereto. Preferably, the hole injection layer of the present invention is selected from 4,4 '-tris [ 2-naphthylphenylamino ] triphenylamine (abbreviated as 2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylamine (abbreviated as HAT-CN), 4' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4 '-tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), copper (II) phthalocyanine (abbreviated as CuPc), N' -bis [4- [ bis (3-methylphenyl) amino ] phenyl ] -N, N '-diphenyl-biphenyl-4, 4' -diamine (abbreviated as DNTPD), etc., the hole injection layer may be a single structure made of a single substance, or a single-layer or multi-layer structure made of different substances, and the hole injection layer material may include other known materials suitable for the hole injection layer, in addition to the above materials and combinations thereof.
The electron blocking layer material may be selected from N, N ' -bis (naphthalene-1-yl) -N, N ' -bis (phenyl) -2,2' -dimethylbenzidine (abbreviated as α -NPD), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (abbreviated as TPD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (abbreviated as Spiro-TAD), etc., which may be a single structure composed of a single substance, and may be a single-layer structure or a multi-layer structure formed of different substances.
The light-emitting layer includes a light-emitting material (i.e., Dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an organic light emitting device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
In the light-emitting layer of the organic light-emitting device of the present invention, a red light-emitting material, a green light-emitting material, or a blue light-emitting material can be used as the light-emitting material, and two or more light-emitting materials can be mixed if necessary. The light-emitting material may be a host material alone or a mixture of a host material and a dopant material, and the light-emitting layer is preferably formed using a mixture of a host material and a dopant material.
Preferably, the host material of the present invention is selected from 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 4-bis (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -AND), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4',1": 4', 1' -tetrabiphenyl ] -4,4' -diamino (4PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), and the like. In addition to the above materials and combinations thereof, the light emitting layer host material may also include other known materials suitable for use as a light emitting layer, such as the following light emitting layer host materials:
Figure BDA0003268998140000341
the blue luminescent layer guest is selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA for short), 2,5,8, 11-tetra-tert-butylperylene (TBPe for short), 4' -di [4- (diphenylamino) styryl group]Biphenyl (BDAVBi for short), 4' -di [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi for short), bis (2-hydroxyphenyl pyridine) beryllium (Bepp for short)2) Bis (4, 6-difluorophenylpyridine-C2, N) picolinyliridium (FIrpic), and the like, and in addition to the above materials and combinations thereof, the guest material of the blue light-emitting layer may further include other known materials suitable for use as a light-emitting layer. The green emissive guest layer is selected from tris (2-phenylpyridine) iridium (Ir (ppy)3) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy)2(acac)), etc., the green light-emitting layer guest material can include other known materials suitable for use as a light-emitting layer in addition to the above materials and combinations thereof. The red light emitting layer guest can be selected from 9, 10-di [ N- (p-tolyl) anilino]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylisoquinoline-C2, N]Iridium (III) (Ir (piq)3) Bis (1-phenylisoquinoline) (acetylacetonato) iridium (Ir (piq))2(acac)) and the like. In addition to the above materials, the red light-emitting layer guest material may also include other known materials suitable for use as a light-emitting layer.
The doping ratio of the host material and the guest material of the light-emitting layer may be preferably varied depending on the materials used, and the doping percentage of the guest material of the light-emitting layer is usually 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.
The electron transport region is located between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
The electron transport layer may include a first electron transport layer material and a second electron transport layer material. Commonly used materials for the electron transport material are known triazine derivatives, oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenoquinone derivatives, and metal complexes of 8-hydroxyquinoline and its derivatives, which may be single structures formed by a single substance or single-layer or multi-layer structures formed by different substances.
The electron injection layer is located between the electron transport layer and the cathode, and the electron injection layer may include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth metal complex, a rare earth metal complex, or any combination thereof. The alkali metal compound, alkaline earth metal compound, and rare earth metal compound may be selected from oxides and halides (e.g., fluoride, chloride, bromide, or iodide) of alkali metals, alkaline earth metals, and rare earth metals. The alkali metal may be selected from Li, Na, K, Rb and Cs. In one embodiment, the alkali metal may be Li, Na or Cs. The alkali metal compound may be selected from alkali metal oxides (e.g., Li)2O、Cs2O and/or K2O) and alkali metal halides (e.g., LiF, NaF, CsF, KF, LiI, NaI, CsI, and/or KI). The alkaline earth metal may be selected from Mg, Ca, Sr and Ba. The alkaline earth metal compound may be selected from alkaline earth metal oxides (e.g., BaO, SrO, CaO). The rare earth metal may be selected from scandium (Sc), yttrium (Y), cerium (Ce), terbium (Tb), ytterbium (Yb) and gadolinium (Gd). The rare earth metal compound may be selected from YbF3、ScF3、Sc2O3、Y2O3、Ce2O3、GdF3And TbF3. It may be a single structure made of a single substance, or a single-layer structure or a multi-layer structure made of different substances.
The hole blocking layer material can be selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tri (N-phenyl-2-benzimidazole) Benzene (BCP), 1,3, 5-tri (N-phenyl-2-benzimidazole)TPBi for short, tris (8-hydroxyquinoline) aluminum (III) for short (Alq for short)3) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.
As the cathode material, a metal material having a small work function is generally preferred. For example, metals or alloys of magnesium (Mg), silver (Ag), aluminum (a1), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and any combination thereof may be used. Among them, when light emission of the light-emitting layer is extracted from the cathode, the light transmittance of the cathode is preferably more than 10%. It is also preferable that the sheet resistivity of the cathode is several hundred Ω/□ or less, and the film thickness is usually 10nm to 1 μm, preferably 50 to 200 nm.
Alq can be used as the cover material of the invention3TPBi or the heterocyclic compound of the invention or a combination of at least two of the same. Preferably, the material of the covering layer according to the present invention is selected from any one or a combination of at least two of the organic compounds for the covering layer according to the present invention.
The film thicknesses of the hole transporting layer and the electron transporting layer may be selected as appropriate depending on the materials used, and may be selected so as to achieve appropriate values of the driving voltage and the light emission efficiency. Therefore, the film thicknesses of the hole transporting layer and the electron transporting layer are, for example, 1nm to 1um, preferably 2nm to 500nm, and more preferably 5nm to 200 nm.
The method for forming each layer in the organic light-emitting device is not particularly limited, and any one of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray, slit coating, and dip coating may be used, and in the present invention, vacuum evaporation is preferably used. The compounds used as the organic layer may be small organic molecules, large organic molecules, and polymers, and combinations thereof.
The organic light-emitting device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.
The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue inventive effort.
Preparation and characterization of the Compounds
Description of raw materials, reagents and characterization equipment:
the raw materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.
The mass spectrum uses British Watts G2-Si quadrupole rod series time-of-flight high resolution mass spectrometer, chloroform is used as solvent;
the elemental analysis was carried out by using a Vario EL cube type organic element analyzer of Elementar, Germany, and the sample mass was 5 to 10 mg.
