CN114914372A - Organic electroluminescent device - Google Patents

Organic electroluminescent device Download PDF

Info

Publication number
CN114914372A
CN114914372A CN202111488167.3A CN202111488167A CN114914372A CN 114914372 A CN114914372 A CN 114914372A CN 202111488167 A CN202111488167 A CN 202111488167A CN 114914372 A CN114914372 A CN 114914372A
Authority
CN
China
Prior art keywords
group
substituted
carbon atoms
unsubstituted
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
CN202111488167.3A
Other languages
Chinese (zh)
Inventor
王静
崔至皓
邝志远
庞惠卿
谢梦兰
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.)
Beijing Summer Sprout Technology Co Ltd
Original Assignee
Beijing Summer Sprout 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 Beijing Summer Sprout Technology Co Ltd filed Critical Beijing Summer Sprout Technology Co Ltd
Priority to US17/649,874 priority Critical patent/US20220359832A1/en
Priority to JP2022016627A priority patent/JP7432950B2/en
Priority to DE102022102796.1A priority patent/DE102022102796B4/en
Priority to KR1020220015428A priority patent/KR20220113876A/en
Publication of CN114914372A publication Critical patent/CN114914372A/en
Priority to JP2023123641A priority patent/JP2023153909A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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

Abstract

An organic electroluminescent device is disclosed. The organic electroluminescent device includes an anode, a cathode, and a first organic layer disposed between the anode and the cathode, the first organic layer including a first compound having a structure of formula 1 and a second compound having a structure of formula 2. The novel material combination consisting of the first compound and the second compound can be used in a hole injection layer in an organic electroluminescent device, so that the organic electroluminescent device has excellent characteristics of low voltage, high efficiency and long service life, and better device performance can be provided. A display module and a compound combination are also disclosed.

Description

Organic electroluminescent device
Technical Field
The present invention relates to organic electronic devices, and in particular, to an organic electroluminescent device. And more particularly, to an organic electroluminescent device including a first compound having a structure of formula 1 and a second compound having a structure of formula 2 in a first organic layer, and a display assembly including the organic electroluminescent device.
Background
Organic electronic devices include, but are not limited to, the following classes: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), Organic Light Emitting Transistors (OLETs), Organic Photovoltaics (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes, and organic plasma light emitting devices.
In 1987, Tang and Van Slyke of Islamic Kodak reported a two-layer organic electroluminescent device comprising an arylamine hole transport layer and a tris-8-hydroxyquinoline-aluminum layer as an electron transport layer and a light-emitting layer (Applied Physics Letters, 1987,51(12): 913-915). Upon biasing the device, green light is emitted from the device. The invention lays a foundation for the development of modern Organic Light Emitting Diodes (OLEDs). State-of-the-art OLEDs may include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light emitting layers between the cathode and anode. Since OLEDs are a self-emissive solid state device, it offers great potential for display and lighting applications. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications, such as in the fabrication of flexible substrates.
OLEDs can be classified into three different types according to their light emitting mechanism. The OLEDs invented by Tang and van Slyke are fluorescent OLEDs. It uses only singlet luminescence. The triplet states generated in the device are wasted through the non-radiative decay channel. Therefore, the Internal Quantum Efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation hinders the commercialization of OLEDs. In 1997, Forrest and Thompson reported phosphorescent OLEDs, which use triplet emission from complex-containing heavy metals as emitters. Thus, singlet and triplet states can be harvested, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributes to the commercialization of active matrix OLEDs (amoleds). Recently, Adachi has achieved high efficiency through Thermally Activated Delayed Fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap, making it possible to return excitons from the triplet state to the singlet state. In TADF devices, triplet excitons are able to generate singlet excitons through reverse intersystem crossing, resulting in high IQE.
OLEDs can also be classified into small molecule and polymer OLEDs depending on the form of the material used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of small molecules can be large, as long as they have a precise structure. Dendrimers with well-defined structures are considered small molecules. The polymeric OLED comprises a conjugated polymer and a non-conjugated polymer having a pendant light-emitting group. Small molecule OLEDs can become polymer OLEDs if post-polymerization occurs during the fabrication process.
Various OLED manufacturing methods exist. Small molecule OLEDs are typically fabricated by vacuum thermal evaporation. Polymer OLEDs are fabricated by solution processes such as spin coating, ink jet printing and nozzle printing. Small molecule OLEDs can also be made by solution processes if the material can be dissolved or dispersed in a solvent.
The light emitting color of the OLED can be realized by the structural design of the light emitting material. An OLED may comprise one light emitting layer or a plurality of light emitting layers to achieve a desired spectrum. Green, yellow and red OLEDs, phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still have the problems of blue unsaturation, short device lifetime, high operating voltage, and the like. Commercial full-color OLED displays typically employ a hybrid strategy using either blue fluorescent and phosphorescent yellow, or red and green. At present, the rapid decrease in efficiency of phosphorescent OLEDs at high luminance is still a problem. In addition, it is desirable to have a more saturated emission spectrum, higher efficiency and longer device lifetime.
Organic electroluminescent devices convert electrical energy into light by applying a voltage across the device. In general, an organic electroluminescent device includes an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer of the electroluminescent device includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer (containing a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. Materials constituting the organic layer may be classified into a hole injection material, a hole transport material, an electron blocking material, a host material, a light emitting material, an electron buffer material, a hole blocking material, an electron transport material, a hole blocking material, and the like according to the function of the material. When a bias is applied to the device, holes are injected from the anode into the light-emitting layer and electrons are injected from the cathode into the light-emitting layer. The holes and electrons meet to form excitons, which recombine to emit light. The hole injection layer is one of important functional layers influencing the performance of the organic electroluminescent device, and the selection and matching of materials of the hole injection layer can have important influence on the performance of the organic electroluminescent device, such as driving voltage, efficiency, service life and the like. Organic electroluminescent devices having characteristics of low driving voltage, high efficiency, long lifetime, etc. are commercially desired, and thus, the development of a novel hole injection layer is a very critical research field.
Most of the early OLED devices only have a layer of organic material arranged between an anode and a light-emitting layer, and have the functions of hole injection, hole transmission and even electron blocking, and the structure of the device is limited by a single hole transmission material, so that the energy level can not be matched ideally, and therefore, the ideal performance is difficult to obtain; with the increasing demand of the industry for the device performance, the performance demand for the hole transport region between the anode and the light-emitting layer is also increasing, and then the hole transport material is further subdivided into two layers, namely a hole injection layer and a hole transport layer, at this time, a single triarylamine material is generally used as the hole injection layer, and the common triarylamine materials are as follows:
Figure BDA0003398928070000021
also for example, US20160190447a1 discloses a spirobifluorene-triarylamine structure
Figure BDA0003398928070000022
The organic compound of (3) can be used as a hole transport material in a hole transport layer or a hole injection layer or an exciton blocking layer or as a host material of a fluorescent light emitter or a phosphorescent light emitter, but the influence of the selection of the compound and a P-type doping material on the performance of the device is not concerned in the document.
In the most advanced device structure in the industry, a plurality of organic layers are usually disposed between the anode and the light-emitting layer to respectively realize the hole injection function, the hole transport function and the electron blocking function. In order to obtain better hole injection effect, a hole transport material (such as arylamine compound) in the hole injection layer is often doped with a certain proportion of p-type doping materials, and the p-type doping materials are commonly used as follows:
Figure BDA0003398928070000031
as another example, U.S. Pat. No. 3,311 discloses a compound having the structure of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole and the like
Figure BDA0003398928070000032
Organic compounds that can be used as p-type doping materials or hole injection materials with deep LUMO, this application only focuses on such p-type doping materials themselves and does not focus on the impact of the choice of the p-type doping material in combination with the hole transport material on the device performance.
The doped hole injection layer achieves a p-type doping effect through the strong electron capturing capacity of the p-type doping material, and effectively improved hole injection and conductivity can be obtained. In such a doped hole injection layer, on the one hand, it is very important to research and develop more excellent p-type doping materials and/or more excellent hole transport materials; on the other hand, matching of the p-type doped material and the hole transport material is more important, and the mismatch often results in great loss of device performance. Therefore, the selection of the p-type doping material and the hole transport material is very critical.
Disclosure of Invention
The present invention aims to provide a novel series of organic electroluminescent devices to solve at least some of the above problems. The novel organic electroluminescent device comprises an anode, a cathode, and a first organic layer disposed between the anode and the cathode, the first organic layer comprising at least a first compound having a structure of formula 1 and a second compound having a structure of formula 2. The novel material combination consisting of the first compound and the second compound can be used in a hole injection layer in an organic electroluminescent device, so that the organic electroluminescent device has excellent characteristics of low voltage, high efficiency and long service life and can provide better device performance.
