CN113717058A - Triarylamine compound containing fluorene derivative group and organic electroluminescent device thereof - Google Patents

Triarylamine compound containing fluorene derivative group and organic electroluminescent device thereof Download PDF

Info

Publication number
CN113717058A
CN113717058A CN202111093689.3A CN202111093689A CN113717058A CN 113717058 A CN113717058 A CN 113717058A CN 202111093689 A CN202111093689 A CN 202111093689A CN 113717058 A CN113717058 A CN 113717058A
Authority
CN
China
Prior art keywords
substituted
group
unsubstituted
butyl
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
CN202111093689.3A
Other languages
Chinese (zh)
Other versions
CN113717058B (en
Inventor
孙敬
杜明珠
韩春雪
周雯庭
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 CN202111093689.3A priority Critical patent/CN113717058B/en
Publication of CN113717058A publication Critical patent/CN113717058A/en
Application granted granted Critical
Publication of CN113717058B publication Critical patent/CN113717058B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
    • C07D207/09—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/26—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection 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
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—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
    • H10K85/657—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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/20—All rings being cycloaliphatic the ring system containing seven carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/40—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/93—Spiro compounds
    • C07C2603/94—Spiro compounds containing "free" spiro atoms
    • 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)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to the technical field of organic photoelectric materials, in particular to a triarylamine compound containing fluorene derivative groups and an organic electroluminescent device thereof. The triarylamine compound containing the fluorene derivative group provided by the invention has the advantages of good hole mobility, high glass transition temperature (Tg), good thermal stability and film-forming property, and proper energy level, is applied to a hole transmission area in an OLED device, and can effectively improve the luminous efficiency, the driving voltage and the service life of the device. Because the organic material has the HOMO and T1 values with higher matching degree with the luminescent layer, when the organic material is used as a luminescent auxiliary layer, the organic material can prevent excitons from migrating to the interface of the luminescent layer and a hole transmission region, avoid interface luminescence, avoid the organic material from being heated and aged due to the interface luminescence, further improve the luminescent efficiency of the device and prolong the service life of the device. In addition, the triarylamine compound containing fluorene derivative groups also has higher refractive index and can be used as a covering layer.