Synthesis example 1 Synthesis of Compound 1
Figure BDA0003268998140000361
Synthesis of intermediate A-1
Under nitrogen protection, a-1(12.69g, 75.00mmol), b-1(21.84g, 75.00mmol), palladium acetate (0.26g, 1.17mmol), sodium tert-butoxide (12.88g, 134.00mmol), tri-tert-butylphosphine (5mL of a 1.0M solution in toluene) and 700mL of toluene were added to a reaction flask and reacted under reflux for 3 h. After the reaction was completed, the mixture was cooled to normal temperature, filtered through celite, the filtrate was rotary evaporated to remove the solvent, and then recrystallized through toluene, and a recrystallized solid, i.e., intermediate a-1(24.20g, yield 85%) was obtained by suction filtration. Mass spectrum m/z: 379.2314 (theoretical value: 379.2300).
Synthesis of intermediate M-1
C-1(11.26g, 40.00mmol), tetrahydrofuran (200mL) and n-butyllithium (25mL of 1.6M in hexane) were added to the flask under nitrogen and the reaction stirred at-78 deg.C for 50 min. Then a solution (80mL) of d-1(10.33g, 40.00mmol) in tetrahydrofuran was added dropwise to the flask, and the reaction was continued with stirring at-78 ℃ for 50min, followed by stirring at room temperature for 4 h. After the reaction was complete, saturated ammonium chloride solution was added, the organic layer was separated and the solvent was removed by rotary evaporation. The residual solid, acetic anhydride (400mL) and hydrochloric acid (15mL) were charged into a reaction flask, and the reaction was stirred at 100 ℃ for 3.5h, after completion of the reaction, cold water (150mL) was added to precipitate a solid product and the solid product was filtered, followed by purification on a silica gel column (petroleum ether/dichloromethane ═ 10: 1) to obtain intermediate M-1(14.71g, yield 83%). Mass spectrum m/z: 442.1135 (theoretical value: 442.1124).
Synthesis of Compound 1
Under nitrogen protection, intermediate M-1(14.17g, 32.00mmol), intermediate A-1(12.15g, 32.00mmol), palladium acetate (0.12g, 0.50mmol), sodium tert-butoxide (5.46g, 56.70mmol), tri-tert-butylphosphine (3mL of a 1.0M solution in toluene) and 500mL of toluene were added to a reaction flask and heated for 5 h. After the reaction, the reaction mixture was cooled to normal temperature, ice water was added to precipitate a solid product, the solid product was filtered, and the collected solid was separated and purified by a silica gel column (petroleum ether: ethyl acetate: 7: 1) to obtain compound 1(20.66g, yield 82%) with a solid purity of 99.75% or more by HPLC. Mass spectrum m/z: 785.3670 (theoretical value: 785.3658). Theoretical element content (%) C59H47NO: c, 90.16; h, 6.03; n, 1.78. Measured elemental content (%): c, 90.17; h, 6.07; n, 1.82.
Synthesis example 2 Synthesis of Compound 8
Figure BDA0003268998140000371
Compound 8 (21.44) was synthesized using the same procedure as that used for the synthesis of Compound 1 in Synthesis example 1, except that a-1 was replaced with equimolar a-8 and intermediate A-1 was replaced with equimolar intermediate A-8g) And the purity of the solid is not less than 99.81 percent through HPLC detection. Mass spectrum m/z: 835.3826 (theoretical value: 835.3814). Theoretical element content (%) C63H49NO: c, 90.50; h, 5.91; n, 1.68. Measured elemental content (%): c, 90.56; h, 5.93; n, 1.69.
Synthesis example 3 Synthesis of Compound 31
Figure BDA0003268998140000372
The same procedure as used for the synthesis of compound 1 in Synthesis example 1 was used, except that a-1 was replaced with an equal mole of a-31 and intermediate A-1 was replaced with an equal mole of intermediate A-31, to synthesize compound 31(22.54g), which had a solid purity of 99.86% or more by HPLC. Mass spectrum m/z: 949.4295 (theoretical value: 949.4284). Theoretical element content (%) C72H55NO: c, 91.01; h, 5.83; and N, 1.47. Measured elemental content (%): c, 91.07; h, 5.81; n, 1.48.
Synthesis example 4 Synthesis of Compound 65
Figure BDA0003268998140000373
Compound 65(22.61g) was synthesized using the same method as that used for the synthesis of Compound 1 in Synthesis example 1, except that a-1 was replaced with an equal molar amount of a-65, b-1 was replaced with an equal molar amount of b-65, and intermediate A-1 was replaced with an equal molar amount of intermediate A-65, and the purity of the solid was 99.78% or more by HPLC. Mass spectrum m/z: 1021.5178 (theoretical value: 1021.5161). Theoretical element content (%) C77H59D4NO: c, 90.46; h, 6.61; n, 1.37. Measured elemental content (%): c, 90.42; h, 6.62; n, 1.41.
Synthesis example 5 Synthesis of Compound 73
Figure BDA0003268998140000381
The same procedure as that for the synthesis of Compound 1 of Synthesis example 1 was used, wherein a-1 was replacedAnd replacing b-1 with equal molar b-73 for equal molar a-73, replacing intermediate A-1 with equal molar intermediate A-73, and synthesizing compound 73(22.39g), wherein the solid purity is not less than 99.88% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 906.4612 (theoretical value: 906.4597). Theoretical element content (%) C68H50D5NO: c, 90.03; h, 6.67; n, 1.54. Measured elemental content (%): c, 90.05; h, 6.64; n, 1.59.
Synthesis example 6 Synthesis of Compound 95
Figure BDA0003268998140000382
The same procedure as used for the synthesis of Compound 1 in Synthesis example 1 was carried out, except that a-1 was replaced with an equivalent mole of a-95 and intermediate A-1 was replaced with an equivalent mole of intermediate A-95, to synthesize Compound 95(21.37g) with a solid purity of 99.92% or more by HPLC. Mass spectrum m/z: 843.4460 (theoretical value: 843.4440). Theoretical element content (%) C63H57NO: c, 89.64; h, 6.81; n, 1.66. Measured elemental content (%): c, 89.69; h, 6.85; n, 1.67.
Synthesis example 7 Synthesis of Compound 99
Figure BDA0003268998140000383
Synthesis of intermediate P-99
100mL of an ether solution in f-99(78.21g, 182.00mmol) was added dropwise to magnesium activated with 1, 2-dibromoethane (7.22g, 297.00mmol) under nitrogen. The mixture was stirred at room temperature for 1h, after completion of the reaction, the ether solution of the grignard reagent was transferred to another flask to remove residual magnesium and the grignard reagent in the ether was concentrated in vacuo to a solid. 140mL of anhydrous dichloromethane in which e-99(12.91g, 60.00mmol) was dissolved was added to the Grignard reagent, the reaction was refluxed for 24h, after the mixture was cooled to room temperature, the mixture was slowly poured into 2N HCI at 0 ℃, then extracted three times with dichloromethane, the organic phases were combined and washed with water, then dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and flash column chromatography on silica gel (N-hexane) gave intermediate P-99(24.16g, 83% yield). Mass spectrum m/z: 484.1976 (theoretical value: 484.1958).
Synthesis of Compound 99
The same procedure as used for the synthesis of Compound 1 of Synthesis example 1 was used, except that a-1 was replaced with an equal mole of a-99, b-1 was replaced with an equal mole of intermediate P-99, intermediate A-1 was replaced with an equal mole of intermediate A-99, and Compound 99(22.37g) was synthesized with a solid purity of 99.72% by HPLC. Mass spectrum m/z: 1103.4171 (theoretical value: 1103.4161). Theoretical element content (%) C82H57NOS: c, 89.18; h, 5.20; n, 1.27. Measured elemental content (%): c, 89.12; h, 5.26; n, 1.29.
