CN116354881A - Triarylamine compound and application thereof in organic electroluminescent device - Google Patents

Triarylamine compound and application thereof in organic electroluminescent device Download PDF

Info

Publication number
CN116354881A
CN116354881A CN202310314973.1A CN202310314973A CN116354881A CN 116354881 A CN116354881 A CN 116354881A CN 202310314973 A CN202310314973 A CN 202310314973A CN 116354881 A CN116354881 A CN 116354881A
Authority
CN
China
Prior art keywords
substituted
unsubstituted
formula
group
triarylamine compound
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.)
Pending
Application number
CN202310314973.1A
Other languages
Chinese (zh)
Inventor
何睦
赵顺峰
王庆华
王湘成
王鹏
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.)
Shandong Yaoyi Material Technology Co ltd
Original Assignee
Shandong Yaoyi Material 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 Shandong Yaoyi Material Technology Co ltd filed Critical Shandong Yaoyi Material Technology Co ltd
Priority to CN202310314973.1A priority Critical patent/CN116354881A/en
Publication of CN116354881A publication Critical patent/CN116354881A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/46—Phenazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D411/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D421/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D421/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing two hetero rings
    • C07D421/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as 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]
    • H10K50/14—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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H10K50/181—Electron blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—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
    • H10K85/624—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
    • H10K85/631—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
    • 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
    • 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
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • 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
    • C07C2603/86—Ring systems containing bridged rings containing four rings
    • 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)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses a triarylamine compound and application thereof in an organic electroluminescent device, wherein the compound has a chemical structure shown as a formula (1), R 1 And R is 2 Each independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C10 linear or branched alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group, or are combined with each other to form a substituted or unsubstituted fluorene ring; a is that 1 To A 3 One and only one is hydrogen, one and only one is selected from the group represented by formula (2), and one and only one is selected from the group represented by formula (3). The triarylamine compound has simple synthesis, stable molecular structure, excellent hole transmission property and electron blocking capability, can reduce the manufacturing cost of the organic electroluminescent device, and improves the luminous efficiency and the service life of the device.