Description

Triarylamine compound containing fluorene derivative group and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a triarylamine compound containing fluorene derivative groups and an organic electroluminescent device thereof.
Background
Organic Light-Emitting diodes (OLEDs) are one of the most developed display technologies, and have the advantages of small thickness, Light weight, wide viewing angle, short response time, wide temperature range, low energy consumption, high efficiency, good color purity, flexibility, and the like, and are widely used in the fields of illumination and display.
The OLED device is of a sandwich structure and comprises a cathode, an anode and an organic layer arranged between the cathode and the anode, wherein the organic layer is divided into a hole transmission area, an electron transmission area, a light emitting area and the like according to different functions. Under the action of an external electric field, holes and electrons are respectively injected from the anode and the cathode, enter the light emitting region through the hole transmission region and the electron transmission region, are recombined to generate excitons, release energy, the excitons migrate under the action of the electric field and transfer the energy to the luminescent substance in the light emitting region, so that the electrons in the luminescent substance molecules are transited from a ground state to an excited state, and in the process that the electrons return to the ground state from the excited state, the energy is released in the form of light to generate a light emitting phenomenon.
The hole transport region mainly plays a role in injecting and transporting holes, and can be subdivided into a hole injection layer, a hole transport layer, a light-emitting auxiliary layer and the like. Hole transport materials used in the hole transport region should generally have high hole mobility, good thermal stability, good film-forming properties, and appropriate energy levels. Aromatic amine compounds are one of the most widely used hole transport materials in the field of OLEDs, and the specific application is different due to the difference in properties of aromatic amine compounds having different structures. For example, according to differences in properties such as the Highest Occupied Molecular Orbital (HOMO), triplet level (T1), hole injection ability, and hole transport ability of the aromatic amine compound, the aromatic amine compounds of different structures are applied to different organic layers, some of which are used for the hole transport layer, some of which are used for the hole injection layer, some of which are used for the light emission auxiliary layer, and some of which are used for a plurality of organic layers. The development of hole transport materials with excellent performance and wide application is a challenge for OLED workers.
In order to optimize the performance of the OLED device, a covering layer is added on the side of the cathode away from the anode by the technical personnel in the field, so that the OLED device has higher refractive index while isolating harmful factors such as air, moisture, ultraviolet rays and the like, and can improve the performances such as luminous efficiency, service life and the like of the device. However, the variety of covering materials which are excellent in performance and widely used at present is limited, and development is urgently needed.
Disclosure of Invention
The invention provides a triarylamine compound containing a fluorene derivative group, which has high hole mobility, good thermal stability, good film forming property, energy level matched with a light-emitting layer, higher refractive index and a structure shown in a formula (I):
Figure BDA0003268517080000011
wherein A, B, E, F is independently selected from one of substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene;
ar is1One selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted carbazolyl group;
ar is2、Ar3Independently selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted carbazolyl, and Ar2、Ar3At least one of the above groups is substituted with one of a substituted or unsubstituted C3-C7 alicyclic group and a substituted or unsubstituted alicyclic heterocyclic group having 5-6 ring atoms;
said L1～L3Independently selected from one of single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted anthrylene and substituted or unsubstituted biphenylene;
said R1、R2Independently selected from one of hydrogen atom, deuterium atom, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted n-propyl group, substituted or unsubstituted isopropyl group, substituted or unsubstituted n-butyl group, substituted or unsubstituted sec-butyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted isobutyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthryl group, and substituted or unsubstituted phenanthryl group, when R is1、R2When one is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl and substituted or unsubstituted phenanthryl, the two can be connected to form a five-membered carbocyclic ring or a six-membered carbocyclic ring;
a and b are independently selected from one of 0,1, 2,3, 4,5, 6 and 7, c and d are independently selected from one of 0,1, 2,3, 4,5, 6,7 and 8;
said R3～R6Independently selected from one of a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group, when a plurality of R's exist3When plural R's are present, they may be the same or different4When plural R's are present, they may be the same or different5When plural R's are present, they may be the same or different6When they are used, they may be the same or different.
The invention also provides an organic electroluminescent device which comprises an anode, a cathode and an organic layer arranged between the anode and the cathode, wherein the organic layer comprises a hole transmission region, a light-emitting layer and an electron transmission region, and the hole transmission region contains more than one of the triarylamine compounds containing fluorene derivative groups.
The invention further provides an organic electroluminescent device which comprises an anode, a cathode, an organic layer arranged between the anode and the cathode, and a covering layer arranged on the side of the cathode, which is far away from the anode, wherein the covering layer contains more than one of the triarylamine compounds containing fluorene derivative groups.
Has the advantages that:
the triarylamine compound containing fluorene derivative groups, provided by the formula (I), has good hole mobility, high glass transition temperature (Tg), good thermal stability and good film forming property, and plays a role in properly adjusting the energy level of molecules and the hole transmission capacity due to the existence of at least one alicyclic group or aliphatic heterocyclic group in molecules, so that the triarylamine compound can be well matched with other organic layers for use, is applied to a hole transmission area in an OLED device, and can effectively improve the luminous efficiency, the driving voltage and the service life of the device. Meanwhile, the organic material further has the HOMO and T1 values which are higher in matching degree with other organic layers, particularly a light-emitting layer, can be used as a light-emitting auxiliary layer, plays a role in preventing excitons from migrating to the interface of the light-emitting layer and a hole transmission region, avoids light emission at the interface between the light-emitting layer and the hole transmission region, further avoids the organic material from being aged due to heat caused by interface light emission, and further improves the light-emitting efficiency and the service life of the device.
In addition, the triarylamine compound containing fluorene derivative groups in the formula (I) also has a high refractive index, and can be applied to OLED devices as a covering layer, so that the luminous efficiency and the service life of the devices are improved.
Detailed Description
The following will clearly and completely describe the technical solutions of the specific 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.
The "substitution" as referred to herein means that a hydrogen atom in some functional groups is replaced with another atom or functional group (i.e., substituent), and the substituted position is not limited as long as the position is a position at which a hydrogen atom is substituted, and when two or more are substituted, two or more substituents may be the same as or different from each other.
The term "substituted or unsubstituted" as used herein means not substituted or substituted with one or more substituents selected from the group consisting of: deuterium atom, halogen atom, amino group, cyano group, nitro group, substituted or unsubstituted alkyl group of C1 to C30, substituted or unsubstituted alicyclic group of C3 to C30, substituted or unsubstituted alkenyl group of C1 to C30, substituted or unsubstituted alkynyl group of C1 to C30, substituted or unsubstituted alkoxy group of C1 to C30, substituted or unsubstituted aryl group of C6 to C60, substituted or unsubstituted aryloxy group of C6 to C60, substituted or unsubstituted heteroaryl group of C2 to C60, preferably deuterium atom, halogen atom, cyano group, nitro group, alkyl group of C1 to C12, alkenyl group of C1 to C12, alkynyl group of C1 to C12, alkoxy group of C1 to C12, cycloalkyl group of C3 to C12, aryl group of C6 to C30, heteroaryl group of C2 to C30, and, when substituted with a plurality of substituents, the same or different groups; preferably, it means unsubstituted or substituted by one or more substituents selected from the group consisting of: deuterium atom, fluorine atom, chlorine atom, cyano group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopropane group, cyclobutane group, cyclopentyl group, cyclohexane group, cycloheptane group, cyclopentenyl group, cyclohexenyl group, cycloheptene group, adamantyl group, norbornyl group, vinyl group, methoxy group, ethoxy group, phenyl group, pentadeuterophenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, triphenylene group, pyrenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, spirobifluorenyl group, pyridyl group, pyrimidyl group, triazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, quinoxalyl group, dibenzofuranyl group, dibenzothienyl group, phenylcarbazolyl group, 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.
In the present specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example,
Figure BDA0003268517080000031
can represent
Figure BDA0003268517080000032
And so on.
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 alicyclic group in the present invention refers to a group formed by removing one hydrogen atom from an alkane molecule having an alicyclic structure, and can be classified into a saturated alicyclic group (i.e., cycloalkyl group) and an unsaturated cycloalkyl group, and also into a monocyclic alkyl group and a fused-ring alkyl group. Preferably from 3 to 15 carbon atoms, more preferably from 3 to 12 carbon atoms, and particularly preferably from 5 to 10 carbon atoms. Examples may include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentenyl, cyclohexenyl, cycloheptenyl, adamantyl, norbornyl, and the like. The alkyl group is preferably a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, a cyclohexenyl group, a 1-adamantyl group, a 2-adamantyl group or a norbornyl group.
The term "alicyclic heterocyclic group" as used herein means a group formed by removing one hydrogen atom from an alicyclic heterocyclic molecule in which ring-constituting atoms contain at least one hetero atom in addition to carbon atoms, and the hetero atom includes a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, etc., preferably a nitrogen atom, an oxygen atom, a sulfur atom, and particularly preferably a nitrogen atom. Preferably 1 to 3 heteroatoms, more preferably 1 to 2 heteroatoms, and particularly preferably 1 heteroatom. Preferably 3 to 15 ring atoms, more preferably 3 to 12 ring atoms, and particularly preferably 5 to 6 ring atoms. Examples may include ethylene oxide, ethylene sulfide, propylidene, tetrahydropyrrole, piperidyl, morpholinyl, thiomorpholinyl, piperazinyl, and the like, but are not limited thereto. The above-mentioned lipid heterocyclic group is preferably tetrahydropyrrolyl, piperidyl, morpholinyl, thiomorpholinyl, piperazinyl.
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 linking to form a cyclic structure according to the present invention means that two groups are linked to each other by a chemical bond and optionally subjected to aromatization. As exemplified below:
Figure BDA0003268517080000051
in the present invention, the ring formed by the connection may be a five-membered carbocyclic ring or a six-membered carbocyclic ring.
The invention provides a triarylamine compound containing a fluorene derivative group, which has a structure shown in a formula (I):
Figure BDA0003268517080000052
wherein A, B, E, F is independently selected from one of substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene;
ar is1One selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted carbazolyl group;
ar is2、Ar3Independently selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted carbazolyl, and Ar2、Ar3At least one of the above groups is substituted with one of a substituted or unsubstituted C3-C15 alicyclic group and a substituted or unsubstituted alicyclic heterocyclic group having 5-6 ring atoms;