Synthesis example 8 Synthesis of Compound 106
Figure BDA0003268998140000391
The same procedure as used for the synthesis of compound 1 in Synthesis example 1 was used, except that a-1 was replaced with an equal molar amount of a-106, b-1 was replaced with an equal molar amount of b-106, and intermediate A-1 was replaced with an equal molar amount of intermediate A-106, to synthesize compound 106(22.44g) with a solid purity of 99.77% or more by HPLC. Mass spectrum m/z: 999.4451 (theoretical value: 999.4440). Theoretical element content (%) C76H57NO: c, 91.26; h, 5.74; and N, 1.40. Measured elemental content (%): c, 91.27; h, 5.78; n, 1.44.
Synthesis example 9 Synthesis of Compound 148
Figure BDA0003268998140000392
The same procedure as that used for the synthesis of Compound 1 in Synthesis example 1 was carried out by substituting a-1 for equimolar a-148, b-1 for equimolar b-148, c-1 for equimolar c-148, d-1 for equimolar d-148, intermediate M-1 for equimolar intermediate M-148, intermediate A-1 for equimolar intermediate A-148, and synthesizing Compound 148(22.90g), and HPLC checking the purity of solid ≧99.83 percent. Mass spectrum m/z: 915.4394 (theoretical value: 915.4378). Theoretical element content (%) C69H49D4NO: c, 90.45; h, 6.27; n, 1.53. Measured elemental content (%): c, 90.46; h, 6.31; n, 1.56.
Synthesis example 10 Synthesis of Compound 157
Figure BDA0003268998140000393
The same procedure as used in Synthesis example 1 was repeated to synthesize Compound 1, except that a-1 was replaced with an equivalent mole of a-157, c-1 was replaced with an equivalent mole of c-157, d-1 was replaced with an equivalent mole of d-157, intermediate M-1 was replaced with an equivalent mole of intermediate M-157, intermediate A-1 was replaced with an equivalent mole of intermediate A-157, and Compound 157(22.28g) was synthesized with a solid purity of 99.89% or more by HPLC. Mass spectrum m/z: 951.4090 (theoretical value: 951.4076). Theoretical element content (%) C71H53NO2: c, 89.56; h, 5.61; and N, 1.47. Measured elemental content (%): c, 89.57; h, 5.63; n, 1.49.
Synthesis example 11 Synthesis of Compound 187
Figure BDA0003268998140000401
Synthesis of intermediate Q-187
Under the protection of nitrogen, adding intermediate M-1(38.39g, 86.67mmol), h-187(24.21g, 95.33mmol), potassium acetate (25.52g, 260mmol), 1,1' -bis-diphenylphosphino ferrocene palladium dichloride (1.95g, 2.66mmol) and N, N-dimethylformamide (480mL) into a reaction flask in sequence, then placing the mixture into an oil bath at 85 ℃, reacting for 4.5h, cooling to room temperature, adding 500mL of water to generate a precipitate, filtering, washing with water and drying. The resulting precipitate was dissolved in 450mL ethyl acetate. Then, insoluble matter was removed by filtration, the filtrate was collected, the solvent was removed by rotary evaporation, and the residual solid was separated and purified by a silica gel column (petroleum ether: ethyl acetate: 5:2) and dried to obtain intermediate Q-187(38.44g, yield 83%). Mass spectrum m/z: 534.2382 (theoretical value: 534.2366).
Synthesis of intermediate M-187
Under nitrogen protection, i-187(13.16g, 54.47mmol), intermediate Q-187(29.11g, 54.47mmol), tetrakistriphenylphosphine palladium (0.61g, 0.53mmol), potassium acetate (7.86g, 80.11mmol) and toluene/ethanol/water 3/1/1(500ml) were added to a reaction flask in this order, the mixture was stirred, and the above system was refluxed for 4.5 hours; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (20: 3 recrystallisation gave intermediate M-187(24.32g, 80% yield). Mass spectrum m/z: 568.1605 (theoretical value: 568.1594).
Synthesis of Compound 187
Compound 187(22.41g) was synthesized using the same method as that used for the synthesis of compound 1 in synthesis example 1, except that a-1 was replaced with an equal molar amount of a-187, intermediate M-1 was replaced with an equal molar amount of intermediate M-187, and intermediate a-1 was replaced with an equal molar amount of intermediate a-187, and the solid purity ≧ 99.91% by HPLC. Mass spectrum m/z: 1027.4764 (theoretical value: 1027.4753). Theoretical element content (%) C78H61NO: c, 91.10; h, 5.98; n, 1.36. Measured elemental content (%): c, 91.06; h, 6.00; and N, 1.40.
Synthesis example 12 Synthesis of Compound 261
Figure BDA0003268998140000402
The same procedure as used for the synthesis of compound 1 in Synthesis example 1 was used, except that a-1 was replaced with an equal molar amount of a-261, b-1 was replaced with an equal molar amount of b-73, c-1 was replaced with an equal molar amount of c-261, intermediate M-1 was replaced with an equal molar amount of intermediate M-261, intermediate A-1 was replaced with an equal molar amount of intermediate A-261, and compound 261(21.60g) was synthesized with a solid purity of 99.85% or more by HPLC. Mass spectrum m/z: 831.3010 (theoretical value: 831.2993). Theoretical element content (%) C59H45NS2: c, 85.16; h, 5.45; n, 1.68. Measured elemental content (%): c, 85.20; h, 5.40; and N, 1.70.
Synthesis example 13 Synthesis of Compound 280
Figure BDA0003268998140000411
The same procedure used for the synthesis of compound 99 of Synthesis example 7 was followed, except that f-99 was replaced with c-1 in an equal molar amount, a-99 was replaced with a-280 in an equal molar amount, intermediate A-99 was replaced with intermediate A-280 in an equal molar amount, intermediate M-1 was replaced with intermediate M-261 in an equal molar amount, and compound 280(22.46g) was synthesized with a purity of 99.85% by HPLC. Mass spectrum m/z: 933.3407 (theoretical value: 933.3389). Theoretical element content (%) C65H47N3O2S: c, 83.57; h, 5.07; and N, 4.50. The measured element content (%) C, 83.58; h, 5.02; n, 4.56.
Synthesis example 14 Synthesis of Compound 286
Figure BDA0003268998140000412
The same procedure as used for the synthesis of compound 1 in synthesis example 1 was used, except that a-1 was replaced with an equal mole of a-286, intermediate a-1 was replaced with an equal mole of intermediate a-286, and compound 286(21.46g) was synthesized with a solid purity of 99.76% or more by HPLC. Mass spectrum m/z: 826.3542 (theoretical value: 826.3559). Theoretical element content (%) C60H46N2O2: c, 87.14; h, 5.61; and N, 3.39. Measured elemental content (%): c, 87.11; h, 5.63; and N, 3.42.