According to an embodiment of the present invention, there is disclosed an organic electroluminescent device including:
an anode, a cathode, a anode and a cathode,
a cathode electrode, which is provided with a cathode,
and a first organic layer disposed between the anode and the cathode, wherein the first organic layer includes at least a first compound and a second compound, wherein the first compound has a structure represented by formula 1:
Figure BDA0003398928070000033
in the formula 1, the first and second groups,
x and Y are, identically or differently on each occurrence, selected from NR ', CR "R'", O, S or Se;
Z 1 and Z 2 Identically or differently on each occurrence is selected from O, S or Se;
r, R ', R "and R'" are, identically or differently at each occurrence, selected from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 A boryl group, a sulfinyl group, a sulfonyl group, a phosphinyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms,a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;
each R may be the same or different and at least one of R, R ', R "and R'" is a group having at least one electron withdrawing group;
adjacent substituents in formula 1 can optionally be linked to form a ring;
the second compound has a structure represented by formula 2:
Figure BDA0003398928070000041
in the case of the formula 2, the reaction mixture,
X 1 to X 8 Each occurrence of the same or different is selected from C, CR 1 Or N; x 9 To X 18 Selected from CR, identically or differently at each occurrence 1 Or N;
q is selected from C, Si or Ge;
L 1 to L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms,substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring.
According to another embodiment of the invention, a display assembly is also disclosed, which comprises the organic electroluminescent device described in the above embodiment.
According to another embodiment of the present invention, there is also disclosed a compound combination comprising a first compound and a second compound, wherein the first compound has a structure represented by formula 1:
Figure BDA0003398928070000051
in the case of the formula 1, the compound,
x and Y are, identically or differently on each occurrence, selected from NR ', CR "R'", O, S or Se;
Z 1 and Z 2 Identically or differently on each occurrence is selected from O, S or Se;
r, R 'and R' are the same at each occurrenceOr variously selected from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 A boryl group, a sulfinyl group, a sulfonyl group, a phosphinyloxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, and combinations thereof;
each R may be the same or different and at least one of R, R ', R "and R'" is a group having at least one electron withdrawing group;
adjacent substituents in formula 1 can optionally be linked to form a ring;
the second compound has a structure represented by formula 2:
Figure BDA0003398928070000052
in the formula 2, the first and second groups,
X 1 to X 8 Selected from C, CR, the same or different at each occurrence 1 Or N; x 9 To X 18 Selected from CR, identically or differently at each occurrence 1 Or N;
q is selected from C, Si or Ge;
L 1 to L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3-20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring.
The invention discloses a novel organic electroluminescent device which comprises an anode, a cathode and a first organic layer arranged between the anode and the cathode, wherein the first organic layer at least comprises a first compound with a structure of a formula 1 and a second compound with a structure of a formula 2. The novel material combination consisting of the first compound and the second compound can be used in a hole injection layer in an organic electroluminescent device, so that the organic electroluminescent device has excellent characteristics of low voltage, high efficiency and long service life, and better device performance can be provided.
Drawings
Fig. 1 is a schematic diagram of an organic light emitting device that may contain the organic electroluminescent devices disclosed herein.
Fig. 2 is a schematic view of another organic light emitting device that may contain the organic electroluminescent devices disclosed herein.
Detailed Description
OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically, but without limitation, illustrates an organic light emitting device 100. The figures are not necessarily to scale, and some of the layer structures in the figures may be omitted as desired. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, an emissive layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the described layers. The nature and function of the layers, as well as exemplary materials, are described in more detail in U.S. patent US7,279,704B2, columns 6-10, which is incorporated herein by reference in its entirety.
There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F at a molar ratio of 50:1 4 TCNQ m-MTDATA as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. patent No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of a metal such as Mg: Ag and an overlying layer of transparent, conductive, sputter-deposited ITO. U.S. patent incorporated by reference in its entiretyThe principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980. Examples of injection layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer may be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.
The above-described hierarchical structure is provided via non-limiting embodiments. The function of the OLED may be achieved by combining the various layers described above, or some layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sub-layers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.
In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include one or more layers.
The OLED also requires an encapsulation layer, as shown in fig. 2, which is a schematic, non-limiting illustration of an organic light emitting device 200, which differs from fig. 1 in that an encapsulation layer 102 may also be included on the cathode 190 to prevent harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or a hybrid organic-inorganic layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film encapsulation is described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.
Devices manufactured according to embodiments of the present invention may be incorporated into various consumer products having one or more electronic component modules (or units) of the device. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, head-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, tablet handsets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and tail lights.
The materials and structures described herein may also be used in other organic electronic devices as previously listed.
As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. In the case where the first layer is described as being "disposed on" the second layer, the first layer is disposed farther from the substrate. Other layers may be present between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode can be described as being "disposed on" an anode even though various organic layers are present between the cathode and the anode.
As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and/or deposited from a liquid medium in the form of a solution or suspension.
A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" when it is believed that the ligand does not contribute to the photoactive properties of the emissive material, but the ancillary ligand may alter the properties of the photoactive ligand.
It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by delaying fluorescence beyond 25% spin statistics. Delayed fluorescence can be generally classified into two types, i.e., P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence results from triplet-triplet annihilation (TTA).
On the other hand, E-type delayed fluorescence does not depend on collision of two triplet states, but on conversion between triplet and singlet excited states. Compounds capable of producing E-type delayed fluorescence need to have a very small mono-triplet gap in order to switch between energy states. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as Thermally Activated Delayed Fluorescence (TADF). A significant feature of TADF is that the retardation component increases with increasing temperature. The fraction of backfill singlet excited states may reach 75% if the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet state. The total singlet fraction may be 100%, far exceeding 25% of the spin statistics of the electrogenerated excitons.
The delayed fluorescence characteristic of type E can be found in excited complex systems or in single compounds. Without being bound by theory, it is believed that E-type delayed fluorescence requires the light emitting material to have a small mono-triplet energy gap (Δ Ε) S-T ). Organic non-metal containing donor-acceptor emissive materials may be able to achieve this. The emission of these materials is generally characterized as donor-acceptor Charge Transfer (CT) type emission. Spatial separation of HOMO from LUMO in these donor-acceptor type compounds generally results in small Δ E S-T . These states may include CT states. Generally, donor-acceptor light emitting materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., a six-membered, N-containing, aromatic ring).
Definitions for substituent terms
Halogen or halide-as used herein, includes fluorine, chlorine, bromine and iodine.
Alkyl-as used herein, includes both straight and branched chain alkyl groups. The alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl are preferred. In addition, the alkyl group may be optionally substituted.
Cycloalkyl-as used herein, comprises a cyclic alkyl group. The cycloalkyl group may be a cycloalkyl group having 3 to 20 ring carbon atoms, preferably a cycloalkyl group having 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4, 4-dimethylcyclohexyl are preferable. In addition, the cycloalkyl group may be optionally substituted.
Heteroalkyl-as used herein, heteroalkyl comprises a alkyl chain wherein one or more carbons are substituted with a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium and boron atoms. The heteroalkyl group may be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, and more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxyethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermylmethyl, trimethylgermylethyl, trimethylgermylisopropyl, dimethylethylgermylmethyl, dimethylisopropylgermylmethyl, tert-butyldimethylgermylmethyl, triethylgermylmethyl, triethylgermylethyl, triisopropylgermylmethyl, triisopropylgermylethyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl, triisopropylsilylmethyl, triisopropylsilylethyl. In addition, heteroalkyl groups may be optionally substituted.
Alkenyl-as used herein, encompasses straight chain, branched chain, and cyclic olefin groups. The alkenyl group may be an alkenyl group containing 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 10 carbon atoms. Examples of the alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, a 1-methylvinyl group, a styryl group, a 2, 2-diphenylvinyl group, a 1-methylallyl group, a1, 1-dimethylallyl group, a 2-methylallyl group, a 3-phenylallyl group, a 3, 3-diphenylallyl group, a1, 2-dimethylallyl group, a 1-phenyl-1-butenyl group, a 3-phenyl-1-butenyl group, a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, a cycloheptenyl group, a cycloheptatrienyl group, a cyclooctenyl group, a cyclooctatetraenyl group and a norbornenyl group. In addition, alkenyl groups may be optionally substituted.