said L1～L3Independently selected from one of single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted anthrylene and substituted or unsubstituted biphenylene；
Said R1、R2Independently selected from one of hydrogen atom, deuterium atom, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted n-propyl group, substituted or unsubstituted isopropyl group, substituted or unsubstituted n-butyl group, substituted or unsubstituted sec-butyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted isobutyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthryl group, and substituted or unsubstituted phenanthryl group, when R is1、R2When one is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl and substituted or unsubstituted phenanthryl, the two can be connected to form a five-membered carbocyclic ring or a six-membered carbocyclic ring;
a and b are independently selected from one of 0,1, 2,3, 4,5, 6 and 7, c and d are independently selected from one of 0,1, 2,3, 4,5, 6,7 and 8;
said R3～R6Independently selected from one of a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group, when a plurality of R's exist3When plural R's are present, they may be the same or different4When plural R's are present, they may be the same or different5When plural R's are present, they may be the same or different6When they are used, they may be the same or different.
Preferably, the triarylamine compound containing a fluorene derivative group has a structure shown in formula (II):
Figure BDA0003268517080000061
a, B, E, F, Ar as described1、Ar2、Ar3、L1～L3、R1、R2、a、b、c、d、R3～R6All as described above.
Preferably, the substituent in the "substituted or unsubstituted" is one selected from deuterium atom, halogen, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, naphthyl and deuterated naphthyl, and when a plurality of substituents are present, they may be the same or different, and two adjacent substituents may be linked to form a ring.
Preferably, the A, B, E, F is independently selected from one of the following structures:
Figure BDA0003268517080000062
wherein
Figure BDA0003268517080000063
Represents the position attached to a carbon atom on the five-membered carbon ring.
Preferably, said A, B, E, F is independently selected from benzene or naphthalene.
Preferably, the A, B, E, F is independently selected from one of the following structures:
Figure BDA0003268517080000071
preferably, A, B, E, F is selected from benzene.
Preferably, Ar is1Selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, and a substituted or unsubstituted isopropyl groupAnd the substituted or unsubstituted phenyl, the substituted or unsubstituted naphthyl, the substituted or unsubstituted anthryl, the substituted or unsubstituted phenanthryl, the substituted or unsubstituted biphenyl, the substituted or unsubstituted fluorenyl, the substituted or unsubstituted dibenzofuranyl, the substituted or unsubstituted dibenzothiophenyl and the substituted or unsubstituted carbazolyl.
Preferably, Ar is1One selected from the group consisting of a hydrogen atom, a deuterium atom, halogen, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, tert-butyl, deuterated tert-butyl, isobutyl, deuterated isobutyl, and a group represented by:
Figure BDA0003268517080000072
wherein e is selected from one of 0,1, 2,3, 4,5, f is selected from one of 0,1, 2,3, 4,5, 6,7, g is selected from one of 0,1, 2,3, 4,5, 6,7,8, 9, h is selected from one of 0,1, 2,3, 4, i is selected from one of 0,1, 2,3, 4,5, 6,7, j is selected from one of 0,1, 2,3, 4,5, 6,7, 8;
said R11One selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an n-propyl group, a deuterated n-propyl group, an isopropyl group, a deuterated isopropyl group, an n-butyl group, a deuterated n-butyl group, a sec-butyl group, a deuterated sec-butyl group, an isobutyl group, a deuterated isobutyl group, a tert-butyl group and a deuterated tert-butyl group, when a plurality of R's are present11Where they are the same or different,
said R12、R13Independently selected from one of hydrogen atom, deuterium atom, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl and deuterated tert-butyl.
Preferably, Ar is1One selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, and a substituted or unsubstituted biphenyl group.
Preferably, Ar is1One selected from hydrogen atom, deuterium atom, methyl, deuterated methyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, anthryl, deuterated anthryl, phenanthryl, deuterated phenanthryl, biphenyl and deuterated biphenyl.
Preferably, Ar is1One selected from a hydrogen atom, a deuterium atom, a methyl group, a deuterated methyl group, and the group shown below:
Figure BDA0003268517080000081
preferably, the substituted or unsubstituted C3-C15 alicyclic group is selected from the group consisting of cyclopropyl, deuterated cyclopropyl, methyl-substituted cyclopropyl, ethyl-substituted cyclopropyl, n-propyl-substituted cyclopropyl, isopropyl-substituted cyclopropyl, n-butyl-substituted cyclopropyl, tert-butyl-substituted cyclopropyl, cyclobutyl, deuterated cyclobutyl, methyl-substituted cyclobutyl, ethyl-substituted cyclobutyl, n-propyl-substituted cyclobutyl, isopropyl-substituted cyclobutyl, n-butyl-substituted cyclobutyl, tert-butyl-substituted cyclobutyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, ethyl-substituted cyclopentyl, n-propyl-substituted cyclopentyl, isopropyl-substituted cyclopentyl, n-butyl-substituted cyclopentyl, tert-butyl-substituted cyclopentyl, cyclohexyl, deuterated cyclohexyl, methyl-substituted cyclohexyl, ethyl-substituted cyclohexyl, n-propyl-substituted cyclohexyl, Isopropyl-substituted cyclohexyl, n-butyl-substituted cyclohexyl, tert-butyl-substituted cyclohexyl, adamantyl, deuterated adamantyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, n-propyl-substituted adamantyl, isopropyl-substituted adamantyl, n-butyl-substituted adamantyl, tert-butyl-substituted adamantyl, norbornyl, deuterated norbornyl, methyl-substituted norbornyl, ethyl-substituted norbornyl, n-propyl-substituted norbornyl, isopropyl-substituted norbornyl, n-butyl-substituted norbornyl, tert-butyl-substituted norbornyl, cyclopentenyl, deuterated cyclopentenyl, methyl-substituted cyclopentenyl, ethyl-substituted cyclopentenyl, n-propyl-substituted cyclopentenyl, isopropyl-substituted cyclopentenyl, n-butyl-substituted cyclopentenyl, tert-butyl-substituted cyclopentenyl, One of cyclohexenyl, deuterated cyclohexenyl, methyl-substituted cyclohexenyl, ethyl-substituted cyclohexenyl, n-propyl-substituted cyclohexenyl, isopropyl-substituted cyclohexenyl, n-butyl-substituted cyclohexenyl and tert-butyl-substituted cyclohexenyl.
Preferably, the substituted or unsubstituted alicyclic group of C3 to C15 is one selected from the group consisting of a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted norbornyl group and a substituted or unsubstituted adamantyl group.
Preferably, the substituted or unsubstituted alicyclic group of C3-C15 is selected from one of the following groups:
Figure BDA0003268517080000082
preferably, the substituted or unsubstituted alicyclic group of C3-C15 is selected from one of the following groups:
Figure BDA0003268517080000083
Figure BDA0003268517080000091
preferably, the aliphatic heterocyclic group having 5 to 6 ring-forming atoms contains at least one nitrogen atom.
Preferably, the substituted or unsubstituted aliphatic heterocyclic group having 5 to 6 ring atoms is selected from one of the following groups:
Figure BDA0003268517080000092
preferably, the substituted or unsubstituted aliphatic heterocyclic group having 5 to 6 ring atoms is selected from one of the following groups:
Figure BDA0003268517080000093
preferably, the substituted or unsubstituted aliphatic heterocyclic group having 5 to 6 ring atoms is selected from one of the following groups:
Figure BDA0003268517080000094
preferably, the substituted or unsubstituted aliphatic heterocyclic group having 5 to 6 ring atoms is selected from one of the following groups:
Figure BDA0003268517080000095
preferably, the substituted or unsubstituted aliphatic heterocyclic group having 5 to 6 ring atoms is selected from one of the following groups:
Figure BDA0003268517080000096
preferably, Ar is2、Ar3At least one of them is selected from one of the following groups:
Figure BDA0003268517080000097
wherein, a is0One selected from 1,2, 3,4 and 5, and b0One selected from 1,2, 3,4, 5,6 and 7, and c0One selected from 1,2, 3,4, 5,6, 7,8 and 9, and d0One selected from 1,2, 3 and 4, e0Selected from one of 1,2 and 3, the f0One selected from 1,2, 3,4, 5,6 and 7, and g0One selected from 1,2, 3,4, 5,6, 7, 8;
said R20、R20'independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an n-propyl group, a deuterated n-propyl group, an isopropyl group, a deuterated isopropyl group, an n-butyl group, a deuterated n-butyl group, a sec-butyl group, a deuterated sec-butyl group, an isobutyl group, a deuterated isobutyl group, a tert-butyl group, a deuterated tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, the above-mentioned substituted or unsubstituted alicyclic group having from C3 to C15, and a substituted or unsubstituted alicyclic group having from 5 to 6 ring-forming atoms, wherein when a plurality of R's are present20When plural R's are present, they may be the same or different, and they may be bonded to form a ring20' when they are the same or different, they may be bonded to form a ring, and at least one R is20At least one R is selected from the group consisting of the above-mentioned substituted or unsubstituted C3-C15 alicyclic group and substituted or unsubstituted alicyclic heterocyclic group having 5-6 ring atoms20' one selected from the group consisting of the above-mentioned substituted or unsubstituted C3-C15 alicyclic group and a substituted or unsubstituted alicyclic heterocyclic group having 5-6 ring atoms;
said R201、R202Independently selected from one of hydrogen atom, deuterium atom, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl and deuterated tert-butyl, and the two can be connected to form a substituted or unsubstituted C3-C15 alicyclic group;
the rest is selected from one of the following groups:
Figure BDA0003268517080000101
wherein, a is0' is selected from one of 1,2, 3,4 and 5, and b is0' is selected from one of 1,2, 3,4, 5,6 and 7, and c is0' is selected from one of 1,2, 3,4, 5,6, 7,8 and 9, and d is0' is selected from one of 1,2, 3 and 4, and e is0' is selected from one of 1,2 and 3, and f is0' is selected from one of 1,2, 3,4, 5,6, 7, and g0' is selected from one of 1,2, 3,4, 5,6, 7, 8;
said R30One selected from the group consisting of a hydrogen atom, a deuterium atom, halogen, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, naphthyl and deuterated naphthyl, when a plurality of R's are present30When they are the same or different, they may be linked to form a ring;
said R301、R302Independently selected from one of hydrogen atom, deuterium atom, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl and deuterated tert-butyl, and the two can be connected to form one of substituted or unsubstituted alicyclic groups of C3-C15.
Preferably, R is20Wherein the number of the alicyclic groups is 1 to 2 selected from the group consisting of the substituted or unsubstituted C3 to C15 alicyclic groups and the substituted or unsubstituted alicyclic heterocyclic groups having 5 to 6 ring atoms.
Preferably, R is20In the formula, 1 to 2 members selected from the group consisting of the above-mentioned substituted or unsubstituted C3 to C15 alicyclic groups and substituted or unsubstituted alicyclic heterocyclic groups having 5 to 6 ring-forming atoms are present.
Preferably, theR is as described20Wherein the number of the (1) is one selected from the group consisting of the substituted or unsubstituted C3-C15 alicyclic group and the substituted or unsubstituted alicyclic heterocyclic group having 5-6 ring atoms.
Preferably, R is20In the formula, 1 is selected from the group consisting of the substituted or unsubstituted C3-C15 alicyclic group and the substituted or unsubstituted alicyclic heterocyclic group having 5-6 ring atoms.
Preferably, Ar is2、Ar3At least one of them is selected from one of the following groups:
Figure BDA0003268517080000111
Figure BDA0003268517080000121
Figure BDA0003268517080000131
Figure BDA0003268517080000141
Figure BDA0003268517080000151
Figure BDA0003268517080000161
Figure BDA0003268517080000171
wherein k is selected from 0,1, 2,3 or 4, l is selected from 0,1, 2,3, 4,5 or 6, m is selected from 0,1 or 2, n is selected from 0,1, 2 or 3, o is selected from 0,1, 2,3, 4 or 5;
said R21One selected from the group consisting of a hydrogen atom, a deuterium atom, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, a n-propyl group, a deuterated n-propyl group, an isopropyl group, a deuterated isopropyl group, a n-butyl group, a deuterated n-butyl group, a sec-butyl group, a deuterated sec-butyl group, an isobutyl group, a deuterated isobutyl group, a tert-butyl group, a deuterated tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group and a deuterated naphthyl group, when a plurality of R's are present21When used, they may be the same or different;
the rest is selected from one of the following groups:
Figure BDA0003268517080000172
Figure BDA0003268517080000181
preferably, said L1～L3Independently selected from single bond, one of the following groups:
Figure BDA0003268517080000182