Description

Triarylamine compound and application thereof in organic electroluminescent device
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to a triarylamine compound and application thereof in an organic electroluminescent device.
Background
The organic electroluminescent device (also called OLED, namely organic light emitting diode) is a self-luminous electronic component, has the characteristics of high contrast ratio, wide visual angle, high response speed, excellent color expressive force and the like, and can be prepared into a flexible display product which can be curled or bent on a flexible substrate. Accordingly, in recent years, OLED displays are widely used in consumer electronics fields such as mobile phones, tablet computers, wall mounted televisions, and in-vehicle display fields.
The OLED device mainly comprises three parts of an electrode, an organic light-emitting layer and an organic functional layer, and a proper organic functional layer material is introduced into the device, so that the light-emitting efficiency of the device can be effectively improved, the power consumption of the device is reduced, and a typical organic electroluminescent device structure comprises: an anode/a Hole Injection Layer (HIL)/a Hole Transport Layer (HTL)/an emitting layer (EML, light emitting host material: light emitting guest material)/an Electron Transport Layer (ETL)/an Electron Injection Layer (EIL)/a cathode, wherein the hole transport layer has a main function of transporting holes injected from the anode into the emitting layer and also has an important function of blocking electrons transferred from the other side of the device.
In the prior art, triarylamine compounds containing fluorene or fluorene derivatives are a common hole transport layer material, which has excellent hole receiving and transporting characteristics, however, it is necessary to further develop a novel functional layer material with excellent performance so as to meet the higher requirements of the display industry on the device performance.
Disclosure of Invention
The invention aims to provide a triarylamine compound and application thereof in an organic electroluminescent device, which are used for solving the problems in the prior art.
To achieve the above and other related objects, according to one aspect of the present invention, there is provided a triarylamine compound having a chemical structure represented by formula (1):
Figure SMS_1
in the formula (1), R 1 And R is 2 Are identical or different from each other and are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C10 straight or branched alkyl, substitutedOr unsubstituted C3-C10 cycloalkyl, or substituted or unsubstituted C6-C20 aryl, or are combined with each other to form a substituted or unsubstituted fluorene ring;
A 1 to A 3 And only one of them is hydrogen, and only one is selected from the group represented by formula (2), and only one is selected from the group represented by formula (3):
Figure SMS_2
in the formula (2), L 0 、L 1 、L 2 Are identical or different from each other and are each independently selected from single bonds, substituted or unsubstituted C6-C20 arylene groups, substituted or unsubstituted C2-C20 heteroarylene groups; ar (Ar) 1 、Ar 2 Are identical or different from each other and are each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C2-C40 heteroaryl;
in the formula (3), Z 1 、Z 2 Are identical or different from each other and are each independently selected from C (R 3 R 4 )、N(R 5 ) O or S; r is R 3 、R 4 、R 5 Each of which is the same or different from the other, and is independently selected from a substituted or unsubstituted C1-C10 linear or branched alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group;
* Represents a bonding site;
wherein the "substituted or unsubstituted" in "means substituted with one or more substituents selected from deuterium, tritium, fluorine, cyano, nitro, trifluoromethyl, C1 to C10 linear or branched alkyl, C3 to C10 cycloalkyl, C1 to C10 alkoxy, C1 to C10 alkylthio, C6 to C20 aryl, C2 to C20 heteroaryl, and when there are a plurality of substituents, the plurality of substituents are the same as or different from each other;
R 1 、R 2 、L 0 、L 1 、L 2 、Z 1 、Z 2 、Ar 1 and Ar is a group 2 The substituents of (2) are the same or different from each other.
In another aspect, the present invention provides an organic layer comprising the foregoing triarylamine compound.
In another aspect, the present invention provides the use of the triarylamine compounds described herein and the organic layers described herein in organic electroluminescent devices.
In another aspect, the present invention provides an organic electroluminescent device, including a first electrode, a second electrode, and an organic layer, where the organic layer is at least one layer selected from a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer, and the organic layer includes the foregoing triarylamine compound.
In another aspect, the present invention provides a display or lighting device comprising an organic electroluminescent device as described above.
Compared with the prior art, the invention has the beneficial effects that: the triarylamine compound has good solubility, is easy to synthesize and purify, has higher singlet state and triplet state energy levels, and excellent hole transmission characteristics and structural stability, and can realize the regulation and control of the front line orbit energy level by connecting different aromatic groups, thereby being applied to hole transmission layer materials with various colors of light, prolonging the service life and improving the luminous efficiency of a device, and reducing the production cost of the device.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device in an embodiment;
fig. 2 is a schematic view of another structure of the organic electroluminescent device in the embodiment;
the reference numerals are as follows: a 101 substrate; 102 a first electrode; 103 a hole injection layer; 104 a first hole transport layer; 105 a second hole transport layer; 106 a light emitting layer; 107 a hole blocking layer; 108 an electron transport layer; 109 a second electrode; 110 a cover layer.
Detailed Description
The invention provides a fluorene-based triarylamine compound, which introduces a dibenzocycloalkyl or heterocycloalkyl structure with a larger volume on one side of a fluorene group connected with triarylamine, is beneficial to improving the triplet energy level of molecules, can effectively block excitons in a luminescent layer from migrating to a hole transport layer, and ensures that the luminescent efficiency of a device is not reduced. Second, in dibenzocycloalkyl or heterocycloalkyl structures, the conjugation between the two benzene rings is interrupted by an sp3 hybridized carbon or heteroatom, so that the fragment has weak conjugation while having electron donating properties. The segment is introduced into a fluorene-based triarylamine structure, so that the molecular structure is more stable, and holes can be more quickly transferred from one molecule to another, thereby being beneficial to the improvement of the service life of the device and the improvement of the luminous efficiency. In addition, the dibenzocycloalkyl or heterocycloalkyl structure belongs to a non-planar structure, can inhibit local crystallization in the molecular film forming process, and is more prone to forming a uniform amorphous film, so that the film layer structure is more stable when the device works, phase change is not easy to occur due to the influence of Joule heat, and the service life of the device is prolonged. On this basis, the present invention has been completed.
The invention provides a triarylamine compound, which has a chemical structure shown in a formula (1):
Figure SMS_3
in the formula (1), R 1 And R is 2 Each of which is the same or different from the others and is independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C10 linear or branched alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group, or is combined with each other to form a substituted or unsubstituted fluorene ring;