[ Synthesis example 15] Synthesis of Compound 295
Figure BDA0003268998140000413
Synthesis of Compound 1 Using the same procedure as in Synthesis example 1, wherein a-1 was replaced with equimolar a-295, b-1 was replaced with equimolar b-73, c-1 was replaced with equimolar c-157, intermediate M-1 was replaced with equimolar intermediate M-295, intermediate A-1 was replaced with equimolar intermediate A-295, a synthetic compound was synthesizedSubstance 295(22.25g), solid purity ≧ 99.87% by HPLC. Mass spectrum m/z: 963.4095 (theoretical value: 963.4076). Theoretical element content (%) C72H53NO2: c, 89.69; h, 5.54; n, 1.45. Measured elemental content (%): c, 89.74; h, 5.50; and N, 1.47.
Synthesis example 16 Synthesis of Compound 298
Figure BDA0003268998140000421
The same procedure as used for the synthesis of compound 1 in synthetic example 1 was used, except that a-1 was replaced with equimolar a-298, b-1 was replaced with equimolar b-73, intermediate a-1 was replaced with equimolar intermediate a-298, and compound 298(21.99g) was synthesized with a solid purity of 99.84% or more by HPLC. Mass spectrum m/z: 965.4244 (theoretical value: 965.4233). Theoretical element content (%) C72H55NO2: c, 89.50; h, 5.74; n, 1.45. Measured elemental content (%): c, 89.56; h, 5.70; n, 1.44.
Synthesis example 17 Compound 308 is synthesized
Figure BDA0003268998140000422
The same procedure as used for the synthesis of compound 1 in Synthesis example 1 was used, except that a-1 was replaced with an equivalent mole of a-308 and intermediate A-1 was replaced with an equivalent mole of intermediate A-308, to synthesize compound 308(22.51g) with a purity of 99.80% or more by HPLC. Mass spectrum m/z: 935.4113 (theoretical value: 935.4127). Theoretical element content (%) C71H53NO: c, 91.09; h, 5.71; and N, 1.50. Measured elemental content (%): c, 91.06; h, 5.72; n, 1.55.
Synthesis example 18 Synthesis of Compound 331
Figure BDA0003268998140000423
The same procedure as that for Synthesis of Compound 1 in Synthesis example 1 was adoptedThe process of (1), wherein a-1 is replaced with an equal mole of a-331, intermediate A-1 is replaced with an equal mole of intermediate A-331, intermediate M-1 is replaced with an equal mole of intermediate M-261, and compound 331(21.21g) is synthesized with a solid purity of 99.88% or more by HPLC. Mass spectrum m/z: 806.3763 (theoretical value: 806.3743). Theoretical element content (%) C59H42D5And NS: c, 87.80; h, 6.49; n, 1.74. Measured elemental content (%): c, 87.84; h, 6.45; n, 1.76.
Synthesis example 19 Synthesis of Compound 337
Figure BDA0003268998140000424
Figure BDA0003268998140000431
Compound 337(22.32g) was synthesized using the same procedure as that used for the synthesis of compound 187 in synthetic example 11, except that M-1 was replaced with M-337, i-187 was replaced with i-337, a-187 was replaced with a-337, intermediate a-187 was replaced with intermediate a-337, and intermediate M-187 was replaced with intermediate M1-337, and the purity of solid was 99.65% by HPLC. Mass spectrum m/z: 966.4019 (theoretical value: 966.4008). Theoretical element content (%) C71H54N2S: c, 88.16; h, 5.63; and N, 2.90. Measured elemental content (%): c, 88.18; h, 5.62; and N, 2.94.
[ Synthesis example 20] Synthesis of Compound 357
Figure BDA0003268998140000432
The same procedure as for the synthesis of Compound 1 in Synthesis example 1 was used, wherein a-1 was replaced with equimolar a-357, b-1 was replaced with equimolar b-357, c-1 was replaced with equimolar c-261, d-1 was replaced with equimolar d-357, intermediate M-1 was replaced with equimolar intermediate M-357, and intermediate A-1 was replaced withEqual mol of the intermediate A-357, and compound 357(18.78g) is synthesized, and the purity of the solid is equal to or more than 99.73% by HPLC. Mass spectrum m/z: 705.3416 (theoretical value: 705.3429). Theoretical element content (%) C51H47And NS: c, 86.76; h, 6.71; n, 1.98. Measured elemental content (%): c, 86.77; h, 6.77; and N, 1.96.
[ Synthesis example 21] Synthesis of Compound 365
Figure BDA0003268998140000433
The same procedure as used for the synthesis of compound 1 of synthesis example 1 was used, except that a-1 was replaced with equimolar a-365, b-1 was replaced with equimolar b-365, c-1 was replaced with equimolar c-261, d-1 was replaced with equimolar d-365, intermediate M-1 was replaced with equimolar intermediate M-365, intermediate a-1 was replaced with equimolar intermediate a-365, and compound 365(22.73g) was synthesized with a solid purity of 99.81% by HPLC. Mass spectrum m/z: 908.4192 (theoretical value: 908.4182). Theoretical element content (%) C67H44D7And NS: c, 88.51; h, 6.43; n, 1.54. Measured elemental content (%): c, 88.56; h, 6.42; n, 1.59.
[ Synthesis example 22] Synthesis of Compound 381
Figure BDA0003268998140000441
The same procedure as used in the synthesis of compound 1 of synthesis example 1 was used, except that a-1 was replaced with equimolar a-381, b-1 was replaced with equimolar b-381, c-1 was replaced with equimolar c-381, intermediate M-1 was replaced with equimolar intermediate M-381, intermediate a-1 was replaced with equimolar intermediate a-381, and compound 381(12.88g) was synthesized with a solid purity of 99.76% by HPLC. Mass spectrum m/z: 673.3943 (theoretical value: 673.3926). Theoretical element content (%) C48H23D15N2O: c, 85.55; h, 7.92; and N, 4.16. Measured elemental content (%): c, 85.57; h, 7.96; n, 4.11.
Synthesis example 23 Synthesis of Compound 382
Figure BDA0003268998140000442
The same procedure as used for the synthesis of compound 1 in synthesis example 1 was used, except that a-1 was replaced with an equal molar amount of a-382, b-1 was replaced with an equal molar amount of b-382, intermediate a-1 was replaced with an equal molar amount of intermediate a-382, intermediate M-1 was replaced with an equal molar amount of intermediate M-295, and compound 382(21.34g) was synthesized with a solid purity of 99.79% or more as determined by HPLC. Mass spectrum m/z: 811.3218 (theoretical value: 811.3199). Theoretical element content (%) C58H41N3O2: c, 85.79; h, 5.09; and N, 5.18. Measured elemental content (%): c, 85.84; h, 5.07; and N, 5.12.
[ Synthesis example 24] Synthesis of Compound 384
Figure BDA0003268998140000443
The same procedure as used for the synthesis of Compound 1 in Synthesis example 1 was carried out by substituting a-1 for an equivalent mole of a-384, b-1 for an equivalent mole of b-384, and intermediate A-1 for an equivalent mole of intermediate A-384, to synthesize Compound 384(21.50g) with a solid purity of 99.68% by HPLC. Mass spectrum m/z: 848.3775 (theoretical value: 848.3767). Theoretical element content (%) C63H48N2O: c, 89.12; h, 5.70; and N, 3.30. Measured elemental content (%): c, 89.18; h, 5.73; and N, 3.26.