wherein, a is1One selected from 0,1, 2,3 and 4, and b1One selected from 0,1, 2,3 and 4, and c1One selected from 0,1, 2;
said R41One selected from the group consisting of a hydrogen atom, a deuterium atom, halogen, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, naphthyl and deuterated naphthyl, when a plurality of R's are present41When they are used, they may be the same or different.
Preferably, said L1～L3Independently selectOne of the following groups is selected from single bonds:
Figure BDA0003268517080000183
most preferably, the triarylamine compound containing a fluorene derivative group is selected from one of the following compounds:
Figure BDA0003268517080000191
Figure BDA0003268517080000201
Figure BDA0003268517080000211
Figure BDA0003268517080000221
Figure BDA0003268517080000231
Figure BDA0003268517080000241
Figure BDA0003268517080000251
Figure BDA0003268517080000261
Figure BDA0003268517080000271
Figure BDA0003268517080000281
Figure BDA0003268517080000291
Figure BDA0003268517080000301
Figure BDA0003268517080000311
Figure BDA0003268517080000321
Figure BDA0003268517080000331
Figure BDA0003268517080000341
the above description only illustrates some specific structural forms of the triarylamine compound having a fluorene derivative group represented by formula (I), but the present invention is not limited to these listed chemical structures, and all the substituents are as defined above and included on the basis of formula (I).
The triarylamine compound containing fluorene derivative groups, shown in formula (I), can be prepared by the following synthetic route:
Figure BDA0003268517080000342
whereinSaid X, Y is independently selected from chlorine atom, bromine atom or iodine atom, said A, B, E, F, Ar1、Ar2、Ar3、L1～L3、R1、R2、a、b、c、d、R3～R6All as described above.
Firstly, arylamine compound (Y3) and halide (A) are subjected to Buchwald reaction to obtain secondary amine compound (B); and reacting the secondary amine compound (B) with halide (C) through Buchwald to obtain the triarylamine compound containing the fluorene derivative group shown in the formula (I). The reaction conditions in the above synthetic route, such as reaction solvent, catalyst, ligand, base and the like, may be any of conventional methods, and are not particularly limited. The preparation method has the advantages of easily available raw materials, simple preparation process and excellent reaction yield.
The invention also provides an organic electroluminescent device which comprises an anode, a cathode and an organic layer arranged between the anode and the cathode, wherein the organic layer comprises a hole transmission area, a luminescent layer and an electron transmission area, and the hole transmission area contains more than one of the triarylamine compounds containing fluorene derivative groups.
Preferably, the hole transport region includes a hole injection layer containing at least one triarylamine compound having a fluorene derivative group as described above.
Preferably, the hole transport region includes a hole transport layer containing at least one triarylamine compound having a fluorene derivative group as described above.
Preferably, the hole transporting region includes a light-emitting auxiliary layer containing at least one of the triarylamine compounds having a fluorene derivative group as described above.
The invention also provides an organic electroluminescent device which comprises an anode, a cathode, an organic layer arranged between the anode and the cathode, and a covering layer arranged on the side of the cathode, which is far away from the anode, wherein the covering layer contains more than one of the triarylamine compounds containing fluorene derivative groups.
The hole injection layer of the present invention may have a single-layer structure composed of a single substance, or may have a single-layer structure or a multi-layer structure composed of different substances. Triarylamine compounds, porphyrin compounds, styrene compounds, polythiophene and its derivatives, phthalocyanine derivatives, allyl compounds, and other substances having high hole injection properties, for example, 4,4',4 ″ -tris [ 2-naphthylphenylamino ] triphenylamine (2-TNATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN), copper phthalocyanine (CuPC), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanodimethyl-p-benzoquinone (F4-TCNQ), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT/PSS), and the triarylamine compounds containing a fluorene derivative group described in the present invention can be used, but are not limited thereto. Preferably, the hole injection layer has a single-layer structure composed of a host material and a dopant material, the host material may be a triarylamine compound, preferably the triarylamine compound containing a fluorene derivative group according to the present invention, and the dopant material may be an allyl compound. More preferably, the mass ratio of the host material to the doping material is 100: 1-100: 10.
The hole transport layer of the present invention may have a single-layer structure composed of a single substance, or may have a single-layer structure or a multi-layer structure composed of different substances. Triarylamine derivatives having two or more triarylamine structures linked by a single bond or arylene group, and other hole mobilities of 10 can be used-6cm2Examples of the material having a/Vs or more include, but are not limited to, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (TDATA), and triarylamine compounds having a fluorene derivative group according to the present invention. Preferably, the hole transport layer uses the triarylamine compound containing a fluorene derivative group according to the present invention.
The light-emitting auxiliary layer of the present invention may be a single-layer structure formed of a single substance, or a single-layer structure or a multilayer structure formed of different substances, and a triarylamine derivative, a spirofluorene derivative, a dibenzofuran derivative, and other materials having appropriate HOMO and T1 energy levels, in which two or more triarylamine structures are connected by a single bond or an arylene group, may be used, for example, TPD, NPB, N4, N4-bis ([1,1 '-biphenyl ] -4-yl) -N4' -phenyl N4'- [1, 1': 4', 1' -terphenyl ] -4-yl- [1,1' -biphenyl ] -4,4' -diamine, N- ([1,1' -diphenyl ] -4-yl) -N- (9, 9-dimethyl-9H-furan-2-yl) -9,9' -spirobifluorene-2-amine, N-bis ([1,1' -biphenyl ] -4-yl) -3' - (dibenzo [ b, d ] furan-4-yl) - [1,1' -biphenyl ] -4-amine, triarylamine compounds containing a fluorene derivative group as described herein, but not limited thereto. Preferably, the light-emitting auxiliary layer uses the triarylamine compound containing a fluorene derivative group according to the present invention.
The covering layer comprises a first covering layer and/or a second covering layer, and when the first covering layer or the second covering layer is included, the covering layer can be a single-layer structure formed by a single substance or a single-layer structure formed by different substances; when the first cover layer and the second cover layer are included, they are a multilayer structure made of a single substance or different substances. The material of the cover layer may be organic or inorganic, and preferably, one or more of the triarylamine compounds containing a fluorene derivative group according to the present invention are used.
The light-emitting layer of the invention may contain only a guest material, or a guest material may be dispersed in a host material. As the guest material, a fluorescent compound such as a pyrene derivative, a fluoranthene derivative, an aromatic amine derivative and the like can be used, and specific examples thereof include 10- (2-benzothiazolyl) -2,3,6, 7-tetrahydro-1, 1,7, 7-tetramethyl-1H, 5H,11H- [ 1H]Benzopyran [6,7,8-ij]Quinolizin-11-one (C545T), 4' -bis (9-ethyl-3-carbazolenyl) -1,1' -biphenyl (BCzVBi), 4' -bis [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi), and the like; phosphorescent light-emitting materials may also be used, for example, metal complexes such as iridium complex, osmium complex, and platinum complex, and specific examples thereof include bis (4, 6-difluorophenylpyridine-N, C2) picolinatoiridium (FIrpic) and tris (2-phenylpyridine) iridium (Ir (ppy)3) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy)2(acac)) and the like. The host material is preferably a material having a higher LUMO and a lower HOMO than the guest material, for exampleA metal complex such as an aluminum complex or a zinc complex, a heterocyclic compound such as an oxadiazole derivative or a benzimidazole derivative, a condensed aromatic compound such as a carbazole derivative or an anthracene derivative, an aromatic amine compound such as a triarylamine derivative or a condensed polycyclic aromatic amine derivative, and specifically 8-hydroxyquinoline aluminum (Alq)3) Bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1,1' -biphenyl-4-hydroxy) aluminum (BAlq), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), TPD, 4' -bis (9-Carbazole) Biphenyl (CBP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (2-naphthyl) Anthracene (ADN), and the like.
The electron transport region comprises at least one of an electron injection layer, an electron transport layer and a hole blocking layer.
The electron injection layer can be a single-layer structure formed by a single substance, or a single-layer structure or a multi-layer structure formed by different substances, and one or more of the following substances can be selected: alkali metals, alkaline earth metals, alkali metal halides, alkaline earth metal halides, alkali metal oxides, alkaline earth metal oxides, alkali metal salts, alkaline earth metal salts, and other substances having a high electron-injecting property. Specific examples thereof include Li, Ca, Sr, LiF, CsF and CaF2、BaO、Li2CO3、CaCO3、Li2C2O4、Cs2C2O4、CsAlF4And LiOx, Yb, Tb, etc.
The electron transport layer of the present invention may have a single-layer structure composed of a single substance, or a single-layer structure or a multilayer structure composed of different substances, and aluminum complexes, beryllium complexes, zinc complexes, imidazole derivatives, benzimidazole derivatives, carbazole derivatives, phenanthroline derivatives, polymer compounds, and the like, which have high electron transport properties, for example, Alq3Bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (BeBq2) BAlq, 2- (4-biphenyl) -5-phenyl oxadiazole (PBD), and the like.
The hole-blocking layer of the present invention may have a single-layer structure made of a single substance, or may have a single-layer structure or a multi-layer structure made of different substances. Selected materialsThe T1 energy level is required to be higher than the light emitting layer so as to block energy loss of the light emitting layer. In addition, the HOMO energy level of the selected material is lower than that of the host material of the light-emitting layer, so that the hole blocking effect is achieved. Further, the electron mobility of the hole blocking layer material used is 10-6cm2Above Vs, it is preferable to use triazine derivatives, azabenzene derivatives, etc. because they facilitate electron transport. Most preferred are triazine derivatives.
Preferably, the organic layer comprises a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer;
preferably, the organic layer comprises a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer;
preferably, the organic layer comprises a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer and an electron injection layer;
preferably, the organic layer includes a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
The anode of the present invention may be a reflective anode, such as a reflective film formed of silver (Ag), magnesium (Mg), aluminum (Al), gold (Au), nickel (Ni), chromium (Cr), ytterbium (Yb), or an alloy thereof, or may have a high work function and be a transparent or semi-transparent layer structure, such as Indium Tin Oxide (ITO), indium zinc oxide (ZnO), Aluminum Zinc Oxide (AZO), Indium Gallium Oxide (IGO), indium oxide (In)2O3) Or tin oxide (SnO)2) And (3) forming a layer structure.
The cathode of the invention can be a thin film with low work function made of lithium, calcium, lithium fluoride/aluminum, silver, magnesium-silver alloy and the like, and can be made into a reflecting electrode, a transparent electrode or a semitransparent electrode by adjusting the thickness of the film.
The organic layers, the cathode, the anode and the cover layer can be prepared by any one of vacuum evaporation, ink-jet printing, sputtering, plasma, ion plating, spin coating, dipping, screen printing and the like, and the film thickness of each layer is not particularly limited so as to obtain good device performance. The respective organic layers are preferably prepared by a method of vacuum evaporation, inkjet printing, or spin coating.
The thickness of each of the organic layer and the capping layer is usually 5nm to 100um, preferably 10nm to 200 nm. The thickness of the anode and the cathode is adjusted according to the required transparency.
The organic electroluminescent device provided by the invention can be applied to the field of OLED illumination and the field of OLED display, and can be specifically listed as a large-size display such as a smart phone display screen, a tablet computer display screen, an intelligent wearable device display screen, a television and the like, VR (virtual reality) and an automobile tail lamp and the like.