A 1 to A 3 And only one of them is hydrogen, and only one is selected from the group represented by formula (2), and only one is selected from the group represented by formula (3):
Figure SMS_4
Figure SMS_5
in the formula (2), L 0 、L 1 、L 2 Are identical or different from each other and are each independently selected from single bonds, substituted or unsubstituted C6-C20 arylene groups, substituted or unsubstituted C2-C20 heteroarylene groups; ar (Ar) 1 、Ar 2 Are identical or different from each other and are each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C2-C40 heteroaryl;
in the formula (3), Z 1 、Z 2 Are identical or different from each other and are each independently selected from C (R 3 R 4 )、N(R 5 ) O or S; r is R 3 、R 4 、R 5 Each of which is the same or different from the other, and is independently selected from a substituted or unsubstituted C1-C10 linear or branched alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group;
* Represents a bonding site;
wherein "substituted or unsubstituted" in "means substituted with one or more substituents selected from deuterium, tritium, fluorine, cyano, nitro, trifluoromethyl, C1-C10 straight or branched alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl, and when there are multiple substituents, the multiple substituents are the same or different from each other;
R 1 、R 2 、L 0 、L 1 、L 2 、Z 1 、Z 2 、Ar 1 and Ar is a group 2 The substituents of (2) are the same or different from each other.
In some embodiments, the chemical structure of formula (1) is represented by formula (2-1) or (2-2):
Figure SMS_6
in the chemical formulas (2-1) and (2-2), R 1 、R 2 、L 0 、L 1 、L 2 、Z 1 、Z 2 、Ar 1 、Ar 2 The meaning of (2) is the same as that of the formula (1).
In some embodiments, the chemical structure of formula (1) is represented by formula (3-1) or (3-2):
Figure SMS_7
in the chemical formulas (3-1) and (3-2), R 1 、R 2 、L 0 、L 1 、L 2 、Z 1 、Z 2 、Ar 1 、Ar 2 The meaning of (2) is the same as that of the formula (1).
In some embodiments, the chemical structure of formula (1) is represented by formula (4-1) or (4-2):
Figure SMS_8
in the chemical formulas (4-1) and (4-2), R 1 、R 2 、L 0 、L 1 、L 2 、Z 1 、Z 2 、Ar 1 、Ar 2 The meaning of (2) is the same as that of the formula (1).
In some embodiments, the substituent of formula (3) is selected from at least one of the following groups:
Figure SMS_9
* Represents the bonding site.
In some embodiments, L 0 、L 1 、L 2 Each of which is the same or different from the other and is independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group; wherein "substituted or unsubstituted" in "means substituted with one selected from deuterium, tritium, fluorine, cyano, nitro, trifluoromethyl, methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthylOr a plurality of substituents, and when a plurality of substituents are present, the plurality of substituents are the same or different from each other.
In some embodiments, ar 1 、Ar 2 Each of which is the same or different from the other and is selected independently from a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted spirofluorenyloxyanthryl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzoselenophenyl group, a substituted or unsubstituted benzofluorenyl group, a substituted or unsubstituted benzonaphthofuranyl group, a substituted or unsubstituted benzonaphthothienyl group; wherein "substituted or unsubstituted" in "means substituted with one or more substituents selected from deuterium, tritium, fluorine, cyano, nitro, trifluoromethyl, methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, and when there are multiple substituents, the multiple substituents are the same as or different from each other.
In some embodiments, the triarylamine compound is selected from at least one of the following chemical structures:
Figure SMS_10
Figure SMS_11
Figure SMS_12
Figure SMS_13
in some embodiments, the triarylamine compound is selected from at least one of the following chemical structures:
Figure SMS_14
Figure SMS_15
/>
Figure SMS_16
/>
Figure SMS_17
/>
Figure SMS_18
in some embodiments, the triarylamine compound is selected from at least one of the following chemical structures:
Figure SMS_19
/>
Figure SMS_20
/>
Figure SMS_21
/>
Figure SMS_22
the present invention also provides an organic electroluminescent device including a cathode, an anode, and a light emitting layer between the cathode and the anode, wherein a triarylamine compound is included in the organic layer provided between the anode and the light emitting layer.
In some embodiments, the triarylamine compound is included in at least one of an electron blocking layer, a hole injection layer, a hole transport layer, and a simultaneous hole transport and injection layer disposed between the anode and the light emitting layer.
In some embodiments, the triarylamine compound is included in a hole transport layer disposed between the anode and the light emitting layer.
The invention provides an organic electroluminescent device, which comprises a first electrode, a second electrode and one or more organic layers arranged between the first electrode and the second electrode, wherein the organic layers can be of a single-layer structure or a multi-layer serial structure laminated with two or more organic layers, and the organic layers comprise at least one of a hole injection layer, a hole transmission layer, a light emitting layer, an electron injection layer or an electron transmission layer. Can be prepared using common methods and materials for preparing organic electroluminescent devices. The organic layer comprises a triarylamine compound according to the present invention.
In the organic electroluminescent device provided by the invention, the first electrode is used as the anode layer, and the anode material can be a material with a large work function, for example, so that holes are smoothly injected into the organic layer; more for example, metals, metal oxides, combinations of metals and oxides, conductive polymers, and the like. The metal oxide may be, for example, indium Tin Oxide (ITO), zinc oxide, indium Zinc Oxide (IZO), or the like.
In the organic electroluminescent device provided by the invention, the second electrode is used as the cathode layer, and the cathode material can be a material with a small work function, for example, so that electrons are smoothly injected into the organic layer. The cathode material may be, for example, a metal or a multi-layer structural material. The metal may be, for example, magnesium, silver, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, tin and lead or alloys thereof, the cathode material preferably being selected from magnesium and silver.
In the organic electroluminescent device provided by the present invention, a material of the hole injection layer, preferably a material having a Highest Occupied Molecular Orbital (HOMO) between a work function of the anode material and a HOMO of the surrounding organic layer, is used as a material that advantageously receives holes from the anode at a low voltage.
In the organic electroluminescent device provided by the invention, the material of the hole transport layer is a material having high mobility to holes and is suitable as a material for receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer. The material of the hole transport layer includes, but is not limited to, an organic material of arylamine, a conductive polymer, a block copolymer having both conjugated and non-conjugated portions, and the like.
In the organic electroluminescent device provided by the present invention, the material of the light emitting layer may be generally selected from materials having good quantum efficiency for fluorescence or phosphorescence as materials capable of emitting light in the visible light region by receiving holes and electrons from the hole transporting layer and from the electron transporting layer, respectively, and combining the holes and electrons.
In the organic electroluminescent device provided by the present invention, the material of the electron transport layer is a material having high mobility for electrons, and is suitable as a material that advantageously receives electrons from the cathode and transports the electrons to the light emitting layer.