[ Synthesis example 25] Synthesis of Compound 399
Figure BDA0003268998140000444
Compound 399(21.30g) was synthesized using the same method as that for the synthesis of Compound 1 in Synthesis example 1, in which a-1 was replaced with equimolar a-399, b-1 was replaced with equimolar b-399, and intermediate A-1 was replaced with equimolar intermediate A-399, followed by HPLCThe detected solid purity is not less than 99.74 percent. Mass spectrum m/z: 851.3892 (theoretical value: 851.3876). Theoretical element content (%) C62H49N3O: c, 87.39; h, 5.80; and N, 4.93. Measured elemental content (%): c, 87.40; h, 5.85; and N, 4.90.
Synthesis example 26 Synthesis of Compound 405
Figure BDA0003268998140000451
The same procedure as used for the synthesis of compound 1 in Synthesis example 1 was used, except that a-1 was replaced with an equal molar amount of a-405, b-1 was replaced with an equal molar amount of b-405, c-1 was replaced with an equal molar amount of c-405, intermediate M-1 was replaced with an equal molar amount of intermediate M-405, intermediate A-1 was replaced with an equal molar amount of intermediate A-405, and compound 405(21.95g) was synthesized with a solid purity of 99.90% or more by HPLC. Mass spectrum m/z: 900.3731 (theoretical value: 900.3716). Theoretical element content (%) C66H48N2O2: c, 87.97; h, 5.37; n, 3.11. Measured elemental content (%): c, 87.99; h, 5.32; and N, 3.15.
Synthesis example 27 Synthesis of Compound 415
Figure BDA0003268998140000452
The same procedure as used for the synthesis of compound 1 in Synthesis example 1 was used, except that a-1 was replaced with an equimolar amount of a-415, b-1 was replaced with an equimolar amount of b-415, and intermediate A-1 was replaced with an equimolar amount of intermediate A-415, to synthesize compound 415(22.65g) with a solid purity of 99.87% or more by HPLC. Mass spectrum m/z: 994.4876 (theoretical value: 994.4862). Theoretical element content (%) C74H62N2O: c, 89.30; h, 6.28; n, 2.81. Measured elemental content (%): c, 89.34; h, 6.29; and N, 2.82.
Synthesis example 28 Synthesis of Compound 420
Figure BDA0003268998140000453
The same procedure as used for the synthesis of compound 1 in synthesis example 1 was used, except that a-1 was replaced with an equal molar amount of a-420, b-1 was replaced with an equal molar amount of b-420, c-1 was replaced with an equal molar amount of c-420, intermediate M-1 was replaced with an equal molar amount of intermediate M-420, intermediate a-1 was replaced with an equal molar amount of intermediate a-420, and compound 420(21.10g) was synthesized with a solid purity of 99.80% or more by HPLC. Mass spectrum m/z: 854.4125 (theoretical value: 854.4143). Theoretical element content (%) C63H42D6N2O: c, 88.49; h, 6.36; and N, 3.28. Measured elemental content (%): c, 88.51; h, 6.41; and N, 3.25.
[ Synthesis example 29] Synthesis of Compound 451
Figure BDA0003268998140000461
The same procedure as used for the synthesis of compound 1 in Synthesis example 1 was used, except that a-1 was replaced with an equal mole of a-451, b-1 was replaced with an equal mole of b-451, c-1 was replaced with an equal mole of c-451, intermediate M-1 was replaced with an equal mole of intermediate M-451, intermediate A-1 was replaced with an equal mole of intermediate A-451, and compound 451(22.12g) was synthesized with a solid purity of 99.71% or more by HPLC. Mass spectrum m/z: 907.4513 (theoretical value: 907.4502). Theoretical element content (%) C66H57N3O: c, 87.29; h, 6.33; and N, 4.63. Measured elemental content (%): c, 87.34; h, 6.39; and N, 4.60.
[ Synthesis example 30] Synthesis of Compound 457
Figure BDA0003268998140000462
Synthesis of intermediate M-457
Intermediate M-457(14.35g) was synthesized using the same procedure as that used to synthesize intermediate M-1 in Synthesis example 1, except that c-1 was replaced with equimolar c-457. Mass spectrum m/z: 442.1143 (theoretical value: 442.1124).
Synthesis of Compound 457
The same procedure as used in Synthesis example 7, in which f-99 was replaced with equal molar f-457, a-99 was replaced with equal molar a-457, intermediate A-99 was replaced with equal molar intermediate A-457, intermediate M-1 was replaced with equal molar intermediate M-457, Compound 457(22.75g) was synthesized with a purity of 99.59% by HPLC. Mass spectrum m/z: 1058.5836 (theoretical value: 1058.5818). Theoretical element content (%) C77H54D11N3O: c, 87.29; h, 7.23; and N, 3.97. Measured elemental content (%): c, 87.25; h, 7.29; and N, 3.99.
Synthesis example 31 Synthesis of Compound 458
Figure BDA0003268998140000463
The same procedure used for the synthesis of compound 1 in synthesis example 1 was used, except that a-1 was replaced with an equal molar amount of a-458, b-1 was replaced with an equal molar amount of b-458, intermediate a-1 was replaced with an equal molar amount of intermediate a-458, intermediate M-1 was replaced with an equal molar amount of intermediate M-261, compound 458(22.64g) was synthesized, and the purity of the solid was 99.82% or more as determined by HPLC. Mass spectrum m/z: 934.3371 (theoretical value: 934.3382). Theoretical element content (%) C69H46N2S: c, 88.62; h, 4.96; and N, 3.00. Measured elemental content (%): c, 88.66; h, 4.90; and N, 3.06.
Synthesis example 32 Synthesis of Compound 484
Figure BDA0003268998140000471
Compound 484(21.42g) was synthesized using the same method as that used for the synthesis of compound 187 in synthetic example 11, except that i-187 was replaced with equimolar c-157, a-187 was replaced with equimolar a-484, b-1 was replaced with equimolar b-484, and intermediate M-187 was replaced with equimolar intermediate M-484, and compound 484(21.42g) was synthesized with a solid purity ≧ 99.89% by HPLC. Mass spectrum m/z: 824.3418 (theoretical value: 824.3403). Theoretical element content (％)C60H44N2O2: c, 87.35; h, 5.38; and N, 3.40. Measured elemental content (%): c, 87.39; h, 5.42; and N, 3.32.
Synthesis example 33 Synthesis of Compound 532
Figure BDA0003268998140000472
The same procedure as used for the synthesis of compound 1 in synthesis example 1 was used, except that a-1 was replaced with an equal molar amount of a-532, b-1 was replaced with an equal molar amount of b-532, intermediate a-1 was replaced with an equal molar amount of intermediate a-532, intermediate M-1 was replaced with an equal molar amount of intermediate M-295, and compound 532(21.04) was synthesized with a solid purity of 99.64% or more by HPLC. Mass spectrum m/z: 824.3423 (theoretical value: 824.3403). Theoretical element content (%) C60H44N2O2: c, 87.35; h, 5.38; and N, 3.40. Measured elemental content (%): c, 87.37; h, 5.32; n, 3.44.