Alkynyl-as used herein, straight chain alkynyl is contemplated. The alkynyl group may be an alkynyl group containing 2 to 20 carbon atoms, preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3, 3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3, 3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl, and the like. Among the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl and phenylethynyl. In addition, alkynyl groups may be optionally substituted.
Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. The aryl group may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,
Figure BDA0003398928070000081
perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methyldiphenyl, 4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-quaterphenyl. In addition, the aryl group may be optionally substituted.
Heterocyclyl or heterocyclic-as used herein, non-aromatic cyclic groups are contemplated. The non-aromatic heterocyclic group includes a saturated heterocyclic group having 3 to 20 ring atoms and an unsaturated non-aromatic heterocyclic group having 3 to 20 ring atoms, at least one of which is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom and a boron atom, and preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, which include at least one hetero atom such as nitrogen, oxygen, silicon or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxolanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepinyl, and tetrahydrosilolyl. In addition, the heterocyclic group may be optionally substituted.
Heteroaryl-as used herein, non-fused and fused heteroaromatic groups that may contain 1 to 5 heteroatoms, at least one of which is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom and a boron atom. Heteroaryl also refers to heteroaryl. The heteroaryl group may be a heteroaryl group having 3 to 30 carbon atoms, preferably a heteroaryl group having 3 to 20 carbon atoms, more preferably a heteroaryl group having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indoline, benzimidazole, indazole, indenozine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, cinnolino, benzoselenophenopyridine, selenobenzene, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-azaborine, 1, 3-azaborine, 1, 4-azaborine, borazole, and aza analogues thereof. In addition, the heteroaryl group may be optionally substituted.
Alkoxy-as used herein, is represented by-O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or-O-heterocyclyl. Examples and preferred examples of the alkyl group, cycloalkyl group, heteroalkyl group and heterocyclic group are the same as those described above. The alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuryloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. In addition, alkoxy groups may be optionally substituted.
Aryloxy-as used herein, is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. The aryloxy group may be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the aryloxy group include a phenoxy group and a biphenyloxy group. In addition, the aryloxy group may be optionally substituted.
Aralkyl-as used herein, encompasses aryl-substituted alkyl groups. The aralkyl group may be an aralkyl group having 7 to 30 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 13 carbon atoms. Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthylethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthylethyl, 2- β -naphthylethyl, 1- β -naphthylisopropyl, 2- β -naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl. Among the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl. In addition, the aralkyl group may be optionally substituted.
Alkylsilyl-as used herein, alkyl substituted silyl is contemplated. The alkylsilyl group may be an alkylsilyl group having 3 to 20 carbon atoms, preferably an alkylsilyl group having 3 to 10 carbon atoms. Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, methyldiethylsilyl group, ethyldimethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, methyldiisopropylsilyl group, dimethylisopropylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, dimethyl-tert-butylsilyl group, and methyl-di-tert-butylsilyl group. Additionally, the alkylsilyl group may be optionally substituted.
Arylsilyl-as used herein, encompasses at least one aryl-substituted silicon group. The arylsilane group may be an arylsilane group having 6 to 30 carbon atoms, preferably an arylsilane group having 8 to 20 carbon atoms. Examples of the arylsilyl group include triphenylsilyl group, phenylbiphenylsilyl group, diphenylbiphenylsilyl group, phenyldiethylsilyl group, diphenylethylsilyl group, phenyldimethylsilyl group, diphenylmethylsilyl group, phenyldiisopropylsilyl group, diphenylisopropylsilyl group, diphenylbutylsilyl group, diphenylisobutylsilyl group, and diphenyltert-butylsilyl group. In addition, the arylsilyl group may be optionally substituted.
Alkylgermyl-as used herein, alkyl-substituted germyl is contemplated. The alkylgermyl group may be an alkylgermyl group having 3 to 20 carbon atoms, preferably an alkylgermyl group having 3 to 10 carbon atoms. Examples of the alkylgermyl group include a trimethylgermyl group, a triethylgermyl group, a methyldiethylgermyl group, an ethyldimethylgermyl group, a tripropylgermyl group, a tributylgermyl group, a triisopropylgermyl group, a methyldiisopropylgermyl group, a dimethylisopropylgermyl group, a tri-tert-butylgermyl group, a triisobutylgermyl group, a dimethyl-tert-butylgermyl group, and a methyl-di-tert-butylgermyl group. In addition, the alkylgermyl group may be optionally substituted.
Arylgermyl-as used herein, encompasses at least one aryl or heteroaryl substituted germyl. The arylgermanium group may be an arylgermanium group having 6 to 30 carbon atoms, preferably an arylgermanium group having 8 to 20 carbon atoms. Examples of the arylgermanium group include a triphenylgermanium group, a phenylbiphenylgermanium group, a diphenylbiphenylgermanium group, a phenyldiethylgermanium group, a diphenylethylgermanium group, a phenyldimethylgermanium group, a diphenylmethylgermanium group, a phenyldiisopropylgermanium group, a diphenylisopropylgermanium group, a diphenylbutylgermanium group, a diphenylisobutylgermanium group, a diphenylt-butylgermanium group. In addition, the arylgermyl group may be optionally substituted.
The term "aza" in azabenzofuran, azabenzothiophene, etc., means that one or more of the C-H groups in the corresponding aromatic moiety are replaced by a nitrogen atom. For example, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives may be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed within the terms described herein.
In this disclosure, unless otherwise defined, when any one of the terms in the group consisting of: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted alkylgermyl, substituted arylgermyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, meaning alkyl, cycloalkyl, heteroalkyl, heterocyclyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, alkylgermyl, arylgermyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups any of which may be substituted with one or more moieties selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted heterocyclyl having 3 to 20 ring atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkynyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted arylsilyl having 6 to 20 carbon atoms, unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, unsubstituted arylgermyl groups having 6 to 20 carbon atoms, unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof.
It will be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name may be written depending on whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or depending on whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered to be equivalent.
In the compounds mentioned in the present disclosure, a hydrogen atom may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred because it enhances the efficiency and stability of the device.
In the compounds mentioned in the present disclosure, multiple substitution means that a double substitution is included up to the range of the maximum available substitutions. When a substituent in a compound mentioned in the present disclosure represents multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), that is, it means that the substituent may exist at a plurality of available substitution positions on its connecting structure, and the substituent existing at each of the plurality of available substitution positions may be the same structure or different structures.
In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless specifically defined, for example, adjacent substituents can be optionally linked to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can be optionally linked to form a ring, including both the case where adjacent substituents may be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic (including spiro, bridged, fused, etc.), as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic rings. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom as well as substituents bonded to carbon atoms directly bonded to each other.
The expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
Figure BDA0003398928070000101
the expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
Figure BDA0003398928070000102
the expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to further away carbon atoms are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
Figure BDA0003398928070000111
further, the expression that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that, in the case where one of the adjacent two substituents represents hydrogen, the second substituent is bonded at the position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following equation:
Figure BDA0003398928070000112
according to an embodiment of the present invention, there is disclosed an organic electroluminescent device including:
an anode, a cathode, an anode and a cathode,
a cathode electrode, which is provided with a cathode,
and a first organic layer disposed between the anode and the cathode, wherein the first organic layer includes at least a first compound and a second compound, wherein the first compound has a structure represented by formula 1:
Figure BDA0003398928070000113
in the case of the formula 1, the compound,
x and Y are, identically or differently on each occurrence, selected from NR ', CR "R'", O, S or Se;
Z 1 and Z 2 Identically or differently on each occurrence is selected from O, S or Se;
r, R ', R "and R'" are, identically or differently on each occurrence, selected from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF 5 A boryl group, a sulfinyl group, a sulfonyl group, a phosphinyloxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atomsSubstituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, and combinations thereof;
each R may be the same or different and at least one of R, R ', R "and R'" is a group having at least one electron withdrawing group;
adjacent substituents in formula 1 can optionally be linked to form a ring;
the second compound has a structure represented by formula 2:
Figure BDA0003398928070000114
in the formula 2, the first and second groups,
X 1 to X 8 Each occurrence of the same or different is selected from C, CR 1 Or N; x 9 To X 18 Selected from CR, identically or differently at each occurrence 1 Or N;
q is selected from C, Si or Ge;
L 1 to L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted with 1 to 20 carbon atomsSubstituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring.
In this example, adjacent substituents in formula 1 can optionally be linked to form a ring, and is intended to mean that, in formula 1, adjacent substituent groups, such as adjacent substituents R "and R '", adjacent substituents R and R' ", and two adjacent substituents R, any one or more of these adjacent substituent groups can be linked to form a ring. Obviously, these adjacent substituent groups may not be connected to form a ring.