The technical scheme and technical effects of the present invention are further described below by examples and comparative examples.
The mass spectrum of the compound of the invention uses a G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer of Watts corporation of England, and chloroform is used as a 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: preparation of Compound 29
Figure BDA0003268517080000371
100mL of an ether solution of Y2-1(106.73g, 546mmol) was added dropwise to 1, 2-dibromoethane-activated magnesium (18.24g, 601mmol) 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. Under nitrogen, 140mL of anhydrous dichloromethane dissolved with Y1-1(43.77g, 180mmol) was added to grignard reagent, 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 a-1(41.66g, yield 83%) was obtained by flash-passing through a silica gel column (N-hexane as eluent) to obtain a mass spectrum m/z: 278.1731 (theoretical value: 278.1739).
Toluene (600mL), A-1(33.46g, 120mmol), Y3-1(20.31g, 120mmol), palladium acetate (0.40g, 1.80mmol), sodium tert-butoxide (23.06g, 240mmol), and tri-tert-butylphosphine (16mL of a 1.0M solution in toluene) were added to the reaction flask in this order under nitrogen. And reacted under reflux for 2 hours. After the reaction had ceased, the mixture was cooled to room temperature, filtered through celite, the filtrate was concentrated, recrystallised from toluene/methanol 20/3, filtered with suction and rinsed with methanol to give a recrystallised solid which gave B-1(39.02g, 79% yield), ms m/z: 411.2872 (theoretical value: 411.2864).
Y5-1(36.71g, 92mmol) and 80mL of tetrahydrofuran solvent are added into a three-necked flask under the protection of nitrogen, after the mixture is cooled to-78 ℃, 14mL of n-hexane mixed solution (1.6M) containing n-butyllithium is added, after the mixture is stirred for 50min, 60mL of tetrahydrofuran solution dissolved with Y4-1(21.70g, 84mmol) is added dropwise, then the mixture is stirred for 50min at-78 ℃, and after the mixture is heated to room temperature, the stirring is continued for 3 h. Adding saturated ammonium chloride solution, separating an organic layer, evaporating a solvent, transferring the obtained residue into a three-neck flask, adding 200mL of acetic anhydride and 8mL of hydrochloric acid, heating at 100 ℃, stirring for 3 hours, pouring the reaction liquid into 80mL of ice water to separate out a solid, filtering to obtain a solid crude product, purifying and refining by a silica gel column (n-hexane/ethyl acetate: 30/1) to obtain C-1(32.78g, yield 76%), mass spectrum m/z: 512.1149 (theoretical value: 512.1140).
Toluene (600mL), C-1(30.81g, 60mmol), B-1(27.16g, 66mmol), palladium acetate (0.20g, 0.90mmol), sodium tert-butoxide (11.53g, 120mmol), and tri-tert-butylphosphine (8mL of a 1.0M solution in toluene) were added to the reaction flask in this order under nitrogen. And reacted for 2h under reflux. After the reaction was stopped, the mixture was cooled to room temperature, filtered through celite, the filtrate was concentrated, recrystallized from toluene/methanol 20/1, filtered with suction and rinsed with methanol to give a recrystallized solid, compound 29(37.99g, 75% yield) having a purity of 99.83% or more by HPLC. Mass spectrum m/z: 843.4751 (theoretical value: 843.4742). Theoretical element content (%) C64H53D4N：C,91.06；H7.28; n, 1.66. Measured elemental content (%): c, 91.08; h, 7.29; n, 1.68.
Synthesis example 2: preparation of Compound 100
Figure BDA0003268517080000381
The same procedures were repeated except for sequentially substituting Y1-1, Y2-1, A-1, Y5-1, C-1 and B-1 in Synthesis example 1 for equimolar amounts of Y1-2, Y2-2, A-2, Y5-2, C-2 and B-2 to obtain 100(41.29g) having a solid purity by HPLC of 99.87% or more. Mass spectrum m/z: 881.4030 (theoretical value: 881.4022). Theoretical element content (%) C68H51N: c, 92.58; h, 5.83; n, 1.59. Measured elemental content (%): c, 92.59; h, 5.84; n, 1.61.
Synthetic example 3: preparation of Compound 103
Figure BDA0003268517080000391
Compound 103(39.65g) was obtained by the same procedure except that Y1-1, Y2-1, A-1, Y3-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of Y1-3, Y2-3, A-3, Y3-3, C-2 and B-3 in this order, and the purity by HPLC was ≧ 99.75%. Mass spectrum m/z: 904.4813 (theoretical value: 904.4805). Theoretical element content (%) C69H52D5N: c, 91.55; h, 6.90; n, 1.55. Measured elemental content (%): c, 91.57; h, 6.91; n, 1.56.
Synthetic example 4: preparation of Compound 105
Figure BDA0003268517080000392
Compound 105(40.41g) was obtained by the same procedure except that A-1, Y3-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of A-4, Y3-4, C-2 and B-4 in that order, and the purity by HPLC was ≧ 99.76%. Mass spectrum m/z: 909.4326 (theoretical value: 909.4335). Theoretical element content(％)C70H55N: c, 92.37; h, 6.09; n, 1.54. Measured elemental content (%): c, 92.38; h, 6.11; n, 1.55.
Synthesis example 5: preparation of Compound 110
Figure BDA0003268517080000393
Compound 110(40.20g) was obtained by the same procedure except for replacing A-1, Y3-1, Y4-1, Y5-1, C-1 and B-1 in Synthesis example 1 with equimolar amounts of A-5, Y3-5, Y4-5, Y5-2, C-5 and B-5 in the same order, and the solid purity by HPLC (HPLC) was ≧ 99.77%. Mass spectrum m/z: 858.3985 (theoretical value: 858.3974). Theoretical element content (%) C65H50N2: c, 90.87; h, 5.87; and N, 3.26. Measured elemental content (%): c, 90.88; h, 5.89; and N, 3.27.
Synthetic example 6: preparation of Compound 114
Figure BDA0003268517080000394
Compound 114(38.66g) was obtained by the same procedure except that A-1, Y3-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of A-6, Y3-4, C-2 and B-6 in that order, and the purity by HPLC (solid purity) was ≧ 99.85%. Mass spectrum m/z: 858.3982 (theoretical value: 858.3974). Theoretical element content (%) C65H50N2: c, 90.87; h, 5.87; and N, 3.26. Measured elemental content (%): c, 90.88; h, 5.89; and N, 3.27.
Synthetic example 7: preparation of Compound 138
Figure BDA0003268517080000401
Compound 138(39.82g) was obtained by the same procedure except that Y4-1, Y5-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of Y4-7, Y5-2, C-7 and B-6 in that order, and the purity by HPLC was ≧ 99.87%. Mass spectrum m/z: 908.4138 (theoretical value): 908.4130). Theoretical element content (%) C69H52N2: c, 91.15; h, 5.77; and N, 3.08. Measured elemental content (%): c, 91.17; h, 5.79; and N, 3.10.
Synthesis example 8: preparation of Compound 181
Figure BDA0003268517080000402
Compound 181(39.92g) was obtained by the same procedure except that A-1, Y3-1, Y4-1, Y5-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of A-8, Y3-8, Y4-5, Y5-8, C-8 and B-8, and the purity by HPLC (solid purity ≧ 99.82%). Mass spectrum m/z: 898.3915 (theoretical value: 898.3923). Theoretical element content (%) C67H50N2O: c, 89.50; h, 5.61; and N, 3.12. Measured elemental content (%): c, 89.52; h, 5.66; and N, 3.13.
Synthetic example 9: preparation of Compound 186
Figure BDA0003268517080000403
Compound 186(40.32g) was obtained by the same procedure except that Y1-1, Y2-1, A-1, Y5-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of Y1-9, Y2-2, A-9, Y5-8, C-9 and B-9 in this order, and the purity by HPLC was ≧ 99.79%. Mass spectrum m/z: 959.4247 (theoretical value: 959.4239). Theoretical element content (%) C72H53N3: c, 90.06; h, 5.56; and N, 4.38. Measured elemental content (%): c, 90.07; h, 5.58; n, 4.39.
Synthetic example 10: preparation of Compound 277
Figure BDA0003268517080000411
The same procedures were repeated except for replacing A-1, Y3-1 and B-1 in Synthesis example 1 with equimolar amounts of A-10, Y3-10 and B-10 in that order to obtain Compound 277(36.93g), HThe purity of the solid is not less than 99.78% by PLC detection. Mass spectrum m/z: 842.4245 (theoretical value: 842.4254). Theoretical element content (%) C63H42D7NO: c, 89.75; h, 6.69; n, 1.66. Measured elemental content (%): c, 89.77; h, 6.69; n, 1.68.
Synthetic example 11: preparation of Compound 312
Figure BDA0003268517080000412
Compound 312(39.63g) was obtained by the same procedure except that Y1-1, Y2-1, A-1, Y3-1, Y4-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of Y1-11, Y2-11, A-11, Y3-11, Y4-11, C-11 and B-11, respectively, and the solid purity by HPLC ≧ 99.74%. Mass spectrum m/z: 929.4001 (theoretical value: 929.3993). Theoretical element content (%) C69H47D4And NS: c, 89.09; h, 5.96; n, 1.51. Measured elemental content (%): c, 89.14; h, 5.97; n, 1.52.
Synthetic example 12: preparation of Compound 331
Figure BDA0003268517080000413
Compound 331(40.61g) was obtained by the same procedure as defined in Synthesis example 1 except that A-1, Y3-1, Y4-1, Y5-1, C-1 and B-1 were sequentially replaced with equimolar amounts of A-12, Y3-12, Y4-5, Y5-12, C-12 and B-12, and the purity by HPLC (solid purity ≧ 99.83%). Mass spectrum m/z: 926.4244 (theoretical value: 926.4236). Theoretical element content (%) C69H54N2O: c, 89.38; h, 5.87; and N, 3.02. Measured elemental content (%): c, 89.42; h, 5.89; and N, 3.03.
Synthetic example 13: preparation of Compound 335
Figure BDA0003268517080000421
A-1, Y3-1, C-1, B-1 in Synthesis example 1 were addedThe same procedures were repeated except for replacing equimolar amounts of A-4, Y3-13, C-2 and B-13 to obtain 335(39.34g) with a purity of 99.74% by HPLC. Mass spectrum m/z: 949.4292 (theoretical value: 949.4284). Theoretical element content (%) C72H55NO: c, 91.01; h, 5.83; and N, 1.47. Measured elemental content (%): c, 91.05; h, 5.85; n, 1.48.
Synthesis example 14: preparation of Compound 338
Figure BDA0003268517080000422
Compound 338(40.96g) was obtained by the same procedure except that A-1, Y3-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of A-6, Y3-14, C-2 and B-14 in that order, and the purity by HPLC (solid content: 99.67%) was not less. Mass spectrum m/z: 974.4247 (theoretical value: 974.4236). Theoretical element content (%) C73H54N2O: c, 89.91; h, 5.58; and N, 2.87. Measured elemental content (%): c, 89.90; h, 5.63; and N, 2.88.
Synthetic example 15: preparation of Compound 380
Figure BDA0003268517080000423
Compound 380(38.12g) was obtained by the same procedure except for replacing A-1, Y3-1, Y4-1, Y5-1, C-1 and B-1 in Synthesis example 1 with equimolar amounts of A-15, Y3-15, Y4-15, Y5-15, C-15 and B-15 in that order, and the solid purity by HPLC ≧ 99.71%. Mass spectrum m/z: 933.4143 (theoretical value: 933.4134). Theoretical element content (%) C68H43D7N2S: c, 87.42; h, 6.15; and N, 3.00. Measured elemental content (%): c, 87.46; h, 6.16; and N, 3.01.
Synthetic example 16: preparation of Compound 382
Figure BDA0003268517080000431
Compound 382(37.80g) was obtained by the same procedure except that A-1, Y3-1, Y4-1, Y5-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of A-16, Y3-13, Y4-15, Y5-16, C-16 and B-16 in this order, and the purity by HPLC (solid purity: 99.68%) was not less than 99.68%. Mass spectrum m/z: 939.4202 (theoretical value: 939.4189). Theoretical element content (%) C69H53N3O: c, 88.15; h, 5.68; and N, 4.47. Measured elemental content (%): c, 88.16; h, 5.72; and N, 4.48.
Synthetic example 17: preparation of Compound 474
Figure BDA0003268517080000432
The same procedures were repeated except for sequentially substituting Y1-1, Y2-1, A-1, Y3-1, C-1 and B-1 in Synthesis example 1 for equimolar amounts of Y1-17, Y2-2, A-17, Y3-17, C-2 and B-17 to obtain Compound 474(40.79) with a solid purity by HPLC ≧ 99.70%. Mass spectrum m/z: 984.4462 (theoretical value: 984.4443). Theoretical element content (%) C75H56N2: c, 91.43; h, 5.73; n, 2.84. Measured elemental content (%): c, 91.44; h, 5.75; and N, 2.86.
Synthetic example 18: preparation of Compound 526
Figure BDA0003268517080000433
The same procedures were repeated except for replacing Y1-1, Y2-1, A-1, Y3-1, Y4-1, C-1 and B-1 in Synthesis example 1 with equimolar amounts of Y1-18, Y2-11, A-18, Y3-18, Y4-5, C-18 and B-18 in that order to obtain compound 526(40.73g) having a solid purity of 99.79% by HPLC. Mass spectrum m/z: 955.5137 (theoretical value: 955.5117). Theoretical element content (%) C73H65N: c, 91.68; h, 6.85; n, 1.46. Measured elemental content (%): c, 91.69; h, 6.87; and N, 1.47.
Synthetic example 19: preparation of Compound 554
Figure BDA0003268517080000441
Compound 554(41.83g) was obtained by the same procedure except that A-1, Y3-1, Y4-1, Y5-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of A-19, A-18, Y4-5, Y5-2, C-19 and B-19 in that order, and the solid purity by HPLC ≧ 99.73%. Mass spectrum m/z: 967.4193 (theoretical value: 967.4178). Theoretical element content (%) C75H53N: c, 93.04; h, 5.52; n, 1.45. Measured elemental content (%): c, 93.05; h, 5.53; n, 1.46.
Synthesis example 20: preparation of Compound 574
Figure BDA0003268517080000442
Compound 574(40.36g) was obtained by the same procedure except that A-1, Y3-1, Y5-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of A-20, Y3-20, Y5-20, C-20 and B-20, and the purity by HPLC ≧ 99.74%. Mass spectrum m/z: 988.4707 (theoretical value: 988.4695). Theoretical element content (%) C75H52D4N2: c, 91.06; h, 6.11; n, 2.83. Measured elemental content (%): c, 91.07; h, 6.13; n, 2.84.
Synthetic example 21: preparation of Compound 600
Figure BDA0003268517080000443