In the organic electroluminescent device provided by the invention, the material of the cover layer generally has a high refractive index, so that the light efficiency of the organic electroluminescent device can be improved, and the improvement of external luminous efficiency is particularly facilitated.
In the organic electroluminescent device provided by the invention, the organic electroluminescent device is an organic photovoltaic device, an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor and the like.
In another aspect, the present invention provides a display or lighting device comprising the organic electroluminescent device of the present invention.
Unless otherwise specified, compounds for which no synthetic method is mentioned in the present invention are commercially available; in the present invention, mass spectrometry was performed by ZABHS type mass spectrometer (manufactured by Micromass Co., UK), and nuclear magnetic resonance was performed by Bruker 400MHz type nuclear magnetic resonance (manufactured by Bruker Co., germany).
Synthetic examples:
the compounds according to the present invention can be prepared by the following general synthetic routes, but are not limited thereto.
Figure SMS_23
Wherein for compound iii, X 1 ,X 2 Independently of each other, from iodine, bromine or chlorine. Preferably, when X 2 When selected from iodine, X 1 Selected from bromine or chlorine; when X is 2 When selected from bromine, X 1 Selected from chlorine.
For compound v, when L 0 X is selected from single bonds 3 Is hydrogen; when L 0 X is not selected from single bonds 3 Selected from boric acid groups or pinacol boron ester groups.
Further, the compound iii can be synthesized by taking a derivative of 9-fluorenone as a starting material, and the specific synthetic route is as follows:
a. when R is 1 ,R 2 Each independently selected from substituted or unsubstituted alkyl or cycloalkyl, or substituted or unsubstituted aryl:
Figure SMS_24
synthesis of compound vi:
into a three-necked flask, elemental iodine (9.1 g,36.0mmol,1.2 eq) and hypophosphorous acid (4.6g,36.0mmol,50%wt in H) were sequentially added under a nitrogen atmosphere 2 O,1.2 eq) and glacial acetic acid (500 mL) were thoroughly mixed and stirred at 80℃for 30 minutes. Subsequently, compound v (30.0 mmol,1 eq) was added in portions to the reaction flask under nitrogen atmosphere, followed by heating to reflux and reacting for 12 hours. Substantially no starting material remained as analyzed by thin layer chromatography, and heating was stopped. And (3) after the reaction system is cooled to room temperature, pouring the reaction solution into a large amount of deionized water, and precipitating a large amount of white solids. Suction filtration, collection of solids, washing with deionized water and drying to give compound vi. The obtained product was directly used in the next reaction.
Synthesis of compound iii:
compound vi (20.0 m) was added sequentially to the reaction flask under nitrogen atmosphereAfter stirring well the solution was cooled to 0℃and potassium tert-butoxide (2.2 g,20.0mmol,1 eq) was added in portions under nitrogen. After the addition was completed, the reaction was slowly returned to room temperature and stirring was continued for 1.5 hours. Subsequently, the iodo compound R is slowly added 1 I (20.0 mmol,1 eq) was observed to give a milky white turbidity. The suspension was stirred at room temperature under nitrogen for 2 hours, then filtered, the filtrate was collected, and the solvent was distilled off under reduced pressure. The intermediate compound obtained was further used as a reaction substrate, and the above experimental procedure was repeated, except that the iodo compound R 1 -I is equivalently replaced by R 2 -I. The obtained crude product was purified by flash column chromatography on silica gel (mobile phase is n-hexane/ethyl acetate mixed solvent) to obtain the objective compound iii.
b. When R is 1 ,R 2 Combined with each other to form a substituted or unsubstituted fluorene ring (illustrated as an unsubstituted fluorene ring, which can be synthesized using the same procedure):
Figure SMS_25
to the dried three-necked flask A, magnesium chips (729 mg,30.0mmol,1.5 eq), two elemental iodine and anhydrous tetrahydrofuran (25 mL) treated with a saturated aqueous ammonium chloride solution were successively added under nitrogen atmosphere, and stirring was started to add dropwise a solution of 2-bromobiphenyl (5.6 g,24.0mmol,1.2 eq) in anhydrous tetrahydrofuran (40 mL). After the completion of the dropwise addition, the temperature was raised to reflux, and the reaction was carried out for 3 hours. Another dry three-necked flask was taken up in the form of a solution of compound vi (20 mmol,1 eq) in anhydrous tetrahydrofuran (40 mL) under nitrogen. Subsequently, the newly prepared grignard reagent in the reaction flask A is transferred into the reaction flask B drop by drop through a steel needle under the nitrogen atmosphere. After the completion of the dropwise addition, the reaction solution in the reaction bottle B was refluxed under a nitrogen atmosphere for 18 hours. Substantially no starting material remained as analyzed by thin layer chromatography, and most of the solvent was distilled off. To the resulting crude product was added dichloromethane (100 mL) and deionized water (100 mL) in this order, and after stirring for 3 min, the mixture was allowed to stand for delamination. The organic phase was separated by a separating funnel, the aqueous phase was extracted with dichloromethane (3×40 mL), combined with the aforementioned remaining organic phase, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off, and the crude product was purified by flash column chromatography (mobile phase is n-hexane/dichloromethane mixed solvent) to give compound iii.
Specifically, in the compounds of the present invention, starting compounds vi (dihalo-9-fluorenone) used according to the different positions of substituents of the formula (2) and the formula (3) may be selected from the following compounds, respectively:
Figure SMS_26
wherein, the compound vi-i (2-bromo-3-iodo-9-fluorenone) can be synthesized by the method described in application publication number CN107573307 a; the compound vi-iv (3-bromo-2-iodo-9-fluorenone) can be synthesized by the method described in non-patent document Organic Letters (2022), 24 (31), 5851-5854; the compound vi-ii (4-bromo-2-chloro-9-fluorenone) and the compound vi-ii (2-bromo-4-chloro-9-fluorenone) can be synthesized by the method described in application publication No. CN 112552275A.
Synthesis of Compound vi-iii (4-bromo-3-chloro-9-fluorenone):
Figure SMS_27
(1) Preparation of compound M1:
1-bromo-2-chloro-6-iodobenzene (31.7 g,100mmol,1 eq), 2- (methoxycarbonyl) phenylboronic acid (18.0 g,100mmol,1 eq), tetrakis (triphenylphosphine) palladium (1155.6 mg,1.0mmol,1% eq), potassium carbonate (20.7 g,150mmol,1.5 eq) and anhydrous 1, 4-dioxane (300 mL) were added to a three-necked flask in this order under nitrogen atmosphere, and after stirring was turned on, the mixture was warmed to reflux, and after 6 hours of reaction, substantially no starting material remained by thin layer chromatography analysis, most of the solvent was removed by distillation under reduced pressure. To the resulting residue was added ethyl acetate (180 mL) and deionized water (120 mL) in this order, and the mixture was stirred for 5 minutes and then allowed to stand for delamination. The organic phase was separated by a separating funnel, the aqueous phase was extracted with ethyl acetate (3×50 mL), combined with the aforementioned remaining organic phase, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under reduced pressure, and the crude product was purified by flash column chromatography (mobile phase was n-hexane/ethyl acetate mixed solvent) to give intermediate compound M1 (27.5 g, yield 84.5%).
(2) Preparation of compound M2:
in a three-necked flask, compound M1 (26.1 g,80mmol,1 eq) was dissolved in tetrahydrofuran (150 mL), an aqueous solution of lithium hydroxide (5.7 g,240mmol,3 eq) (water volume: 70 mL) was added, and the mixture was stirred at room temperature and reacted for 6 hours, and substantially no starting material remained by thin layer chromatography analysis. Hydrochloric acid having a concentration of 6M was slowly added to the reaction system, the pH of the reaction system was adjusted to 1, followed by extraction with ethyl acetate (2×250 mL), and the resultant organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain an intermediate compound M2 (24.9 g). The crude product obtained was used directly in the next reaction.
(3) Preparation of compound vi-iii (4-bromo-3-chloro-9-fluorenone):
in a three-necked flask, compound M2 (24.9 g,80mmol,1 eq) was dissolved in dichloromethane (200 mL), then the reaction system was cooled to 0 ℃, polyphosphoric acid (PPA, 60 g) was added with vigorous stirring, then the reaction system was slowly warmed to room temperature, and vigorous stirring was continued at room temperature for 12 hours. Analysis by thin layer chromatography showed substantially no starting material remained, stirring was stopped, the organic phase was separated, and the organic phase was washed 2 times with 1M aqueous sodium hydroxide solution, followed by drying over anhydrous magnesium sulfate, filtration, distillation to remove the solvent, and the crude product was purified by flash column chromatography (mobile phase was n-hexane/dichloromethane mixed solvent) to give 4-bromo-3-chloro-9-fluorenone (20.0 g, yield 85.2%).
The synthesis of the compound vi-vi (3-bromo-4-chloro-9-fluorenone) can be referred to 4-bromo-3-chloro-9-fluorenone, except that 1-bromo-2-chloro-6-iodobenzene is replaced with 1-bromo-2-chloro-3-iodobenzene in an equivalent amount as the starting material.
Synthesis of compound H2:
Figure SMS_28
(1) Synthesis of compound ii-H2:
to a dry three-necked flask, compound i-H2 (15.8 g,50.0mmol,1 eq), pinacol biborate (17.8 g,70.0mmol,1.4 eq), potassium acetate (14.7 g,150.0mmol,3 eq) and anhydrous 1, 4-dioxane (200 mL) were added sequentially under nitrogen atmosphere, and after thorough mixing, 1' -bis (diphenylphosphine) ferrocene palladium dichloride (1.8 g,2.5mmol,5% eq) was added. After stirring uniformly, the reaction system was warmed to reflux under nitrogen atmosphere. After 4 hours of reaction, substantially no starting material remained as analyzed by thin layer chromatography, and heating was stopped. After the reaction system was cooled to room temperature, ethyl acetate (150 mL) and deionized water (100 mL) were sequentially added to the reaction flask, and the mixture was stirred for 3 minutes and then allowed to stand for delamination. The organic phase was separated by a separating funnel, the aqueous phase was extracted with ethyl acetate (3×40 mL), combined with the aforementioned remaining organic phase, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under reduced pressure, and the crude product was purified by flash column chromatography (mobile phase was n-hexane/ethyl acetate mixed solvent) to give compound ii-H2 (17.0 g, yield 93.8%).
(2) Synthesis of Compound iv-H2:
to a dry three-necked flask, compound ii-H2 (14.5 g,40.0mmol,1 eq), compound iii-H2 (16.0 g,40.0mmol,1 eq) and degassed toluene (200 mL) were added sequentially under nitrogen atmosphere, and after stirring well, tetrakis triphenylphosphine palladium (924.4 mg,0.8mmol,2% eq), potassium carbonate (13.8 g,100.0mmol,2.5 eq), degassed ethanol (120 mL) and deionized water (80 mL) were added sequentially. After stirring thoroughly, the reaction system was warmed to reflux under nitrogen atmosphere, and after 8 hours of reaction, no starting material remained substantially by thin layer chromatography analysis, and heating was stopped. When the reaction solution was cooled to room temperature, 100mL of toluene was added to the reaction system, stirred for 3 minutes, and then allowed to stand for separation, the organic phase was retained by separation with a separating funnel, the aqueous phase was extracted with toluene (3×40 mL), and the organic phase was combined with the above-mentioned retained organic phase, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under reduced pressure, and the crude product was purified by flash column chromatography (mobile phase was n-hexane/dichloromethane mixed solvent) to give compound iv-H2 (16.3 g, yield 80.3%).
(3) Synthesis of target compound H2:
to a three-necked flask, compound iv-H2 (10.2 g,20.0mmol,1 eq), bis (4-biphenylyl) amine (compound v-H2,6.4g,20.0mmol,1 eq) and anhydrous toluene (120 mL) were sequentially added under nitrogen atmosphere, and sodium t-butoxide (2.9 g,30.0mmol,1.5 eq), bis (dibenzylideneacetone palladium (113.2 mg,0.2mmol,1% eq), and tri (t-butylphosphine (1.0 mL,10% n-hexane solution, 0.4mmol,2% eq) were each added with thorough stirring. Stirring is started, the reaction system is fully mixed, the temperature is raised to reflux under the nitrogen atmosphere, after the reaction is carried out for 8 hours, no raw materials basically remain through thin layer chromatography analysis, and the heating is stopped. After the temperature of the reaction system was lowered to room temperature, a mixed solution of 5mL of concentrated hydrochloric acid (37% aqueous solution) and 100mL of deionized water was added thereto, and the mixture was left to stand for delamination, the organic phase was separated by a separating funnel, the aqueous phase was extracted with toluene (3X 30 mL), the organic phase was combined with the aforementioned remaining organic phase, the solvent was distilled off under reduced pressure, and the crude product was separated by silica gel column chromatography (mobile phase was n-hexane/toluene mixed solvent), and the toluene/ethanol mixed solvent was recrystallized to give the objective compound H2 (11.0 g, yield 75.3%). Mass spectrum (m/z) =748.39 [ m+h ]] + . The total yield of the three-step reaction is 55.4 percent.
The compound (x) shown in Table 1 was synthesized by the above-mentioned production method, except that the starting compounds i-x, iii-x, v-x were used in place of the compounds i-H2 iii-H2, v-H2, respectively, in equivalent amounts. The main raw materials, the synthesized intermediates, the yields and the mass spectrum characterization data are shown in table 1.
TABLE 1
Figure SMS_29
/>
Figure SMS_30
/>
Figure SMS_31
/>
Figure SMS_32
Synthesis of compound H100:
Figure SMS_33
firstly, obtaining an intermediate compound iv-H100 through a two-step reaction according to a synthesis method of a reference compound iv-H2; subsequently, referring to a preparation method for synthesizing the compound iv-H100 by taking the compound ii-H100 and the compound iii-H100 as raw materials, a final target product H100 is synthesized, except that two raw material compounds containing boron and halogen are respectively replaced by the compound v-H100 and the compound iv-H100. Mass spectrum (m/z) =847.36 [ m+h ]] + . The total yield of the three-step reaction is 54.3 percent.
With reference to the above preparation method, the compound (x) listed in Table 2 was synthesized, except that the starting compounds i-x, iii-x, v-x were used in place of the compounds i-H100 iii-H100, v-H100, respectively, in equivalent amounts. The main raw materials, the synthesized intermediates, the yields and the mass spectrum characterization data are shown in table 2.
TABLE 2
Figure SMS_34
/>
Figure SMS_35
The nuclear magnetic data of representative compounds involved in the synthesis examples are shown in table 3.
TABLE 3 Table 3
Figure SMS_36
/>
Figure SMS_37
Device example:
the compounds of the invention used in the device are purified by sublimation, and the purity is more than 99.98 percent.
The compound can be used as a hole transport layer material or an electron blocking layer material of OLED devices with various colors such as red light, green light and the like. Specific device fabrication methods and test results are given below.
Preparation of red organic electroluminescent device
Red light device example 1:
the red bottom-emitting organic electroluminescent device was fabricated according to the structure shown in fig. 1, and the fabrication process was: a transparent ITO film layer (thickness 150 nm) was formed on a glass substrate 101 by a magnetron sputtering process to obtain a first electrode 102 as an anode. Evaporating a mixed material of the compound 1 and the compound 2 on the surface of the anode to form a hole injection layer 103, wherein the mixing ratio is 3:97 (mass ratio), and the thickness is 10nm; then, compound 2 (thickness 100 nm) and compound H2 of the present invention (thickness 20 nm) were sequentially deposited on the surface of the hole injection layer to obtain a first hole transport layer 104 and a second hole transport layer 105, respectively. Next, on the surface of the second hole transport layer 105, co-evaporation was performed with respect to the compound 3 and the compound 4 at a mass ratio of 95:5, to form an organic light-emitting layer 106 (thickness 40 nm). Subsequently, the hole blocking layer 107 (thickness 10 nm) was formed by vapor deposition of the compound 5 on the surface of the organic light-emitting layer in this order, and the electron transport layer 108 (thickness 30 nm) was formed by mixing the compound 6 and LiQ in a ratio of 4:6 (mass ratio). Finally, magnesium (Mg) and silver (Ag) were deposited on the surface of the electron transport layer 108 at a deposition rate of 1:9 in a mixed manner to form a second electrode 109 having a thickness of 10nm as a cathode, thereby completing the fabrication of the organic light emitting device.
The chemical structures of compounds 1 to 6 and LiQ are shown in Table 4.
TABLE 4 Table 4
Figure SMS_38
Red light device examples 2 to 24
An organic electroluminescent device was fabricated in the same manner as in example 1 of the red light device, except that the compound in table 5 below was substituted for the compound H2, respectively, at the time of forming the light emitting layer.
Comparative examples 1 to 2
An organic electroluminescent device was fabricated in the same manner as in example 1 of the red light device, except that compound HT-A and compound HT-B (chemical structures shown below) were used instead of compound H2 in forming the light emitting layer.
Figure SMS_39
The operating voltage and efficiency of the organic electroluminescent device thus prepared were calculated by a computer-controlled Keithley 2400 test system. Device lifetime in dark conditions was obtained using a polar onix (McScience co.) lifetime measurement system equipped with a power supply and a photodiode as detection units. Each set of red device examples was produced and tested in the same batch as the devices of comparative example 1, the operating voltage, efficiency and lifetime of the devices of comparative example 1 were each recorded as 1, and the ratios of the corresponding indices of the red device examples 1 to 24 and the devices of comparative example 2 were calculated, respectively, as shown in table 5.
TABLE 5
Figure SMS_40
Figure SMS_41
Preparation of green organic electroluminescent device
Green light device example 1:
the green bottom-emitting organic electroluminescent device was fabricated according to the structure shown in fig. 2, and the fabrication process was: a transparent ITO film layer (thickness 150 nm) was formed on a glass substrate 101 by a magnetron sputtering process to obtain a first electrode 102 as an anode. Evaporating a mixed material of the compound 1 and the compound 2 on the surface of the anode to form a hole injection layer 103, wherein the mixing ratio is 3:97 (mass ratio), and the thickness is 10nm; then, compound 2 (thickness 100 nm) and compound H16 of the present invention (thickness 40 nm) were sequentially deposited on the surface of the hole injection layer to obtain a first hole transport layer 104 and a second hole transport layer 105, respectively. Next, on the surface of the second hole transport layer 105, the compound 3-3A, the compound 3-3B, and the compound 3-4 were co-evaporated at a mass ratio of 45:45:10 to form an organic light emitting layer 106 (thickness 40 nm). Subsequently, the hole blocking layer 107 (thickness 10 nm) was formed by vapor deposition of the compound 5 on the surface of the organic light-emitting layer in this order, and the electron transport layer 108 (thickness 30 nm) was formed by mixing the compound 6 and LiQ in a ratio of 4:6 (mass ratio). Finally, magnesium (Mg) and silver (Ag) were deposited on the surface of the electron transport layer 108 at a deposition rate of 1:9 in a mixed manner to form a second electrode 109 having a thickness of 10nm as a cathode, thereby completing the fabrication of the organic light emitting device.
Chemical structures of Compounds 1,5,6,7 and LiQ as described above, chemical structures of Compounds 3-3A,3-3B and 3-4 are shown in Table 6.
TABLE 6
Figure SMS_42
Green light device examples 2 to 15
An organic electroluminescent device was fabricated in the same manner as in example 1 of a green device, except that the compounds shown in table 7 below were used instead of the compound H13, respectively, when luminescence was formed.
Comparative example 3
Except for the compound HT-C in forming the light-emitting layer
Figure SMS_43
An organic electroluminescent device was fabricated in the same manner as in example 1 of a green device, except that compound H13 was replaced.
The operating voltage and efficiency of the organic electroluminescent device thus prepared were calculated by a computer-controlled Keithley 2400 test system. Device lifetime in dark conditions was obtained using a polar onix (McScience co.) lifetime measurement system equipped with a power supply and a photodiode as detection units. Each set of example devices was produced and tested in the same batch as the devices of comparative example 3, the operating voltage, efficiency and lifetime of the devices of comparative example 3 were each recorded as 1, and the ratios of the corresponding indices of the green devices of examples 1 to 12 and the devices of comparative example 3 were calculated, respectively, as shown in table 7.
TABLE 7
A second hole transport layer Relative operating voltage Relative efficiency Relative life span
Comparative example 3 HT-C 1 1 1
Green light device example 1 H13 0.924 1.168 1.346
Green light device example 2 H71 0.933 1.179 1.251
Green light device example 3 H74 0.909 1.155 1.268
Green light device example 4 H252 0.950 1.240 1.235
Green light device example 5 H258 0.932 1.159 1.187
Green light device example 6 H269 0.913 1.207 1.280
Green light device example 7 H271 0.918 1.219 1.306
Green light device example 8 H285 0.905 1.116 1.336
Green light device example 9 H291 0.940 1.090 1.310
Green light device example 10 H308 0.902 1.133 1.282
Green light device example 11 H319 0.918 1.167 1.247
Green light device example 12 H321 0.942 1.235 1.181
Green light device example 13 H332 0.901 1.136 1.304
Green light device example 14 H359 0.927 1.247 1.267
Green light device example 15 H360 0.917 1.237 1.254
Referring to table 5, it can be seen that the red light device examples 1 to 24 using the compound of the present application as the material of the second hole transport layer of the organic electroluminescent red light device have at least 4.5% lower device voltage, at least 15.2% higher device efficiency and at least 20.5% longer lifetime than the comparative examples 1 to 2.
Referring to table 7, it can be seen that the green device examples 1 to 12 using the compounds of the present application as the material of the second hole transport layer of the organic electroluminescent green device have at least 5.0% lower device voltage, at least 9.0% higher device efficiency and at least 18.1% longer lifetime than the comparative examples 1 to 3.
Compared with comparative examples 1 and 3, the groups connected to fluorene in the compound have weaker conjugation effect and the capability of attracting electron cloud, the electron distribution on the C-N bond of triarylamine is more average, and the C-N bond is less prone to break, so that the stability of molecules is higher, and the service life of the device is prolonged. In comparative example 2, the fluorene moiety in the spirofluorene xanthene group is not located on the conjugated plane of the molecule and does not substantially participate in hole transport, which may be the cause of higher device voltage and lower luminous efficiency.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (13)