In this context, L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring, is intended to mean, in formula 2, an adjacent substituent group, for example an adjacent substituent R 1 Adjacent substituents R 1 And L 3 Adjacent substitution L 1 And L 2 Adjacent takingSubstituent L 1 And L 3 Adjacent substituents L 2 And L 3 Adjacent substituent Ar 1 And Ar 2 Adjacent substituent Ar 1 And L 3 Adjacent substituent Ar 2 And L 3 Adjacent substituent Ar 1 And R 1 And adjacent substituent Ar 2 And R 1 Any one or more of these adjacent substituent groups can be linked to form a ring. Obviously, these adjacent substituent groups may not be connected to form a ring.
According to one embodiment of the invention, wherein in formula 1, X and Y are selected from CR "R '" or NR ', R "and R '" on each occurrence, identically or differently, being groups with at least one electron-withdrawing group.
According to one embodiment of the invention, wherein, in formula 1, R ', R "and R'" are groups having at least one electron withdrawing group.
According to one embodiment of the invention, wherein in formula 1, X and Y are selected, identically or differently on each occurrence, from O, S or Se, at least one of R is a group with at least one electron-withdrawing group.
According to one embodiment of the invention, wherein, in formula 1, each R is a group having at least one electron-withdrawing group.
According to an embodiment of the invention, the Hammett constant of the electron-withdrawing group is ≧ 0.05, preferably ≧ 0.3, more preferably ≧ 0.5.
The Hammett substituent constant value of the electron withdrawing group is more than or equal to 0.05, the electron withdrawing capability is strong, the LUMO energy level of the compound can be remarkably reduced, and the effect of improving the charge mobility is achieved.
Note that the hammett substituent constant value includes a hammett substituent para-constant and/or a meta-constant, and any one of the para-constant and the meta-constant satisfies 0.05 or more may be used as a preferable optional group in the present invention.
According to an embodiment of the invention, wherein the electron withdrawing group is selected from the group consisting of: halogen, nitrosoNitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 Boryl, sulfinyl, sulfonyl, phosphinoxy, azaaryl, and substituted with halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 Boryl, sulfinyl, sulfonyl, phosphinoxy, an azaaryl group, substituted with one or more of any of the following: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and combinations thereof.
According to an embodiment of the invention, wherein the electron withdrawing group is selected from the group consisting of: f, CF 3 ，OCF 3 ，SF 5 ，SO 2 CF 3 Cyano, isocyano, SCN, OCN, pyrimidinyl, triazinyl, and combinations thereof.
According to one embodiment of the invention, wherein X and Y are selected, identically or differently at each occurrence, from the group consisting of:
O，S，Se，
Figure BDA0003398928070000131
Figure BDA0003398928070000132
Figure BDA0003398928070000141
R 2 the same or different at each occurrence is selected from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acidGroup, ester group, cyano group, isocyano group, SCN, OCN, SF 5 A boryl group, a sulfinyl group, a sulfonyl group, a phosphinyloxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, and combinations thereof;
preferably, R 2 The same or different at each occurrence is selected from the group consisting of: f, CF 3 ，OCF 3 ，SF 5 ，SO 2 CF 3 Cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazinyl, and combinations thereof;
v and W are selected, identically or differently on each occurrence, from CR v R w ，NR v O, S or Se;
ar is the same or different at each occurrence and is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;
A，R a ，R b ，R c ，R d ，R e ，R f ，R g ，R h ，R v and R w The same or different at each occurrence is selected from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF 5 Boryl, sulfinyl, sulfonyl, phosphinyl, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkyl groups having 3 to 20 ring carbon atomsA cycloalkyl group, a substituted or unsubstituted heteroalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having from 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having from 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having from 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having from 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having from 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having from 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having from 6 to 20 carbon atoms, and combinations thereof;
a is a group having at least one electron withdrawing group, and for either structure, when R a ，R b ，R c ，R d ，R e ，R f ，R g ，R h ，R v And R w When one or more of them occur, R a ，R b ，R c ，R d ，R e ，R f ，R g ，R h ，R v And R w At least one of which is a group having at least one electron-withdrawing group; preferably, the group having at least one electron withdrawing group is selected from the group consisting of: f, CF 3 ，OCF 3 ，SF 5 ，SO 2 CF 3 Cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazinyl, and combinations thereof.
In the present embodiment, ""' indicates a position where the X and Y are linked to a dehydrobenzodioxazole ring, a dehydrobenzodithiazole ring or a dehydrobenzodiselenazole ring in the formula 1.
According to one embodiment of the invention, wherein X and Y are selected, identically or differently at each occurrence, from the group consisting of:
O，S，Se，
Figure BDA0003398928070000142
Figure BDA0003398928070000151
in this embodiment, "' indicates a position in the X and Y to which the dehydrobenzodioxazole ring, the dehydrobenzodithiazole ring or the dehydrobenzodiselenazole ring in formula 1 is bonded.
According to one embodiment of the invention, wherein R is selected, identically or differently on each occurrence, from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF 5 Boryl, sulfinyl, sulfonyl, phosphinoxy, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, and substituted with halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 Any of the following substituted with one or more of boryl, sulfinyl, sulfonyl and phosphinyl: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein R is selected, identically or differently on each occurrence, from the group consisting of: hydrogen, deuterium, methyl, isopropyl, NO 2 ，SO 2 CH 3 ，SCF 3 ，C 2 F 5 ，OC 2 F 5 ，OCH 3 Diphenylmethylsilyl, phenyl, methoxyphenyl, p-methylphenyl, 2, 6-diisopropylphenyl, biphenyl, polyfluorophenyl, difluoropyridyl, nitrophenyl, dimethylthiazolyl, optionally substituted with CN or CF 3 By CN or CF 3 Substituted ethynyl, dimethylphosphinoxy, diphenylphosphinoxy, F, CF 3 ，OCF 3 ，SF 5 ，SO 2 CF 3 Cyano, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis (trifluoromethyl) phenyl, bis (trifluoromethoxy) phenyl, 4-cyanotetrafluorophenyl, by F, CN or CF 3 One or more substituted phenyl or biphenyl groups of (a), a tetrafluoropyridyl group, a pyrimidinyl group, a triazinyl group, a diphenylboryl group, a oxaboro-anthracenyl group, and combinations thereof.
According to one embodiment of the invention, wherein X and Y are
Figure BDA0003398928070000152
According to one embodiment of the invention, wherein R, on each occurrence, is selected, identically or differently, from the group consisting of:
Figure BDA0003398928070000153
Figure BDA0003398928070000161
Figure BDA0003398928070000171
in the present embodiment, it is preferred that,
Figure BDA0003398928070000172
represents a position where the R group is linked to a dehydrobenzodioxazole ring, a dehydrobenzodithiazole ring or a dehydrobenzodiselenazole ring in formula 1.
According to an embodiment of the present invention, wherein two R are the same in one first compound represented by formula 1.
According to an embodiment of the present invention, wherein said first compound is selected from the group consisting of compound 1 to compound 1356; the specific structures of said compounds 1 to 1356 are found in claim 10.
According to an embodiment of the present invention, wherein the second compound has a structure represented by any one of formula 2-1 to formula 2-12:
Figure BDA0003398928070000173
Figure BDA0003398928070000181
X 1 to X 18 Selected from CR, identically or differently at each occurrence 1 ；
L 1 To L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl group having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermyl group having 6 to 20 carbon atomsAn arylgermanyl group of atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring.
According to an embodiment of the present invention, wherein the second compound has a structure represented by formula 2-1, formula 2-2, formula 2-3, formula 2-4, formula 2-6, or formula 2-10.
According to one embodiment of the present invention, wherein, in formula 2, X 1 To X 18 At least one of which is N.
According to an embodiment of the present invention, wherein the second compound has a structure represented by any one of formulas 2-13 to 2-24:
Figure BDA0003398928070000191
X 1 to X 18 Selected from CR, identically or differently at each occurrence 1 Or N;
L 1 to L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene having 3 to 30 carbon atoms, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted heteroarylAn aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring.
According to an embodiment of the present invention, wherein the second compound has a structure represented by formula 2-13, formula 2-14, formula 2-15, formula 2-16, formula 2-18, or formula 2-22.
According to an embodiment of the present invention, wherein, in formulae 2-13 to 2-24, X 1 To X 18 Selected from CR, identically or differently at each occurrence 1 。
According to one embodiment of the present invention, wherein, in the formulas 2-13 to 2-24, X 1 To X 18 At least one of which is selected from N.