Compound 600(41.41g) was obtained by the same procedure except that Y1-1, Y2-1, A-1, Y3-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of Y1-21, Y2-21, A-21, Y3-4, C-2 and B-21 in the order named, and the purity by HPLC was ≧ 99.70%. Mass spectrum m/z: 999.4453 (theoretical value: 999.4440). Theoretical element content (%) C76H57NO: c, 91.26; h, 5.74; and N, 1.40. Measured elemental content (%): c, 91.30; h, 5.75; n, 1.42.
Synthetic example 22: preparation of Compound 702
Figure BDA0003268517080000451
Compound 702(38.10g) was obtained by the same procedure except for replacing A-1, Y3-1, C-1 and B-1 in Synthesis example 1 with equimolar amounts of A-22, A-18, C-2 and B-22 in that order, and the purity of the solid was 99.86% by HPLC. Mass spectrum m/z: 857.4038 (theoretical value: 857.4022). Theoretical element content (%) C66H51N: c, 92.38; h, 5.99; n, 1.63. Measured elemental content (%): c, 92.39; h, 6.01; n, 1.65.
Synthetic example 23: preparation of Compound 720
Figure BDA0003268517080000452
Compound 720(39.49g) was obtained by the same procedure except for replacing A-1, Y3-1, Y4-1, Y5-1, C-1 and B-1 in Synthesis example 1 with equimolar amounts of A-6, Y3-23, Y4-23, Y5-8, C-23 and B-23 in that order, and the solid purity by HPLC ≧ 99.82%. Mass spectrum m/z: 939.4563 (theoretical value: 939.4552). Theoretical element content (%) C70H57N3: c, 89.42; h, 6.11; and N, 4.47. Measured elemental content (%): c, 89.44; h, 6.13; and N, 4.48.
Synthetic example 24: preparation of Compound 804
Figure BDA0003268517080000453
Compound 804(40.77g) was obtained by the same procedures except for replacing A-1, Y3-1, C-1 and B-1 in Synthesis example 1 with equimolar amounts of A-24, Y3-13, C-9 and B-24 in that order, and the purity of the solid was 99.78% by HPLC. Mass spectrum m/z: 998.4244 (theoretical value: 998.4236). Theoretical element content (%) C75H54N2O: c, 90.15; h, 5.45; and N, 2.80. Measured elemental content (%): c, 90.16; h, 5.50; n, 2.79.
Synthetic example 25: preparation of Compound 818
Figure BDA0003268517080000454
Preparation of intermediate B-25:
the equimolar amounts of A-6 and Y3-4 were sequentially substituted for A-1 and Y3-1 in the synthesis examples to obtain intermediate B-25(30.85g, 85% yield). Mass spectrum m/z: 302.1790 (theoretical value: 302.1783).
Preparation of intermediate D-25:
under the protection of nitrogen, C-2(45.91g, 72.00mmol), Y2-25(11.48g, 73.44mmol), palladium tetratriphenylphosphine (0.82g, 0.71mmol), potassium acetate (10.59g, 107.99mmol) and 100mL of toluene, 50mL of ethanol and 50mL of water are sequentially added into a reaction bottle, the mixture is stirred, and the system is refluxed and reacted 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: 3 recrystallization to give D-25(38.54g, 80% yield). Mass spectrum m/z: 668.2278 (theoretical value: 668.2271).
Preparation of compound 818:
compound 818(40.40g) was obtained by substituting C-1 and B-1 in Synthesis example 1 with equimolar amounts of D-25 and B-25 in that order, and had a solid purity of 99.81% by HPLC. Mass spectrum m/z: 934.4295 (theoretical value: 934.4287). Theoretical element content (%) C71H54N2: c, 91.18; h, 5.82; and N, 3.00. Measured elemental content (%): c, 91.21; h, 5.81; and N, 3.02.
Synthetic example 26: preparation of Compound 840
Figure BDA0003268517080000461
Compound 840(43.16g) was obtained by the same procedure except that A-1, Y3-1, C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of A-26, Y3-23, C-9 and B-26 in that order, and the purity of the solid was 99.79% by HPLC. Mass spectrum m/z: 984.4434(Theoretical value: 984.4443). Theoretical element content (%) C75H56N2: c, 91.43; h, 5.73; n, 2.84. Measured elemental content (%): c, 91.45; h, 5.74; and N, 2.82.
Synthetic example 27: preparation of Compound 872
Figure BDA0003268517080000462
Preparation of intermediate A-27:
by substituting C-2 with an equal molar amount of C-9 in synthesis example 25, intermediate a-27(38.43g, yield 80%) was obtained, which had a solid purity ≧ 99.42% by HPLC. Mass spectrum m/z: 666.212 (theoretical value: 666.2114).
Preparation of compound 872:
compound 872(41.74g) was obtained by the same procedure except that C-1 and B-1 in Synthesis example 1 were replaced with equimolar amounts of A-27 and B-23 in this order, and the purity by HPLC was ≧ 99.76%. Mass spectrum m/z: 965.4718 (theoretical value: 965.4709). Theoretical element content (%) C72H59N3: c, 89.50; h, 6.15; and N, 4.35. Measured elemental content (%): c, 89.52; h, 6.14; n, 4.37.
Synthetic example 28: preparation of Compound 874
Figure BDA0003268517080000471
Compound 874(42.40g) was prepared by the same procedure except for replacing A-1, Y3-1, Y5-1, C-1 and B-1 in Synthesis example 1 with equimolar amounts of A-5, Y3-28, Y5-28, C-28 and B-28, and the purity by HPLC ≧ 99.87%. Mass spectrum m/z: 994.4853 (theoretical value: 994.4862). Theoretical element content (%) C74H62N2O: c, 89.30; h, 6.28; n, 2.81. Measured elemental content (%): c, 89.34; h, 6.27; n, 2.83.
Synthetic example 29: preparation of Compound 875
Figure BDA0003268517080000472
Compound 875(41.41g) was prepared by replacing Y5-1, C-1 and B-1 in Synthesis example 1 with equimolar amounts of Y5-29, C-29 and B-13 in that order, and the purity ≧ 99.83% by HPLC. Mass spectrum m/z: 999.4449 (theoretical value: 999.4440). Theoretical element content (%) C76H57NO: c, 91.26; h, 5.74; and N, 1.40. Measured elemental content (%): c, 91.31; h, 5.73; and N, 1.40.
The organic materials in the preparation examples are purified by sublimation, and the purity is over 99.99 percent. The ITO glass substrate and the ITO/Ag/ITO glass substrate used in the preparation examples were commercially available.
The following are other compounds used in the preparation examples in addition to the triarylamine compound containing a fluorene derivative group of the present invention:
Figure BDA0003268517080000473
Figure BDA0003268517080000481
a combined IVL test system is formed by test software, a computer, a K2400 digital source meter of Keithley company in the United states and a PR788 spectral scanning luminance meter of Photo Research company in the United states, and the device prepared by the invention is tested at the current density of 15mA/cm at the atmospheric pressure and the room temperature2Luminous efficiency and driving voltage at the time of the formation of the electrodes. The lifetime (luminance decay to 95% of the initial luminance) of the devices prepared according to the invention was tested at atmospheric pressure and room temperature using the McScience M6000 OLED lifetime test system. The test results are shown in tables 1 to 4.
Comparative device preparation example 1: comparison device 1
Firstly, the ITO glass substrate is ultrasonically cleaned for 20 minutes by deionized water for 2 times, then is ultrasonically cleaned for 20 minutes by isopropanol, acetone and methanol in sequence, is exposed in ultraviolet rays and ozone for 30 minutes, and is finally placed in vacuum evaporation equipment for standby.
Evaporating each organic material layer and the cathode layer by layer on the ITO glass substrate, and specifically comprises the following steps: a. 2-TNATA is taken as a hole injection layer and has the thickness of 50 nm; b. HT-1 is used as a hole transport layer and has the thickness of 40 nm; c. ADN and BD (97: 3 by mass) as a light emitting layer, and the thickness of the light emitting layer was 30 nm; d. BAlq is used as a hole blocking layer and has the thickness of 20 nm; e. alq3As an electron transport layer, the thickness is 30 nm; f. LiF is used as an electron injection layer and has the thickness of 0.2 nm; g. al as a cathode and having a thickness of 150 nm.
Comparative device preparation example 2: comparison device 2
Comparative device 2 was obtained by replacing HT-1 with HT-2 and the other steps were the same as in comparative device preparation example 1.
Device preparation examples 1 to 29: light emitting device 1 to 29
HT-1 is replaced by the triarylamine compound containing fluorene derivative groups in synthesis examples 1-29, and the remaining steps are the same as in comparative device preparation example 1, so that light-emitting devices 1-29 can be obtained.
TABLE 1
Figure BDA0003268517080000482
Figure BDA0003268517080000491
Comparative device preparation example 3: comparison device 3
Firstly, the ITO glass substrate is ultrasonically cleaned for 20 minutes by deionized water for 2 times, then is ultrasonically cleaned for 20 minutes by isopropanol, acetone and methanol in sequence, is exposed in ultraviolet rays and ozone for 30 minutes, and is finally placed in vacuum evaporation equipment for standby.
Evaporating each organic material layer and the cathode layer by layer on the ITO glass substrate, and specifically comprises the following steps: a. 2-TNATA is taken as a hole injection layer and has the thickness of 60 nm; b. NPB as holesA transmission layer with a thickness of 50 nm; c. HT-1 is used as a luminescence auxiliary layer and has the thickness of 30 nm; d. CBP and Ir (piq)3(95: 5 by mass) as a light-emitting layer, and the thickness is 30 nm; e. BAlq is used as a hole blocking layer and has the thickness of 15 nm; f. alq3As an electron transport layer, the thickness is 30 nm; g. LiF is used as an electron injection layer and has the thickness of 0.2 nm; h. al as a cathode and having a thickness of 150 nm.
Comparative device preparation example 4: comparison device 4
HT-1 was replaced with HT-2, and other steps were the same as in comparative device preparation example 3, to obtain comparative device 4.
Device preparation examples 30 to 58: light emitting devices 30-58
HT-1 was replaced with the triarylamine compound containing fluorene derivative groups of the present invention in Synthesis examples 1 to 29, and the remaining steps were the same as in comparative device preparation example 3, to obtain light emitting devices 30 to 58.
TABLE 2
Figure BDA0003268517080000501
Figure BDA0003268517080000511
Comparative device preparation example 5: comparison device 5
Firstly, the ITO glass substrate is ultrasonically cleaned for 20 minutes by deionized water for 2 times, then is ultrasonically cleaned for 20 minutes by isopropanol, acetone and methanol in sequence, is exposed in ultraviolet rays and ozone for 30 minutes, and is finally placed in vacuum evaporation equipment for standby.
Evaporating each organic material layer and the cathode layer by layer on the ITO glass substrate, and specifically comprises the following steps: a. HT-1 and p-1 (the mass ratio is 100:3) are used as hole injection layers, and the thickness is 40 nm; b. NPB is used as a hole transport layer and has the thickness of 60 nm; c. CBP and Ir (ppy)3(mass ratio 96: 4) as a light-emitting layer, and the thickness is 35 nm; d. alq3As an electron transport layer, the thickness is 40 nm; f. LiF asAn electron injection layer with a thickness of 0.2 nm; g. al as a cathode and having a thickness of 150 nm.
Comparative device preparation example 6: comparison device 6
HT-1 was replaced with HT-2, and other steps were the same as in comparative device preparation example 5, to obtain comparative device 6.
Device preparation examples 59 to 87: light emitting devices 59 to 87
HT-1 was replaced with the triarylamine compound containing fluorene derivative groups of the present invention in Synthesis examples 1 to 29, and the remaining steps were the same as in comparative device preparation example 5, to obtain light-emitting devices 59 to 87.
TABLE 3
Figure BDA0003268517080000512
Figure BDA0003268517080000521
Comparative device preparation example 7: comparison device 7
Firstly, the ITO/Ag/ITO glass substrate is ultrasonically cleaned for 20 minutes by deionized water for 2 times, then sequentially ultrasonically cleaned for 20 minutes by isopropanol, acetone and methanol, then exposed in ultraviolet rays and ozone for 30 minutes, and finally placed in a vacuum evaporation device for standby.
Evaporating each organic material layer and the cathode layer by layer on the glass substrate, specifically: a. 2-TNATA is taken as a hole injection layer and has the thickness of 50 nm; b. NPB is used as a hole transport layer and has the thickness of 40 nm; c. ADN and BD (97: 3 by mass) as a light emitting layer, and the thickness of the light emitting layer was 30 nm; d. alq3As an electron transport layer, the thickness is 40 nm; e. LiF is used as an electron injection layer and has the thickness of 0.2 nm; f. mg and Ag (mass ratio of 1: 9) are used as cathodes, and the thickness is 10 nm; g: CP-1 was used as a cap layer with a thickness of 60 nm.
Device preparation examples 88 to 116: light emitting devices 88-116
CP-1 was replaced with the triarylamine compound containing a fluorene derivative group of the present invention described in Synthesis examples 1 to 29, and the remaining steps were the same as in comparative device preparation example 7, to obtain light-emitting devices 88 to 116.
TABLE 4
Figure BDA0003268517080000522
Figure BDA0003268517080000531
The device data in tables 1-3 show that the triarylamine compound containing fluorene derivative groups, which is shown in formula (I), is applied to a hole transport layer, a light-emitting auxiliary layer or a hole injection layer, so that the driving voltage, the light-emitting efficiency and the service life of the device are remarkably improved.
The device data in table 4 show that the triarylamine compound containing fluorene derivative groups, as shown in formula (I), can be applied to OLED devices as a capping layer material, which can improve the luminous efficiency and the service life of the devices.
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 (11)