1. A triarylamine compound having a chemical structure represented by formula (1):
Figure FDA0004149981770000011
in the formula (1), R 1 And R is 2 Each of which is the same or different from the others and is independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C10 linear or branched alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group, or is combined with each other to form a substituted or unsubstituted fluorene ring;
A 1 to A 3 And only one of them is hydrogen, and only one is selected from the group represented by formula (2), and only one is selected from the group represented by formula (3):
Figure FDA0004149981770000012
in the formula (2), L 0 、L 1 、L 2 Are identical or different from each other and are each independently selected from single bonds, substituted or unsubstituted C6-C20 arylene groups, substituted or unsubstituted C2-C20 heteroarylene groups; ar (Ar) 1 、Ar 2 Are identical or different from each other and are each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C2-C40 heteroaryl;
in the formula (3), Z 1 、Z 2 Are identical or different from each other and are each independently selected from C (R 3 R 4 )、N(R 5 ) O or S; r is R 3 、R 4 、R 5 Each of which is the same or different from the other, and is independently selected from a substituted or unsubstituted C1-C10 linear or branched alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group;
* Represents a bonding site;
wherein the "substituted or unsubstituted" in "means substituted with one or more substituents selected from deuterium, tritium, fluorine, cyano, nitro, trifluoromethyl, C1 to C10 linear or branched alkyl, C3 to C10 cycloalkyl, C1 to C10 alkoxy, C1 to C10 alkylthio, C6 to C20 aryl, C2 to C20 heteroaryl, and when there are a plurality of substituents, the plurality of substituents are the same as or different from each other;
R 1 、R 2 、L 0 、L 1 、L 2 、Z 1 、Z 2 、Ar 1 and Ar is a group 2 The substituents of (2) are the same or different from each other.
2. The triarylamine compound according to claim 1, wherein the chemical structure represented by formula (1) is represented by formula (2-1) or (2-2):
Figure FDA0004149981770000021
in the chemical formulas (2-1) and (2-2), R 1 、R 2 、L 0 、L 1 、L 2 、Z 1 、Z 2 、Ar 1 、Ar 2 The meaning of (2) is the same as that of the formula (1).
3. The triarylamine compound according to claim 1, wherein the chemical structure represented by formula (1) is represented by formula (3-1) or (3-2):
Figure FDA0004149981770000022
in the chemical formulas (3-1) and (3-2), R 1 、R 2 、L 0 、L 1 、L 2 、Z 1 、Z 2 、Ar 1 、Ar 2 The meaning of (2) is the same as that of the formula (1).
4. The triarylamine compound according to claim 1, wherein the chemical structure represented by formula (1) is represented by formula (4-1) or (4-2):
Figure FDA0004149981770000023
in the chemical formulas (4-1) and (4-2), R 1 、R 2 、L 0 、L 1 、L 2 、Z 1 、Z 2 、Ar 1 、Ar 2 The meaning of (2) is the same as that of the formula (1).
5. The triarylamine compound of claim 1 wherein the substituent represented by formula (3) is selected from at least one of the following groups:
Figure FDA0004149981770000031
* Represents the bonding site.
6. The triarylamine compound as set forth in claims 1-4 wherein L 0 、L 1 、L 2 Each of which is the same or different from the other and is independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group; wherein:
the "substituted or unsubstituted" in "means substituted with one or more substituents selected from deuterium, tritium, fluorine, cyano, nitro, trifluoromethyl, methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, and when a plurality of substituents are present, the plurality of substituents are the same as or different from each other.
7. The triarylamine compound as set forth in claim 1 to 4, wherein Ar 1 、Ar 2 Are identical or different from each other and are each independently selected from the group consisting of substituentsOr unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted spirofluorenyloxy, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzoselenophenyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothienyl; wherein:
the "substituted or unsubstituted" in "means substituted with one or more substituents selected from deuterium, tritium, fluorine, cyano, nitro, trifluoromethyl, methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, and when a plurality of substituents are present, the plurality of substituents are the same as or different from each other.
8. The triarylamine compound of claim 2 wherein said triarylamine compound is selected from at least one of the following chemical structures:
Figure FDA0004149981770000032
Figure FDA0004149981770000041
Figure FDA0004149981770000051
Figure FDA0004149981770000061
Figure FDA0004149981770000071
9. the triarylamine compound of claim 3 wherein said triarylamine compound is selected from at least one of the following chemical structures:
Figure FDA0004149981770000072
Figure FDA0004149981770000081
Figure FDA0004149981770000091
Figure FDA0004149981770000101
/>
Figure FDA0004149981770000111
10. the triarylamine compound of claim 4 wherein the triarylamine compound is selected from at least one of the following chemical structures:
Figure FDA0004149981770000112
/>
Figure FDA0004149981770000121
/>
Figure FDA0004149981770000131
/>
Figure FDA0004149981770000141
11. an organic electroluminescent device comprising a cathode, an anode, and a light-emitting layer between the cathode and the anode, wherein the triarylamine compound of any one of claims 1 to 10 is contained in an organic layer provided between the anode and the light-emitting layer.
12. The organic electroluminescent device according to claim 11, wherein the triarylamine compound is contained in at least one layer of an electron blocking layer, a hole injection layer, a hole transport layer, and a hole transport and injection layer that are provided between the anode and the light-emitting layer.
13. The organic electroluminescent device according to claim 12, wherein the triarylamine compound is contained in a hole transport layer provided between the anode and the light-emitting layer.
CN202310314973.1A 2023-03-24 2023-03-24 Triarylamine compound and application thereof in organic electroluminescent device Pending CN116354881A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310314973.1A CN116354881A (en) 2023-03-24 2023-03-24 Triarylamine compound and application thereof in organic electroluminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310314973.1A CN116354881A (en) 2023-03-24 2023-03-24 Triarylamine compound and application thereof in organic electroluminescent device