In this embodiment, in formulae 2-13 to 2-24, X 1 To X 18 At least one of which is selected from N, intended to mean: in the formulae 2 to 13, 2 to 17 and 2 to 21, X 1 To X 7 、X 9 To X 12 And X 15 To X 18 At least one of which is N; in the formulae 2 to 14, 2 to 18 and 2 to 22, X 1 To X 6 、X 8 To X 12 And X 15 To X 18 At least one of which is N; in formulae 2-15, formulae 2-19, and formulae 2-23, X 1 To X 5 、X 7 To X 12 And X 15 To X 18 At least one of which is N; and in formulae 2-16, formulae 2-20, and formulae 2-24, X 1 To X 4 、X 6 To X 12 And X 15 To X 18 At least one of which is N.
According to an embodiment of the present invention, wherein said L 1 To L 3 The same or different at each occurrence is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 24 carbon atoms, or a combination thereof.
According to an embodiment of the invention, wherein L 1 To L 3 Each occurrence, identically or differently, is selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted silafluorenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dibenzoselenophenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted spirobifluorenylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted pyrenylene group, or a combination thereof.
According to an embodiment of the invention, wherein L 1 To L 3 Each occurrence, the same or different, is selected from the group consisting of:
Figure BDA0003398928070000201
in this embodiment, "+" indicates the position bonded to the nitrogen in formula 2 in the L-1 to L-13, and the dotted line indicates X in formula 2 in the L-1 to L-13 1 To X 8 Any one of, Ar 1 Or Ar 2 The location of the connection.
According to an embodiment of the present invention, wherein, Ar 1 And Ar 2 Each occurrence, the same or different, has a structure represented by any one of formulas 3-1 to 3-4:
Figure BDA0003398928070000211
e is selected, identically or differently on each occurrence, from O, S, Se, C (R) 4 ) 2 ，Si(R 4 ) 2 Or Ge (R) 4 ) 2 (ii) a When two R are simultaneously present 4 When two R are present 4 May be the same or different;
R 3 the same or different at each occurrence is indicative of mono-, poly-or unsubstituted;
R 3 and R 4 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents R 3 ，R 4 Can optionally be linked to form a ring.
In this example, the adjacent substituents R 3 ，R 4 Can optionally be linked to form a ring, are intended to mean wherein adjacent groups of substituents, for example, adjacent substituents R 3 And R 3 Adjacent substituents R 3 And R 4 And adjacent substituents R 4 And R 4 And any one or more of these adjacent substituent groups can be linked to form a ring. Obviously, none of these adjacent substituent groups may be linked to form a ring.
In this embodiment, the dotted line represents the Ar 1 In the structure of (1) and the L 1 The location of the connection; the dotted line also represents said Ar 2 In the structure of (1) and the L 2 The location of the connection.
According to one embodiment of the invention, wherein R 3 And R 4 Each occurrence, the same or different, is selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, or a combination thereof.
According to an embodiment of the present invention, wherein, Ar 1 And Ar 2 Each occurrence, identically or differently, is selected from the group consisting of G1 to G37:
Figure BDA0003398928070000212
Figure BDA0003398928070000221
R 4 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aralkyl having 1 to 20 carbon atomsAn alkoxy group of 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, cyano, isocyano, hydroxy, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;
adjacent substituents R 4 Can optionally be linked to form a ring.
In this example, the adjacent substituents R 4 Can optionally be linked to form a ring, intended to denote any adjacent two substituents R 4 Can be linked to form a ring. Obviously, any two adjacent substituents R 4 Or may not be connected to form a ring.
According to one embodiment of the invention, wherein R 4 Each occurrence, the same or different, is selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a combination thereof.
According to one embodiment of the invention, wherein R 4 Each occurrence, which is the same or different, is selected from hydrogen, deuterium, methyl, ethyl, isopropyl, fluorene, phenyl, biphenyl, naphthyl, or a combination thereof.
According to one embodiment of the invention, wherein R 1 Each occurrence being the same or different and is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted hetero groups having 3 to 30 carbon atomsAryl, or a combination thereof.
According to an embodiment of the invention, wherein X 1 To X 18 At least 1 or 2, at each occurrence, are selected, identically or differently, from CR 1 And said R is 1 Each occurrence, the same or different, is selected from deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, or a combination thereof.
According to an embodiment of the present invention, wherein, in formulae 2-1 to 2-24, X 9 To X 18 At least 1 or 2, at each occurrence, are selected, identically or differently, from CR 1 And said R is 1 Each occurrence, the same or different, is selected from deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, or a combination thereof.
According to one embodiment of the invention, wherein R 1 Each occurrence, identically or differently, is selected from hydrogen, deuterium, fluorine, methyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, or a combination thereof.
According to an embodiment of the present invention, wherein said Ar in said second compound 1 And Ar 2 Joined to form a ring.
According to an embodiment of the invention, wherein L 1 And L 2 Is a single bond.
According to an embodiment of the present invention, wherein the second compound has a structure represented by formulas 2 to 25:
Figure BDA0003398928070000231
X 1 to X 8 Selected from C, CR, the same or different at each occurrence 1 Or N;
X 9 to X 18 Selected from CR, identically or differently at each occurrence 1 Or N;
q is selected at each occurrence from C, Si or Ge;
t is selected, identically or differently on each occurrence, from CR 5 ’R 5 ', O, S or NR 5 ’；
R 5 The same or different at each occurrence is indicative of mono-, poly-or unsubstituted;
R 5 and R 5 ' each occurrence, identically or differently, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
L 3 each occurrence, identically or differently, being selected from single bonds, substituted or unsubstituted arylenes having 6 to 30 carbon atoms, substituted or unsubstituted arylenes having 3 to 30 carbon atomsThe heteroarylene of (a), or a combination thereof;
adjacent substituents R 1 ，R 5 And R 5 ' can optionally be linked to form a ring.
In this example, the adjacent substituents R 1 ，R 5 And R 5 ' optionally linked to form a ring, is intended to mean a group in which adjacent substituents are present, e.g. adjacent substituents R 1 And R 1 Adjacent substituents R 5 And R 5 Adjacent substituents R 5 And R 5 ', and adjacent substituents R 5 ' and R 5 ', any one or more of these adjacent substituent groups can be linked to form a ring. Obviously, these adjacent substituent groups may not be connected to form a ring.
According to one embodiment of the invention, wherein the second compound is selected from the group consisting of compound I-1 to compound I-7, compound I-12 to compound I-182, compound I-185 to compound I-229, compound I-232 to compound I-273, compound II-1 to compound II-7, compound II-9 to compound II-30, compound II-32 to compound II-35, compound II-39 to compound II-79, compound II-81 to compound II-95, compound II-97 to compound II-110, compound II-112 to compound II-208, compound II-210 to compound II-221, compound II-225 to compound II-243, compound II-245 to compound II-273, compound II-275 to compound II-286, compound II-288, compound II-290 to compound II-308, compound II-310 to compound II-332, compound III-1 to compound III-7, compound III-12 to compound III-182, compound III-185 to compound III-229, compound III-232 to compound III-273, compound IV-1 to compound IV-7, compound IV-12 to compound IV-182, compound IV-185 to compound IV-229, compound IV-232 to compound IV-273, compound V-1 to compound V-7, compound V-12 to compound V-182, compound V-185 to compound V-229, compound V-232 to compound V-273, compound VI-1 to compound VI-7, compound VI-12 to compound VI-182, compound VI-185 to compound VI-229, compound VI-232 to compound VI-273, compound VII-1 to compound VII-7, compound VII-12 to compound VII-182, compound VII-185 to compound VII-229, compound VII-232 to compound VII-273, compound VIII-1 to compound VIII-7, compound VIII-12 to compound VIII-182, compound VIII-185 to compound VIII-229, compound VIII-232 to compound VIII-273, compound IX-1 to compound IX-7, compound IX-12 to compound IX-182, compound IX-185 to compound IX-229, compound IX-232 to compound IX-273, compound X-1 to compound X-7, compound X-12 to compound X-182, compound X-185 to compound X-229, or compound X-232 to compound X-273. The compounds I-1 to I-7, I-12 to I-182, I-185 to I-229, I-232 to I-273, II-1 to II-7, II-9 to II-30, II-32 to II-35, II-39 to II-79, II-81 to II-95, II-97 to II-110, II-112 to II-208, II-210 to II-221, II-225 to II-243, II-245 to II-273, II-275 to II-286, compound II-288, compound II-290 to compound II-308, compound II-310 to compound II-332, compound III-1 to compound III-7, compound III-12 to compound III-182, compound III-185 to compound III-229, compound III-232 to compound III-273, compound IV-1 to compound IV-7, compound IV-12 to compound IV-182, compound IV-185 to compound IV-229, compound IV-232 to compound IV-273, compound V-1 to compound V-7, compound V-12 to compound V-182, compound V-185 to compound V-229, compound V-232 to compound V-273, compound VI-1 to compound VI-7, compound VI-12 to compound VI-182, compound VI-185 to compound VI-229, compound VI-232 to compound VI-273, compound VII-1 to compound VII-7, compound VII-12 to compound VII-182, compound VII-185 to compound VII-229, compound VII-232 to compound VII-273, compound VIII-1 to compound VIII-7, compound VIII-12 to compound VIII-182, compound VIII-185 to compound VIII-229, compound VIII-232 to compound VIII-273, compound IX-1 to compound IX-7, compound IX-12 to compound IX-182, compound IX-185 to compound IX-229, specific structures of compound IX-232 to compound IX-273, compound X-1 to compound X-7, compound X-12 to compound X-182, compound X-185 to compound X-229, and compound X-232 to compound X-273 are given in claim 19.