Synthesis example 34 Synthesis of Compound 534
Figure BDA0003268998140000473
The same procedure as used in Synthesis example 1 was repeated to synthesize Compound 1, except that a-1 was replaced with an equal molar amount of a-534, b-1 was replaced with an equal molar amount of b-534, intermediate A-1 was replaced with an equal molar amount of intermediate A-534, and Compound 534(21.47g) was synthesized with a solid purity of 99.75% or more by HPLC. Mass spectrum m/z: 816.2829 (theoretical value: 816.2810). Theoretical element content (%) C57H40N2O2S: c, 83.80; h, 4.94; n, 3.43. Measured elemental content (%): c, 83.86; h, 4.95; and N, 3.40.
Synthesis example 35 Synthesis of Compound 536
Figure BDA0003268998140000474
By using the compound of synthetic example 1The same procedure as for Compound 1 was followed, except that a-1 was replaced with equimolar a-536, b-1 was replaced with equimolar b-536, and intermediate A-1 was replaced with equimolar intermediate A-536, to synthesize Compound 536(21.20g) with a solid purity of 99.79% or more by HPLC. Mass spectrum m/z: 858.3262 (theoretical value: 858.3246). Theoretical element content (%) C63H42N2O2: c, 88.09; h, 4.93; and N, 3.26. Measured elemental content (%): c, 88.14; h, 4.98; and N, 3.20.
Synthesis example 36 Synthesis of Compound 578
Figure BDA0003268998140000481
The same procedure used for the synthesis of compound 1 in synthesis example 1 was used, except that a-1 was replaced with an equal molar amount of a-578, b-1 was replaced with an equal molar amount of b-578, intermediate a-1 was replaced with an equal molar amount of intermediate a-578, intermediate M-1 was replaced with an equal molar amount of intermediate M-261, and compound 578(21.62g) was synthesized with a solid purity of 99.82% or more by HPLC. Mass spectrum m/z: 842.3647 (theoretical value: 842.3633). Theoretical element content (%) C61H42D4N2S: c, 86.90; h, 5.98; and N, 3.32. Measured elemental content (%): c, 86.94; h, 5.97; and N, 3.35. Blue organic light emitting device (hole transport layer)
Comparative examples 1-2 device preparation examples:
comparative example 1: the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: and (3) putting the ITO substrate into distilled water for cleaning for 3 times, ultrasonically cleaning for 15 minutes, after the cleaning of the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying at 120 ℃, and conveying to an evaporation plating machine.
A hole injection layer DNTPD/18nm, a hole transport layer HT-1/85nm, a luminescent layer (host DNA: DPAVBi (98%: 2% mixed))/22 nm, an electron transport layer ET and Liq (doping ratio 1:1)/25nm, an electron injection layer LiF/1nm and a cathode Al/125nm are evaporated on the prepared ITO transparent electrode in a layer-by-layer vacuum evaporation mode. And the device was sealed in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is as follows:
Figure BDA0003268998140000482
comparative example 2: the hole transport layer material HT-1 in comparative example 1 was replaced with HT-2, and an organic light emitting device of comparative example 2 was fabricated in the same manner as in comparative example 1.
[ examples 1 to 28]
Examples 1 to 28: the hole transport layer material HT-1 of the organic light emitting device was sequentially changed to the compounds 1, 8, 31, 65, 73, 95, 99, 106, 157, 261, 298, 331, 337, 357, 365, 381, 382, 384, 399, 405, 415, 420, 451, 457, 458, 532, 536, 578 of the present invention, and the other steps were the same as in comparative example 1.
The test software, computer, K2400 digital source manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic light emitting device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 1. Table 1 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.
Table 1 test of light emitting characteristics of light emitting device
Figure BDA0003268998140000491
Figure BDA0003268998140000501
Note: t97 is referred to asThe current density is 10mA/cm2In the case, the time taken for the luminance of the device to decay to 97%;
as can be seen from the results in table 1, the heterocyclic compound of the present invention, when applied to an organic light emitting device, as a hole transport layer material, exhibits the advantage of higher light emitting efficiency as compared to comparative examples 1-2, and is a hole transport material for an organic light emitting device with good performance.
Green organic light emitting device (second hole transport layer)
Comparative examples 3-4 device preparation examples:
comparative example 3: the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: and (3) putting the ITO transparent substrate into distilled water for cleaning for 3 times, ultrasonically cleaning for 15 minutes, after the cleaning of the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying at 120 ℃, drying, and conveying to an evaporation plating machine.
A hole injection layer DNTPD/30nm, a first hole transport layer HT1/75nm, a second hole transport layer HT2-1/44nm, a luminescent layer (a main body H-7: H-11: Ir (3mppy)3 (47%: 47%: 6% mixed))/25 nm, an electron transport layer TMPYPB/28nm, an electron injection layer LiF/0.5nm and a cathode Al/110nm are evaporated on an ITO transparent substrate electrode which is prepared in a layer-by-layer vacuum evaporation mode. And the device was sealed in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is as follows:
Figure BDA0003268998140000502
comparative example 4: the organic light emitting device of comparative example 4 was fabricated in the same manner as in comparative example 3, except that the second hole transport layer material HT2-1 in comparative example 3 was changed to HT 2-2.
[ examples 29 to 54]
Examples 29 to 54: the second hole transport layer material of the organic light emitting device was sequentially changed to the compounds 1, 8, 31, 73, 95, 148, 157, 187, 261, 286, 295, 298, 308, 331, 357, 365, 381, 399, 405, 420, 451, 457, 484, 532, 534, 536 of the present invention, and the other steps were the same as in comparative example 3.
The driving voltage and the luminous efficiency of the organic light emitting device were tested by combining test software, a computer, a K2400 digital source manufactured by Keithley, usa, and a PR788 spectral scanning luminance meter manufactured by Photo Research, usa, into a combined IVL test system. The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 2. Table 2 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.
Table 2 test of light emitting characteristics of light emitting device
Figure BDA0003268998140000511
Figure BDA0003268998140000521
Note: t97 denotes a current density of 10mA/cm2In the case, the time taken for the luminance of the device to decay to 97%;
as can be seen from the results of table 2, the heterocyclic compound of the present invention applied to the organic light emitting device, especially as the second hole transport layer material, significantly improved the light emitting efficiency of the organic light emitting device and reduced the driving voltage compared to comparative examples 3-4, and is an organic light emitting material with good performance.
Blue organic light emitting device (cover layer)
Comparative example 5 device preparation example:
comparative example 5: the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: and (3) putting the ITO-Ag-ITO substrate into distilled water for cleaning for 3 times, ultrasonically cleaning for 15 minutes, after the cleaning of the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying at 120 ℃, and conveying to an evaporation plating machine.
A hole injection layer DNTPD/26nm, a hole transport layer NPB/95nm, a luminescent layer (host H-27: BD (97%: 3%) mixed))/25 nm, an electron transport layer ET-2 and Liq (doping ratio of 1:1)/32nm, an electron injection layer LiF/1nm, a cathode Mg-Ag/16nm and a cover layer CP-1/73nm are evaporated on the prepared ITO-Ag-ITO transparent electrode in a layer-by-layer vacuum evaporation mode. And the device was sealed in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is as follows:
Figure BDA0003268998140000522
comparative example 6: the cap material CP-1 of comparative example 5 was changed to CP-2, and an organic light emitting device of comparative example 6 was fabricated in the same manner as in comparative example 5.