1. A triarylamine compound containing a fluorene derivative group is characterized in that the triarylamine compound containing a fluorene derivative group has a structure shown in a formula (I):
Figure FDA0003268517070000011
wherein A, B, E, F is independently selected from one of substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene;
ar is1One selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted carbazolyl group;
ar is2、Ar3Independently selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted carbazolyl, and Ar2、Ar3At least one of the above groups is substituted with one of a substituted or unsubstituted C3-C15 alicyclic group and a substituted or unsubstituted alicyclic heterocyclic group having 5-6 ring atoms;
said L1～L3Independently selected from one of single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted anthrylene and substituted or unsubstituted biphenylene;
said R1、R2Independently selected from one of hydrogen atom, deuterium atom, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted n-propyl group, substituted or unsubstituted isopropyl group, substituted or unsubstituted n-butyl group, substituted or unsubstituted sec-butyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted isobutyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthryl group, and substituted or unsubstituted phenanthryl groupWhen R is1、R2When one is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl and substituted or unsubstituted phenanthryl, the two can be connected to form a five-membered carbocyclic ring or a six-membered carbocyclic ring;
a and b are independently selected from one of 0,1, 2,3, 4,5, 6 and 7, c and d are independently selected from one of 0,1, 2,3, 4,5, 6,7 and 8;
said R3～R6Independently selected from one of a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group, when a plurality of R's exist3When plural R's are present, they may be the same or different4When plural R's are present, they may be the same or different5When plural R's are present, they may be the same or different6When they are used, they may be the same or different.
2. A triarylamine compound containing fluorene derivative groups according to claim 1 wherein A, B, E, F is independently selected from benzene or naphthalene.
3. A triarylamine compound containing fluorene derivative groups according to claim 1 wherein Ar is an aromatic amine compound1Selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or aAnd (b) one of a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted carbazolyl group.
4. The triarylamine compound containing a fluorene derivative group according to claim 1, wherein the alicyclic group having 5 to 6 ring atoms contains at least one nitrogen atom.
5. The triarylamine compound having a fluorene derivative group according to claim 1, wherein the substituted or unsubstituted C3-C15 alicyclic group is selected from the group consisting of cyclopropyl, deuterated cyclopropyl, methyl-substituted cyclopropyl, ethyl-substituted cyclopropyl, n-propyl-substituted cyclopropyl, isopropyl-substituted cyclopropyl, n-butyl-substituted cyclopropyl, tert-butyl-substituted cyclopropyl, cyclobutyl, deuterated cyclobutyl, methyl-substituted cyclobutyl, ethyl-substituted cyclobutyl, n-propyl-substituted cyclobutyl, isopropyl-substituted cyclobutyl, n-butyl-substituted cyclobutyl, tert-butyl-substituted cyclobutyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, ethyl-substituted cyclopentyl, n-propyl-substituted cyclopentyl, isopropyl-substituted cyclopentyl, n-butyl-substituted cyclopentyl, tert-butyl-substituted cyclopentyl, cyclohexyl, Deuterated cyclohexyl, methyl-substituted cyclohexyl, ethyl-substituted cyclohexyl, n-propyl-substituted cyclohexyl, isopropyl-substituted cyclohexyl, n-butyl-substituted cyclohexyl, tert-butyl-substituted cyclohexyl, adamantyl, deuterated adamantyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, n-propyl-substituted adamantyl, isopropyl-substituted adamantyl, n-butyl-substituted adamantyl, tert-butyl-substituted adamantyl, norbornyl, deuterated norbornyl, methyl-substituted norbornyl, ethyl-substituted norbornyl, n-propyl-substituted norbornyl, isopropyl-substituted norbornyl, n-butyl-substituted norbornyl, tert-butyl-substituted norbornyl, cyclopentenyl, deuterated cyclopentenyl, methyl-substituted cyclopentenyl, ethyl-substituted cyclopentenyl, n-propyl-substituted cyclopentenyl, And the functional group is one of an isopropyl substituted cyclopentenyl group, an n-butyl substituted cyclopentenyl group, a tert-butyl substituted cyclopentenyl group, a cyclohexenyl group, a deuterated cyclohexenyl group, a methyl substituted cyclohexenyl group, an ethyl substituted cyclohexenyl group, an n-propyl substituted cyclohexenyl group, an isopropyl substituted cyclohexenyl group, an n-butyl substituted cyclohexenyl group and a tert-butyl substituted cyclohexenyl group.
6. The triarylamine compound containing a fluorene derivative group according to claim 1, wherein the substituted or unsubstituted aliphatic heterocyclic group having 5 to 6 ring atoms is selected from one of the following groups:
Figure FDA0003268517070000021
7. a triarylamine compound containing fluorene derivative groups according to claim 1 wherein Ar is an aromatic amine compound2、Ar3At least one of them is selected from one of the following groups:
Figure FDA0003268517070000031
wherein, a is0One selected from 1,2, 3,4 and 5, and b0One selected from 1,2, 3,4, 5,6 and 7, and c0One selected from 1,2, 3,4, 5,6, 7,8 and 9, and d0One selected from 1,2, 3 and 4, e0Selected from one of 1,2 and 3, the f0One selected from 1,2, 3,4, 5,6 and 7, and g0One selected from 1,2, 3,4, 5,6, 7, 8;
said R20、R20' is independently selected from hydrogen atom, deuterium atom, halogen, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl and deuterated n-butylA group selected from the group consisting of sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, naphthyl and deuterated naphthyl, and Ar2、Ar3In the definition, when a plurality of R's are present, one of a substituted or unsubstituted C3-C15 alicyclic group and a substituted or unsubstituted alicyclic heterocyclic group having 5-6 ring atoms20When plural R's are present, they may be the same or different, and they may be bonded to form a ring20' when they are the same or different, they may be bonded to form a ring, and at least one R is20At least one R is selected from the group consisting of the substituted or unsubstituted C3-C15 alicyclic group and the substituted or unsubstituted alicyclic heterocyclic group having 5-6 ring atoms20' is one selected from the group consisting of the substituted or unsubstituted alicyclic group having from C3 to C15, and the substituted or unsubstituted alicyclic heterocyclic group having from 5 to 6 ring atoms;
said R201、R202Independently selected from one of hydrogen atom, deuterium atom, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl and deuterated tert-butyl, and the two can be connected to form a substituted or unsubstituted C3-C15 cycloalkyl;
the rest is selected from one of the following groups:
Figure FDA0003268517070000032
wherein, a is0' is selected from one of 1,2, 3,4 and 5, and b is0' is selected from one of 1,2, 3,4, 5,6 and 7, and c is0' is selected from one of 1,2, 3,4, 5,6, 7,8 and 9, and d is0' is selected from one of 1,2, 3 and 4, and e is0' is selected from one of 1,2 and 3, and f is0' is selected from one of 1,2, 3,4, 5,6, 7, and g0' is selected from 1,2, 3,4, 5,6, 7,8;
said R30One selected from the group consisting of a hydrogen atom, a deuterium atom, halogen, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, naphthyl and deuterated naphthyl, when a plurality of R's are present30When they are the same or different, they may be linked to form a ring;
said R301、R302Independently selected from a hydrogen atom, a deuterium atom, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, a n-propyl group, a deuterated n-propyl group, an isopropyl group, a deuterated isopropyl group, a n-butyl group, a deuterated n-butyl group, a sec-butyl group, a deuterated sec-butyl group, an isobutyl group, a deuterated isobutyl group, a tert-butyl group and a deuterated tert-butyl group, and the two can be connected to form one of substituted or unsubstituted C3-C15 cycloalkyl groups.
8. A triarylamine compound containing fluorene derivative groups according to claim 1, wherein L is1～L3Independently selected from single bond, one of the following groups:
Figure FDA0003268517070000041
wherein, a is1One selected from 0,1, 2,3 and 4, and b1One selected from 0,1, 2,3 and 4, and c1One selected from 0,1, 2;
said R41One selected from the group consisting of a hydrogen atom, a deuterium atom, halogen, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, naphthyl and deuterated naphthyl, when a plurality of R's are present41When they are, they may beThe same or different.
9. The triarylamine compound containing fluorene derivative groups according to claim 1, wherein the triarylamine compound containing fluorene derivative groups is selected from one of the following compounds:
Figure FDA0003268517070000042
Figure FDA0003268517070000051
Figure FDA0003268517070000061
Figure FDA0003268517070000071
Figure FDA0003268517070000081
Figure FDA0003268517070000091
Figure FDA0003268517070000101
Figure FDA0003268517070000111
Figure FDA0003268517070000121
Figure FDA0003268517070000131
Figure FDA0003268517070000141
Figure FDA0003268517070000151
Figure FDA0003268517070000161
Figure FDA0003268517070000171
Figure FDA0003268517070000181
Figure FDA0003268517070000191
Figure FDA0003268517070000201
10. an organic electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a hole transport region, a light emitting layer, and an electron transport region, and wherein the hole transport region contains at least one triarylamine compound containing a fluorene derivative group as defined in any one of claims 1 to 9.
11. An organic electroluminescent device comprising an anode, a cathode, an organic layer interposed between the anode and the cathode, and a cover layer disposed on the side of the cathode away from the anode, wherein the cover layer contains at least one triarylamine compound having a fluorene derivative group as defined in any one of claims 1 to 9.
CN202111093689.3A 2021-09-17 2021-09-17 Triarylamine compound containing fluorene derivative group and organic electroluminescent device thereof Active CN113717058B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111093689.3A CN113717058B (en) 2021-09-17 2021-09-17 Triarylamine compound containing fluorene derivative group and organic electroluminescent device thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111093689.3A CN113717058B (en) 2021-09-17 2021-09-17 Triarylamine compound containing fluorene derivative group and organic electroluminescent device thereof