According to an embodiment of the present invention, wherein the first organic layer is a hole injection layer, and the hole injection layer is in contact with an anode.
According to one embodiment of the invention, in the first organic layer, the weight ratio of the first compound to the second compound is between 10000:1 and 1: 10000; preferably, the weight ratio of the first compound to the second compound is between 100:1 and 1: 10000; more preferably, the weight ratio of the first compound and the second compound is between 10:1 and 1: 10000.
According to an embodiment of the present invention, wherein, in the first organic layer, the first compound accounts for 0.01% to 10% of the total weight of the first organic layer; or the first compound comprises 0.01% to 5% of the total weight of the first organic layer; or the first compound comprises 0.01% to 3% of the total weight of the first organic layer or the first compound comprises 0.01% to 2% of the total weight of the first organic layer; or the first compound comprises 0.01% to 1.5% of the total weight of the first organic layer; or the first compound accounts for 0.01-1% of the total weight of the first organic layer.
According to one embodiment of the present invention, wherein the organic electroluminescent device further comprises at least one light emitting layer.
According to one embodiment of the present invention, wherein the at least one light emitting layer comprises at least one host material and at least one dopant material.
According to one embodiment of the invention, the maximum emission wavelength of the organic electroluminescent device is between 300 and 1200 nm.
According to one embodiment of the present invention, wherein the organic electroluminescent device further comprises a second organic layer, and the second organic layer is disposed between the first organic layer and the at least one light emitting layer.
According to an embodiment of the present invention, wherein the second organic layer comprises a compound comprising any one or more of the following chemical structural units selected from the group of: triarylamines, carbazoles, fluorenes, spirobifluorenes, thiophenes, furans, phenyls, oligophenylethylenes, oligofluorenes, and combinations thereof.
According to an embodiment of the invention, wherein the one compound in the second organic layer is the second compound.
According to one embodiment of the present invention, wherein the organic electroluminescent device further comprises a third organic layer disposed between the second organic layer and the light emitting layer.
According to an embodiment of the invention, wherein the third organic layer comprises a further compound comprising any one or more chemical building blocks selected from the group of: triarylamines, carbazoles, fluorenes, spirobifluorenes, thiophenes, furans, phenyls, oligophenylenes, oligofluorenes, and combinations thereof.
According to an embodiment of the invention, wherein the further compound in the third organic layer is the second compound.
According to an embodiment of the invention, wherein, in the device, only a first organic layer of all organic layers arranged between the anode and the light emitting layer is p-type doped.
According to one embodiment of the present invention, the thickness of the first organic layer is between 0.1nm and 40nm, and the thickness of the second organic layer is between 0.1nm and 300 nm.
According to another embodiment of the invention, a display assembly is also disclosed, which comprises an organic electroluminescent device, and the specific structure of the organic electroluminescent device is shown in any one of the embodiments.
According to another embodiment of the present invention, there is also disclosed a compound combination comprising a first compound and a second compound, wherein the first compound has a structure represented by formula 1:
Figure BDA0003398928070000261
in the formula 1, the first and second groups,
x and Y are, identically or differently on each occurrence, selected from NR ', CR "R'", O, S or Se;
Z 1 and Z 2 Identically or differently on each occurrence is selected from O, S or Se;
r, R ', R "and R'" are, identically or differently at each occurrence, selected from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 A boryl group, a sulfinyl group, a sulfonyl group, a phosphinyloxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, and combinations thereof;
each R may be the same or different and at least one of R, R ', R "and R'" is a group having at least one electron withdrawing group;
adjacent substituents in formula 1 can optionally be linked to form a ring;
the second compound has a structure represented by formula 2:
Figure BDA0003398928070000262
in the formula 2, the first and second groups,
X 1 to X 8 Selected from C, CR, the same or different at each occurrence 1 Or N; x 9 To X 18 Selected from CR, identically or differently at each occurrence 1 Or N;
q is selected from C, Si or Ge;
L 1 to L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring.
In combination with other materials
The materials described herein for use in particular layers in an organic light emitting device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application Ser. No. 0132-0161 of U.S. 2016/0359122A1, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
Materials described herein as being useful for particular layers in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the compound combinations disclosed herein may be used in conjunction with a variety of light emitting dopants, hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. US2015/0349273A1, paragraph 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that can be used in combination.
In the device of the present invention, charge injection, transport layers such as a hole transport layer, an electron transport layer, and an electron injection layer; the luminescent layer at least comprises a luminescent dopant and at least a host compound, and the luminescent dopant can be a fluorescent luminescent dopant and/or a phosphorescent luminescent dopant; blocking layers such as hole blocking layers, electron blocking layers, and the like may also be included.
Conventional hole transport materials of the prior art may be used in the hole transport layer, for example, the hole transport layer may typically, but not by way of limitation, comprise the following hole transport materials:
Figure BDA0003398928070000271
Figure BDA0003398928070000281
conventional electron transport materials of the prior art may be used in the electron transport layer, for example, the electron transport layer may typically, but not exclusively, comprise the following electron transport materials:
Figure BDA0003398928070000282
conventional luminescent materials and host materials in the prior art may be used in the luminescent layer, for example, the luminescent layer may typically, but not limited to, contain the following fluorescent luminescent materials and fluorescent host materials:
Figure BDA0003398928070000291
Figure BDA0003398928070000301
Figure BDA0003398928070000311
the light emitting layer may also typically, but not by way of limitation, comprise phosphorescent light emitting materials and phosphorescent host materials as follows:
Figure BDA0003398928070000312
Figure BDA0003398928070000321
Figure BDA0003398928070000331
Figure BDA0003398928070000341
Figure BDA0003398928070000351
Figure BDA0003398928070000361
conventional electron blocking materials of the prior art may be used in the electron blocking layer, for example, the electron blocking layer may typically, but not exclusively, comprise the following electron blocking materials:
Figure BDA0003398928070000362
the first compound and the second compound used in the present invention can be obtained by referring to the preparation method in the prior art, or can be easily prepared by referring to patent applications with publication numbers of US20200087311a1, US20160190447a1, etc., and are not described herein again. The method of fabricating the electroluminescent device is not limited, and the method of fabricating the following examples is only an example and should not be construed as limiting. The preparation of the following examples can be reasonably modified by those skilled in the art in light of the prior art. For example, the ratio of each material in each organic layer is not particularly limited, and those skilled in the art can reasonably select the material within a certain range according to the prior art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, an evaporator manufactured by Angstrom Engineering, an optical test system manufactured by Fushida, Suzhou, an ellipsometer manufactured by Beijing Mass., etc.) in a manner well known to those skilled in the art. Since the relevant contents of the above-mentioned device usage, testing method, etc. are known to those skilled in the art, the inherent data of the sample can be obtained with certainty and without being affected, and therefore, the relevant contents are not described in detail in this patent.
Device embodiments
Example 1-1: and preparing the fluorescent organic electroluminescent device.