[ examples 55 to 66]
Examples 55 to 66: the capping layer material CP-1 of the organic light emitting device was sequentially changed to the compounds 8, 99, 106, 187, 280, 286, 295, 308, 415, 451, 458, 534 of the present invention, and the other steps were the same as in comparative example 5.
The test software, computer, K2400 digital source manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic light emitting device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 3. Table 3 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.
Table 3 test of light emitting characteristics of light emitting device
Figure BDA0003268998140000531
Note: t95 denotes a current density of 10mA/cm2In this case, the time taken for the luminance of the device to decay to 95%;
as can be seen from the results in table 3, the heterocyclic compound of the present invention, when applied to an organic light emitting device as a capping layer material, can effectively improve the light extraction efficiency and thus the light emitting efficiency of the organic light emitting device, compared to comparative examples 5 to 6, and is a capping layer material for an organic light emitting device with good performance.
It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims (10)

1. A heterocyclic compound, characterized in that the molecular structure is represented by formula I:
Figure FDA0003268998130000011
wherein X is selected from O or S;
ar is1One selected from the following groups:
Figure FDA0003268998130000012
the R is0One or adjacent R selected from hydrogen, deuterium, halogen atoms, cyano, C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl0Can be connected into a ring;
ar is selected from one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;
k is1Selected from 0,1 or 2;
k is2Selected from 0,1, 2,3 or 4;
k is3Selected from 0,1, 2,3, 4,5 or 6;
k is4Selected from 0,1, 2,3, 4,5, 6,7 or 8;
k is5Selected from 0,1, 2,3, 4,5, 6,7, 8,9 or 10;
k is6Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11;
k is7Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10,11 or 12;
k is8Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10,11, 12, 13 or 14;
k is9Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10,11, 12, 13, 14 or 15;
ar is2One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C25 heteroaryl;
the R is selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;
said L0、L1、L2、LaIndependently selected from a single bond, substituted or unsubstituted arylene of C6-C25, substituted or unsubstituted heteroarylene of C2-C20;
the R is1、R2、R3、R4Are identical or different from each other and are each independently selected from hydrogen, deuterium, halogenAtom, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, or adjacent R1Adjacent R2Adjacent R3Adjacent R4Can be connected into a ring structure;
a is selected from 0,1, 2,3 or 4; b is selected from 0,1, 2,3 or 4;
c is selected from 0,1, 2 or 3; d is selected from 0,1, 2 or 3;
in the above "substituted or unsubstituted …", the term "substituted …" means substituted with one or more substituents independently selected from the group consisting of deuterium, cyano, substituted or unsubstituted C1 to C15 alkyl, substituted or unsubstituted C3 to C15 cycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 cycloalkenyl, substituted or unsubstituted C6 to C25 aryl, and substituted or unsubstituted C2 to C20 heteroaryl.
2. The heterocyclic compound according to claim 1, wherein R is0One or more selected from hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl, or adjacent R0May be linked to a benzene ring or a naphthalene ring, and in the case of being substituted with a plurality of substituents, the plurality of substituents may be the same as or different from each other;
ar is selected from one of deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl and naphthyl.
3. The heterocyclic compound according to claim 1, wherein Ar is one of a group consisting of2Any one selected from the following groups:
Figure FDA0003268998130000021
Figure FDA0003268998130000031
the R is12One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl;
the R is13One of deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or adjacent R13Can be connected into a ring structure;
wherein said R13Can also be substituted by R23Substituted, R23One or more substituents selected from the group consisting of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl, and, in the case of substitution with a plurality of substituents, the plurality of substituents may be the same or different from each other;
the at least oneX is selected from N, and the rest is selected from CR13；
A' is 0,1 or 2; a is a0Is 0,1, 2 or 3; a is a1Is 0,1, 2,3 or 4; a is a2Is 0,1, 2,3, 4 or 5; a is a3Is 0,1, 2,3, 4,5, 6 or 7; a is a4Is 0,1, 2,3, 4,5, 6,7 or 8; a is a5Is 0,1, 2,3, 4,5, 6,7, 8 or 9.
4. The heterocyclic compound according to claim 1, wherein R is one selected from the group consisting of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, and dibenzofuranyl.
5. The heterocyclic compound according to claim 1, wherein R is1、R2、R3、R4Identical to or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, a halogen atom, cyano, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, adamantyl, norbornyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, phenyl-naphthyl, acridinyl, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazolyl, 9-phenylcarbazolyl, pyrenyl, indolyl, acridinyl, pyridyl, furyl, thienyl, benzothienyl, benzofuryl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzothienyl, dibenzofuryl, phenothiazinyl, phenoxazinyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl-phenylfuranyl, and the like, Deuterated naphthyl, deuterated biphenyl, deuterated terphenyl, deuterated anthracenyl, deuterated phenanthrenyl, deuterated triphenylenyl, deuterated benzeneOne of phenyl-naphthyl, deuterated phenyl-deuterated naphthyl, deuterated dibenzothienyl, deuterated dibenzofuranyl, deuterated 9, 9-dimethylfluorenyl, deuterated 9, 9-diphenylfluorenyl and deuterated spirobifluorenyl, or adjacent R1Adjacent R2Adjacent R3Adjacent R4Can be connected into a ring structure.
6. The heterocyclic compound according to claim 1, wherein L is0、L1、L2、LaIndependently selected from a single bond or one of the following groups:
Figure FDA0003268998130000041
wherein R isaOne or more selected from deuterium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, and pentadeuterated phenyl, and in the case of substitution with a plurality of substituents, the plurality of substituents may be the same or different from each other;
m is 0,1 or 2; n is 0,1, 2 or 3; p is 0,1, 2,3 or 4; q is 0,1, 2,3, 4 or 5; and r is 0,1, 2,3, 4,5 or 6.
7. The heterocyclic compound according to claim 1, characterized in that the heterocyclic compound is selected from any one of the following chemical structures:
Figure FDA0003268998130000051
Figure FDA0003268998130000061
Figure FDA0003268998130000071
Figure FDA0003268998130000081
Figure FDA0003268998130000091
Figure FDA0003268998130000101
Figure FDA0003268998130000111
Figure FDA0003268998130000121
Figure FDA0003268998130000131
Figure FDA0003268998130000141
Figure FDA0003268998130000151
Figure FDA0003268998130000161
Figure FDA0003268998130000171
8. an organic light-emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode or outside one or more electrodes selected from the anode and the cathode, wherein the organic layer contains any one or a combination of at least two of the heterocyclic compounds according to any one of claims 1 to 7.
9. An organic light-emitting device according to claim 8, wherein the organic layer comprises a hole transport layer containing any one or a combination of at least two of the heterocyclic compounds according to any one of claims 1 to 7.
10. An organic light-emitting device according to claim 8, wherein the organic layer comprises a capping layer containing any one or a combination of at least two of the heterocyclic compounds according to any one of claims 1 to 7.