Publications (2)

Publication Number Publication Date
CN113717058A true CN113717058A (en) 2021-11-30
CN113717058B CN113717058B (en) 2023-08-15

Family

ID=78684178

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111093689.3A Active CN113717058B (en) 2021-09-17 2021-09-17 Triarylamine compound containing fluorene derivative group and organic electroluminescent device thereof

Country Status (1)

Country Link
CN (1) CN113717058B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114436942A (en) * 2022-02-18 2022-05-06 长春海谱润斯科技股份有限公司 Arylamine compound containing carbazole group and organic electroluminescent device thereof
CN114835591A (en) * 2022-06-02 2022-08-02 南京高光半导体材料有限公司 Compound containing cycloalkyl group and organic electroluminescent device
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
CN115850093A (en) * 2022-11-28 2023-03-28 上海钥熠电子科技有限公司 Fluorene compound and application thereof in organic electroluminescent device
CN116589366A (en) * 2023-07-17 2023-08-15 吉林奥来德光电材料股份有限公司 Organic light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
CN117105893A (en) * 2023-07-28 2023-11-24 浙江八亿时空先进材料有限公司 Amino compound containing trans-cyclohexyl and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180287062A1 (en) * 2017-04-03 2018-10-04 Samsung Display Co., Ltd. Amine compound and organic electroluminescence device including the same
CN108752221A (en) * 2018-06-22 2018-11-06 上海道亦化工科技有限公司 A kind of triaromatic amine compound containing fluorenes and application thereof and luminescent device
CN109037483A (en) * 2018-08-07 2018-12-18 长春海谱润斯科技有限公司 A kind of organic electroluminescence device
CN111808042A (en) * 2020-07-31 2020-10-23 长春海谱润斯科技有限公司 Triarylamine compound and organic electroluminescent device thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180287062A1 (en) * 2017-04-03 2018-10-04 Samsung Display Co., Ltd. Amine compound and organic electroluminescence device including the same
CN108752221A (en) * 2018-06-22 2018-11-06 上海道亦化工科技有限公司 A kind of triaromatic amine compound containing fluorenes and application thereof and luminescent device
CN109037483A (en) * 2018-08-07 2018-12-18 长春海谱润斯科技有限公司 A kind of organic electroluminescence device
CN111808042A (en) * 2020-07-31 2020-10-23 长春海谱润斯科技有限公司 Triarylamine compound and organic electroluminescent device thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114436942A (en) * 2022-02-18 2022-05-06 长春海谱润斯科技股份有限公司 Arylamine compound containing carbazole group and organic electroluminescent device thereof
CN114436942B (en) * 2022-02-18 2023-11-03 长春海谱润斯科技股份有限公司 Arylamine compound containing carbazole group and organic electroluminescent device thereof
CN114835591A (en) * 2022-06-02 2022-08-02 南京高光半导体材料有限公司 Compound containing cycloalkyl group and organic electroluminescent device
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
CN115850093A (en) * 2022-11-28 2023-03-28 上海钥熠电子科技有限公司 Fluorene compound and application thereof in organic electroluminescent device
CN116589366A (en) * 2023-07-17 2023-08-15 吉林奥来德光电材料股份有限公司 Organic light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
CN116589366B (en) * 2023-07-17 2023-12-26 吉林奥来德光电材料股份有限公司 Organic light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
CN117105893A (en) * 2023-07-28 2023-11-24 浙江八亿时空先进材料有限公司 Amino compound containing trans-cyclohexyl and application thereof

Also Published As

Publication number Publication date
CN113717058B (en) 2023-08-15

Similar Documents

Publication Publication Date Title
CN113372313B (en) Triarylamine compound and organic electroluminescent device thereof
CN113501812B (en) Triarylamine compound and organic electroluminescent device thereof
CN113717058B (en) Triarylamine compound containing fluorene derivative group and organic electroluminescent device thereof
CN112661714B (en) Heterocyclic compound and organic electroluminescent device containing same
CN113735808B (en) Triarylamine compound and organic electroluminescent device thereof
WO2017043757A1 (en) Organic compound, organic optoelectronic diode, and display device
KR20160018458A (en) Material for organic electroluminescent elements, organic electroluminescent element using same, and electronic device
CN114436942B (en) Arylamine compound containing carbazole group and organic electroluminescent device thereof
CN114634419B (en) Aromatic amine compound and organic electroluminescent device thereof
CN114394929B (en) Carbazole-based triarylamine derivative and organic electroluminescent device thereof
CN115057838B (en) Aromatic amine organic compound and organic light-emitting device thereof
CN114920720A (en) Aromatic amine compound and organic electroluminescent device thereof
CN113788759A (en) Triarylamine compound containing fluorene group and organic electroluminescent device thereof
CN114940650A (en) Aromatic amine compound containing phenylfluorene and organic electroluminescent device thereof
CN115974822A (en) Arylamine compound and organic electroluminescent device thereof
CN116283854A (en) Aromatic amine compound and organic electroluminescent device thereof
CN107759559A (en) Compound and its organic electronic device
TW202140748A (en) Organic electroluminescent device
CN117003716A (en) Triarylamine derivative based on fluorenyl heterocycle and organic electroluminescent device thereof
CN115583912A (en) Carbazole-containing aromatic amine compound and organic electroluminescent device thereof
CN115745906A (en) Compound containing heterocycle and organic electroluminescent device thereof
CN112701238B (en) Organic light-emitting device comprising covering layer and sealing layer
KR102554747B1 (en) Heterocyclic compound, organic light emitting device comprising the same, and composition for organic layer of organic light emitting device
CN113429370B (en) Aromatic amine compound and organic electroluminescent device thereof
CN115498132A (en) Organic electroluminescent device

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