First, a 0.7mm thick glass substrate is used with a pre-patterned layer thereon
Figure BDA0003398928070000363
Thick Indium Tin Oxide (ITO) was used as the anode and the ITO surface was treated with oxygen plasma and UV ozone after washing the substrate with deionized water and detergent. The substrate was then dried in a glove box to remove moisture and loaded onto a rack into a vacuum chamber. The organic layer specified below was in a vacuum of about 10 degrees -6 In the case of Torr
Figure BDA0003398928070000364
The evaporation is carried out on the anode layer in sequence by vacuum thermal evaporation: first, compound II-130 and compound 70 were simultaneously evaporated as a hole injection layer (HIL, 99:1,
Figure BDA0003398928070000367
) The evaporated compound II-130 was used as a hole transport layer (HTL,
Figure BDA0003398928070000365
) Next, compound EB1 was evaporated to serve as an electron blocking layer (EBL,
Figure BDA0003398928070000368
) On which a compound BH and a compound BD are simultaneously evaporated as a light emitting layer (EML, 96:4,
Figure BDA0003398928070000366
) The compound HB1 was deposited as a hole blocking layer (HBL,
Figure BDA00033989280700003711
) The compounds ET and Liq were co-deposited as electron transport layers (ETL, 40:60,
Figure BDA00033989280700003712
) Vapor deposition of
Figure BDA0003398928070000373
Liq in thickness as an Electron Injection Layer (EIL). Finally, metal aluminum is evaporated as a Cathode (Cathode,
Figure BDA0003398928070000375
). The device was then transferred back to the glove box and encapsulated with a glass cover to complete the device.
Examples 1 to 2: the same procedure as in example 1-1 was conducted, except that the compound II-7 and the compound 70 were evaporated as a hole injection layer (HIL, 99:1,
Figure BDA0003398928070000372
) And the evaporated compound II-7 was used as a hole transport layer (HTL,
Figure BDA0003398928070000374
)。
comparative example 1-1: the same preparation method as in example 1-1 was performed except that compound HT and compound 70 were evaporated as a hole injection layer (HIL, 99:1,
Figure BDA0003398928070000377
) And an evaporation compound HT as a hole transport layer (HTL,
Figure BDA0003398928070000376
)。
comparative examples 1 to 2: the same preparation method as in example 1-1 was conducted except that the compound II-130 and the compound PD-1 were evaporated as a hole injection layer (HIL, 99:1,
Figure BDA0003398928070000378
)。
comparative examples 1 to 3: the same preparation method as that of example 1-2 was used except that evaporation was combinedThe compound II-7 and the compound PD-1 were used as a hole injection layer (HIL, 99:1,
Figure BDA00033989280700003710
)。
comparative examples 1 to 4: the same procedure as in comparative example 1-1 was conducted except that the compound HT and the compound PD-1 were evaporated as a hole injection layer (HIL, 99:1,
Figure BDA0003398928070000379
)。
the detailed device layer structure and thickness are shown in the table below. Wherein more than one layer of the materials used is obtained by doping different compounds in the stated weight ratios.
TABLE 1 device structures of organic layer portions of examples 1-1 to 1-2 and comparative examples 1-1 to 1-4
Figure BDA0003398928070000371
The structure of the materials used in the device is as follows:
Figure BDA0003398928070000381
table 2 shows device properties of examples 1-1 to 1-2 and comparative examples 1-1 to 1-4. Wherein the color Coordinate (CIE), voltage, and Power Efficiency (PE) are measured at a current density of 10mA/cm 2 The device lifetime (LT95) was measured at 80mA/cm 2 The luminance decays to 95% of the original luminance under the constant current drive of (1).
TABLE 2 device Performance of examples 1-1 to 1-2 and comparative examples 1-1 to 1-4
Device numbering CIEx CIEy Voltage (V) PE(lm/W) LT95(h)
Examples 1 to 1 0.141 0.104 4.1 4.3 112
Examples 1 to 2 0.140 0.105 4.0 4.8 85
Comparative example 1-1 0.140 0.094 4.9 3.6 102
Comparative examples 1 to 2 0.141 0.110 10.5 2.2 3
Comparative examples 1 to 3 0.141 0.105 8.4 3.0 1
Comparative examples 1 to 4 0.140 0.094 12.8 1.7 19
As can be seen from the data in Table 2, the color coordinates of the examples substantially agree with those of the comparative examples.
Compared with comparative example 1-1, the voltage of example 1-1 was reduced by 0.8V, the power efficiency was improved by 0.7lm/W, and the lifetime was further significantly improved by almost 10% at the very high lifetime level of comparative example 1-1, which is very rare. Compared with comparative example 1-2, the voltage of example 1-1 was greatly reduced by 6.4V, the power efficiency was improved by 2.1lm/W, and the lifetime was greatly improved by 36 times. Compared with comparative examples 1-4, the voltage of example 1-1 was greatly reduced by 8.7V, the power efficiency was improved by 2.6lm/W, and the lifetime was greatly improved by 5 times.
The voltage of example 1-2 was lowered by 0.9V, the power efficiency was improved by 1.2lm/W, and the lifetime was lowered relative to that of comparative example 1-1, but the lifetime data of example 1-2 was still at a very high level in the industry. Compared with comparative examples 1-3, the voltage of examples 1-2 was greatly reduced by 4.4V, the power efficiency was improved by 1.8lm/W, and the lifetime was greatly improved by 84 times. Compared with comparative examples 1-4, the voltage of examples 1-2 was greatly reduced by 8.8V, the power efficiency was improved by 3.1lm/W, and the lifetime was greatly improved by 3.5 times.
From the comparison, when the combination of the first compound and the second compound selected by the invention is used in a fluorescent organic electroluminescent device, the organic electroluminescent device can obtain lower voltage, higher efficiency and longer service life, and the combination of the first compound and the second compound selected by the invention is proved to have excellent performance and wide application prospect.
Example 2-1: and preparing the phosphorescent organic electroluminescent device.
First, a 0.7mm thick glass substrate is used with a pre-patterned layer thereon
Figure BDA0003398928070000395
Thick Indium Tin Oxide (ITO) was used as the anode and the ITO surface was treated with oxygen plasma and UV ozone after washing the substrate with deionized water and detergent water. The substrate was then dried in a glove box to remove moisture and loaded onto a rack into a vacuum chamber. The organic layer specified below was in a vacuum of about 10 degrees -6 In the case of Torr
Figure BDA0003398928070000394
The evaporation is carried out on the anode layer in sequence by vacuum thermal evaporation: first, compound II-130 and compound 70 were simultaneously evaporated as a hole injection layer (HIL, 99:1,
Figure BDA0003398928070000392
) The evaporated compound II-130 was used as a hole transport layer (HTL,
Figure BDA0003398928070000393
) Next, compound EB2 was evaporated to serve as an electron blocking layer (EBL,
Figure BDA00033989280700003915
) On which a compound RH and a compound RD are simultaneously evaporated as a light emitting layer (EML, 98:2,
Figure BDA00033989280700003918
) The compound HB2 was deposited as a hole blocking layer (HBL,
Figure BDA00033989280700003917
) The compounds ET and Liq were co-deposited as electron transport layers (ETL, 40:60,
Figure BDA00033989280700003914
) Vapor deposition of
Figure BDA00033989280700003916
Liq in thickness as an Electron Injection Layer (EIL). Finally, metal aluminum is evaporated as a Cathode (Cathode,
Figure BDA00033989280700003913
). The device was then transferred back to the glove box and encapsulated with a glass cover to complete the device.
Example 2-2: the same preparation method as in example 2-1 was conducted except that the compound II-7 and the compound 70 were evaporated as a hole injection layer (HIL, 99:1,
Figure BDA0003398928070000399
) And the evaporated compound II-7 was used as a hole transport layer (HTL,
Figure BDA0003398928070000396
)。
comparative example 2-1: the same preparation method as in example 2-1 was performed except that compound HT and compound 70 were evaporated as a hole injection layer (HIL, 99:1,
Figure BDA0003398928070000398
) And an evaporation compound HT as a hole transport layer (HTL,
Figure BDA0003398928070000397
)。
comparative example 2-2: the same preparation method as in example 2-1 was conducted except that the compound II-130 and the compound PD-1 were evaporated as a hole injection layer (HIL, 99:1,
Figure BDA00033989280700003910
)。
comparative examples 2 to 3: example 2-2, except that the compound II-7 and the compound PD-1 were evaporated as a hole injection layer (HIL, 99:1,
Figure BDA00033989280700003911
)。
comparative examples 2 to 4: the same procedure as in comparative example 2-1 was followed, except that the compound HT and the compound PD-1 were evaporated as a hole injection layer (HIL, 99:1,
Figure BDA00033989280700003912
)。
the detailed device layer structure and thickness are shown in the table below. Wherein more than one layer of the materials used is obtained by doping different compounds in the stated weight ratios.