CN202111095320.6A 2021-09-17 2021-09-17 Heterocyclic compound and organic light-emitting device thereof Active CN113651785B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111095320.6A CN113651785B (en) 2021-09-17 2021-09-17 Heterocyclic compound and organic light-emitting device thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111095320.6A CN113651785B (en) 2021-09-17 2021-09-17 Heterocyclic compound and organic light-emitting device thereof

Publications (2)

Publication Number Publication Date
CN113651785A true CN113651785A (en) 2021-11-16
CN113651785B CN113651785B (en) 2024-01-26

Family

ID=78483854

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111095320.6A Active CN113651785B (en) 2021-09-17 2021-09-17 Heterocyclic compound and organic light-emitting device thereof

Country Status (1)

Country Link
CN (1) CN113651785B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114773286A (en) * 2022-05-10 2022-07-22 长春海谱润斯科技股份有限公司 Nitrogen-containing heterocyclic organic compound and organic light-emitting device thereof
WO2022264974A1 (en) * 2021-06-15 2022-12-22 保土谷化学工業株式会社 Amine compound having azabenzoxazole ring structure, and organic electroluminescent element using same
CN115557920A (en) * 2022-09-22 2023-01-03 吉林奥来德光电材料股份有限公司 Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
CN115594652A (en) * 2022-09-30 2023-01-13 长春海谱润斯科技股份有限公司（Cn） Amine compound and organic light-emitting device thereof
CN116444467A (en) * 2023-06-19 2023-07-18 吉林奥来德光电材料股份有限公司 Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
CN116987054A (en) * 2023-09-26 2023-11-03 吉林奥来德光电材料股份有限公司 Light-emitting auxiliary material, preparation method thereof, organic electroluminescent device and organic electroluminescent device
CN117209460A (en) * 2023-11-09 2023-12-12 浙江华显光电科技有限公司 Organic photoelectric compound, composition with same and organic light-emitting device
WO2024002424A1 (en) * 2022-06-29 2024-01-04 Heliatek Gmbh Organic electronic construction element with a chemical compound of general formula i, and use of such a chemical compound as n-dopant in an organic electronic construction element
WO2024016687A1 (en) * 2022-07-20 2024-01-25 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic element, and electronic apparatus
CN115594652B (en) * 2022-09-30 2024-05-24 长春海谱润斯科技股份有限公司 Amine compound and organic light-emitting device thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107652189A (en) * 2017-11-08 2018-02-02 长春海谱润斯科技有限公司 A kind of fluorene kind derivative and its organic luminescent device
WO2021141356A1 (en) * 2020-01-10 2021-07-15 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using same, and electronic device thereof
CN113620917A (en) * 2021-09-09 2021-11-09 长春海谱润斯科技股份有限公司 Triarylamine compound and organic light-emitting device thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107652189A (en) * 2017-11-08 2018-02-02 长春海谱润斯科技有限公司 A kind of fluorene kind derivative and its organic luminescent device
WO2021141356A1 (en) * 2020-01-10 2021-07-15 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using same, and electronic device thereof
CN113620917A (en) * 2021-09-09 2021-11-09 长春海谱润斯科技股份有限公司 Triarylamine compound and organic light-emitting device thereof

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022264974A1 (en) * 2021-06-15 2022-12-22 保土谷化学工業株式会社 Amine compound having azabenzoxazole ring structure, and organic electroluminescent element using same
CN114773286A (en) * 2022-05-10 2022-07-22 长春海谱润斯科技股份有限公司 Nitrogen-containing heterocyclic organic compound and organic light-emitting device thereof
CN114773286B (en) * 2022-05-10 2024-02-20 长春海谱润斯科技股份有限公司 Nitrogen-containing heterocyclic organic compound and organic light-emitting device thereof
WO2024002424A1 (en) * 2022-06-29 2024-01-04 Heliatek Gmbh Organic electronic construction element with a chemical compound of general formula i, and use of such a chemical compound as n-dopant in an organic electronic construction element
WO2024016687A1 (en) * 2022-07-20 2024-01-25 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic element, and electronic apparatus
CN115557920A (en) * 2022-09-22 2023-01-03 吉林奥来德光电材料股份有限公司 Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
CN115557920B (en) * 2022-09-22 2024-02-20 吉林奥来德光电材料股份有限公司 Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
CN115594652A (en) * 2022-09-30 2023-01-13 长春海谱润斯科技股份有限公司（Cn） Amine compound and organic light-emitting device thereof
CN115594652B (en) * 2022-09-30 2024-05-24 长春海谱润斯科技股份有限公司 Amine compound and organic light-emitting device thereof
CN116444467B (en) * 2023-06-19 2023-10-13 吉林奥来德光电材料股份有限公司 Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
CN116444467A (en) * 2023-06-19 2023-07-18 吉林奥来德光电材料股份有限公司 Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
CN116987054B (en) * 2023-09-26 2023-12-26 吉林奥来德光电材料股份有限公司 Light-emitting auxiliary material, preparation method thereof, organic electroluminescent device and organic electroluminescent device
CN116987054A (en) * 2023-09-26 2023-11-03 吉林奥来德光电材料股份有限公司 Light-emitting auxiliary material, preparation method thereof, organic electroluminescent device and organic electroluminescent device
CN117209460A (en) * 2023-11-09 2023-12-12 浙江华显光电科技有限公司 Organic photoelectric compound, composition with same and organic light-emitting device
CN117209460B (en) * 2023-11-09 2024-05-03 浙江华显光电科技有限公司 Organic compound, OLED (organic light-emitting diode) with organic compound and organic light-emitting device

Also Published As

Publication number Publication date
CN113651785B (en) 2024-01-26

Similar Documents

Publication Publication Date Title
CN110407829B (en) Arylamine compound and organic light-emitting device thereof
CN113527181B (en) Nitrogen-containing heterocyclic organic compound and organic light-emitting device thereof
CN113651785B (en) Heterocyclic compound and organic light-emitting device thereof
CN113620917B (en) Triarylamine compound and organic light-emitting device thereof
CN113443998B (en) Triarylamine organic compound and organic light-emitting device thereof
CN112341449B (en) Triarylamine organic compound containing spirofluorene and organic light-emitting device thereof
CN113620818B (en) Triarylamine compound containing condensed rings and organic light-emitting device thereof
CN111875580B (en) Dibenzothiophene derivative and organic light-emitting device thereof
CN113816863A (en) Triarylamine compound, preparation method thereof and organic light-emitting device
CN111116505B (en) Amine compound and organic light-emitting device thereof
CN110964002A (en) Arylamine derivative and organic light-emitting device thereof
CN111933818A (en) Organic light-emitting device
CN113717122A (en) Adamantane spirofluorene derivative and organic electroluminescent device thereof
CN113816921B (en) Heterocyclic compound and organic electroluminescent device thereof
CN115286601B (en) Triarylamine organic compound containing heterocycle and organic light-emitting device thereof
CN115057838B (en) Aromatic amine organic compound and organic light-emitting device thereof
CN115057849B (en) Triarylamine organic compound and organic light-emitting device thereof
CN114621181B (en) Star-shaped tetramine derivative and organic electroluminescent device thereof
CN113717196B (en) Azabenzoxazole or thiazole compound and organic electroluminescent device thereof
CN113582855B (en) Diamine organic compound and organic light-emitting device thereof
CN112750957B (en) Organic electroluminescent device
CN113845512A (en) Compound containing heterocycle and organic electroluminescent device thereof
CN113582857A (en) Fluorene compound and organic electroluminescent device thereof
CN112510160B (en) Organic light-emitting device
CN111969120B (en) Organic electroluminescent device containing fluorene derivative

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