Publications (1)

Publication Number Publication Date
CN116354881A true CN116354881A (en) 2023-06-30

Family

ID=86936097

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310314973.1A Pending CN116354881A (en) 2023-03-24 2023-03-24 Triarylamine compound and application thereof in organic electroluminescent device

Country Status (1)

Country Link
CN (1) CN116354881A (en)

Similar Documents

Publication Publication Date Title
KR102584939B1 (en) Metal complex with fluorine substitution
KR101574704B1 (en) Novel compounds, organic light emitting device display and organic solar battery using the same
CN107011183B (en) Compounds and organic electronic device comprising it
CN112250585B (en) Hole transport material and organic electroluminescent device using same
CN111675718B (en) Compound, organic light-emitting device comprising compound, display panel and display device
CN110536887B (en) Novel compound and organic light emitting device comprising the same
CN113402507B (en) Triphenylene derivative, light-emitting device material, and light-emitting device
CN112625042B (en) Organic electroluminescent material and application thereof
CN114213376B (en) Compound containing fused fluorene derivative fragment and application thereof in organic electroluminescent device
CN110437081B (en) Organic compound containing tricycloheptane, preparation method thereof and organic electroluminescent device comprising the same
CN110256473B (en) Compound, organic photoelectric device and electronic equipment
WO2019078443A1 (en) Novel compound and organic light emitting device using same
CN107652221A (en) A kind of derivative containing benzo carbazole structure and preparation method thereof and organic electroluminescence device
CN107573328B (en) Indenoimidazole compound, material containing same and organic electroluminescent device
CN116063229A (en) Organic compound and application thereof in organic electroluminescent device
CN114790145A (en) Arylamine compound containing indenofluorene group and organic electroluminescent device
CN112707908B (en) Organic electronic material and application thereof
CN114736148A (en) Triarylamine compound, organic material containing triarylamine compound, and organic light-emitting device
CN116354881A (en) Triarylamine compound and application thereof in organic electroluminescent device
CN108117511B (en) Spirofluorene ring compound, use thereof, and organic electroluminescent device using the same
CN115073307B (en) Fluorene compound and application thereof in organic electroluminescent device
CN115304574B (en) Heterocyclic compound and application thereof in organic electroluminescent device
CN111747894A (en) Compound with dibenzo-nitrogen-containing six-membered heterocyclic ring as core and application of compound in organic electroluminescent device
CN114230597B (en) Organic compound and application thereof
CN112745318B (en) Compound and application thereof

Legal Events

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