TABLE 3 device structures of organic layer portions of examples 2-1 to 2-2 and comparative examples 2-1 to 2-4
Figure BDA0003398928070000391
Figure BDA0003398928070000401
The structure of the new materials used in the device is as follows:
Figure BDA0003398928070000402
table 4 shows device properties of examples 2-1 to 2-2 and comparative examples 2-1 to 2-4. Wherein the color Coordinate (CIE), voltage, and Power Efficiency (PE) are measured at a current density of 10mA/cm 2 The device lifetime (LT95) was measured at 80mA/cm 2 The luminance decays to 95% of the original luminance under the constant current drive of (1).
TABLE 4 device Performance of examples 2-1 to 2-2 and comparative examples 2-1 to 2-4
Device numbering CIEx CIEy Voltage (V) PE(lm/W) LT95(h)
Example 2-1 0.681 0.318 4.5 14.7 132
Examples 2 to 2 0.680 0.318 4.3 15.2 131
Comparative example 2-1 0.681 0.318 6.4 11.4 81
Comparative examples 2 to 2 0.679 0.319 14.6 6.8 20
Comparative examples 2 to 3 0.678 0.320 12.8 7.4 65
Comparative examples 2 to 4 0.678 0.320 25.9 3.1 1
Compared with comparative example 2-1, the voltage of example 2-1 was reduced by 1.9V, the power efficiency was improved by 3.3lm/W, and the lifetime was improved by 0.6 times. Compared with comparative example 2-2, the voltage of example 2-1 was greatly reduced by 10.1V, the power efficiency was improved by 7.9lm/W, and the lifetime was greatly improved by 5.6 times. Compared with comparative example 2-4, the voltage of example 2-1 is greatly reduced by 21.4V, the power efficiency is improved by 11.6lm/W, and the service life is greatly improved by 131 times.
Compared with comparative example 2-1, the voltage of example 2-2 was reduced by 2.1V, the power efficiency was improved by 3.8lm/W, and the lifetime was improved by 0.6 times. Compared with comparative example 2-3, the voltage of example 2-2 is greatly reduced by 8.5V, the power efficiency is improved by 7.8lm/W, and the service life is improved by 1 time. Compared with comparative examples 2-4, the voltage of example 2-2 was greatly reduced by 21.6V, the power efficiency was improved by 12.1lm/W, and the lifetime was greatly improved by 130 times.
From the comparison, when the combination of the first compound and the second compound selected by the invention is used in a phosphorescent organic electroluminescent device, the organic electroluminescent device can obtain lower voltage, higher efficiency and longer service life, and the combination of the first compound and the second compound selected by the invention is proved to have excellent performance and wide application prospect.
In conclusion, the material combination of the first compound and the second compound selected by the invention can realize excellent effects of reducing voltage, improving efficiency and greatly improving or maintaining high-level device service life in both fluorescent organic electroluminescent devices and phosphorescent organic electroluminescent devices, and indicates wide application prospects in commercial application.
It should be understood that the various embodiments described herein are illustrative only and are not intended to limit the scope of the invention. Thus, the invention as claimed may include variations from the specific embodiments and preferred embodiments described herein, as will be apparent to those skilled in the art. Many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present invention. It should be understood that various theories as to why the invention works are not intended to be limiting.

Claims (26)

1. An organic electroluminescent device, comprising:
an anode, a cathode, a anode and a cathode,
a cathode electrode, which is provided with a cathode,
and a first organic layer disposed between the anode and the cathode, wherein the first organic layer includes at least a first compound and a second compound, wherein the first compound has a structure represented by formula 1:
Figure FDA0003398928060000011
in the case of the formula 1, the compound,
x and Y are, identically or differently on each occurrence, selected from NR ', CR "R'", O, S or Se;
Z 1 and Z 2 Identically or differently on each occurrence is selected from O, S or Se;
R，r ', R "and R'" are selected, identically or differently on each occurrence, from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF 5 A boryl group, a sulfinyl group, a sulfonyl group, a phosphinyloxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, and combinations thereof;
each R may be the same or different and at least one of R, R ', R "and R'" is a group having at least one electron withdrawing group;
adjacent substituents in formula 1 can optionally be linked to form a ring;
the second compound has a structure represented by formula 2:
Figure FDA0003398928060000012
in the case of the formula 2, the reaction mixture,
X 1 to X 8 Selected from C, CR, the same or different at each occurrence 1 Or N; x 9 To X 18 Is selected, identically or differently on each occurrence, from CR 1 Or N;
q is selected from C, Si or Ge;
L 1 to L 3 Each occurrence being the same or different and selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted arylene group having 3 to 30 carbon atomsHeteroaryl, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3-20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring.
2. The organic electroluminescent device of claim 1, wherein in formula 1, X and Y are selected, identically or differently on each occurrence, from CR "R '" or NR ', R "and R '" are groups having at least one electron-withdrawing group; preferably, R ', R "and R'" are groups having at least one electron withdrawing group.
3. The organic electroluminescent device of claim 1, wherein in formula 1, X and Y are selected, identically or differently on each occurrence, from O, S or Se, at least one of R being a group having at least one electron-withdrawing group; preferably, each R is a group having at least one electron withdrawing group.
4. An organic electroluminescent device as claimed in any one of claims 1 to 3, wherein the Hammett constant of the electron-withdrawing group is ≥ 0.05, preferably ≥ 0.3, more preferably ≥ 0.5.
5. The organic electroluminescent device of any one of claims 1 to 4, wherein the electron-withdrawing group is selected from the group consisting of: halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 Boryl, sulfinyl, sulfonyl, phosphinoxy, azaaryl, and substituted with halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 Boryl, sulfinyl, sulfonyl, phosphinoxy, an azaaryl group, substituted with one or more of any of the following: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;
preferably, the electron withdrawing group is selected from the group consisting of: f, CF 3 ，OCF 3 ，SF 5 ，SO 2 CF 3 Cyano, isocyano, SCN, OCN, pyrimidinyl, triazinyl, and combinations thereof.
6. The organic electroluminescent device of any one of claims 1,4 and 5, wherein X and Y, the same or different at each occurrence, are selected from the group consisting of:
O，S，Se，
Figure FDA0003398928060000021
Figure FDA0003398928060000022
Figure FDA0003398928060000031
R 2 the same or different at each occurrence is selected from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF 5 A boryl group, a sulfinyl group, a sulfonyl group, a phosphinyloxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6-20 carbon atoms, and combinations thereof;
preferably, R 2 The same or different at each occurrence is selected from the group consisting of: f, CF 3 ，OCF 3 ，SF 5 ，SO 2 CF 3 Cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazinyl, and combinations thereof;
v and W are selected, identically or differently on each occurrence, from CR v R w ，NR v O, S or Se;
ar is the same or different at each occurrence and is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;
A，R a ，R b ，R c ，R d ，R e ，R f ，R g ，R h ，R v and R w The same or different at each occurrence is selected from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF 5 A boryl group, a sulfinyl group, a sulfonyl group, a phosphinyloxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, and combinations thereof;
a is a group having at least one electron withdrawing group, and for either structure, when R a ，R b ，R c ，R d ，R e ，R f ，R g ，R h ，R v And R w When one or more of them occur, R a ，R b ，R c ，R d ，R e ，R f ，R g ，R h ，R v And R w At least one of which is a group having at least one electron-withdrawing group; preferably, the device has at least one pull-upThe group of the child group is selected from the group consisting of: f, CF 3 ，OCF 3 ，SF 5 ，SO 2 CF 3 Cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazinyl, and combinations thereof;
preferably, wherein X and Y are, identically or differently on each occurrence, selected from the group consisting of:
O，S，Se，
Figure FDA0003398928060000041
Figure FDA0003398928060000042
"" denotes a position in said X and Y to which a dehydrobenzodioxazole ring, a dehydrobenzodithiazole ring or a dehydrobenzodiselenazole ring in said formula 1 is bonded.
7. The organic electroluminescent device of any one of claims 1 to 6, wherein R, identically or differently at each occurrence, is selected from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 Boryl, sulfinyl, sulfonyl, phosphinoxy, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, and substituted with halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF 5 Any of the following substituted with one or more of boryl, sulfinyl, sulfonyl and phosphinyl: alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 ring carbon atoms, alkoxy having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 30 carbon atoms, heteroaryl having 3 to 30 carbon atomsAnd combinations thereof;
preferably, R is selected, identically or differently on each occurrence, from the group consisting of: hydrogen, deuterium, methyl, isopropyl, NO 2 ，SO 2 CH 3 ，SCF 3 ，C 2 F 5 ，OC 2 F 5 ，OCH 3 Diphenylmethylsilyl, phenyl, methoxyphenyl, p-methylphenyl, 2, 6-diisopropylphenyl, biphenyl, polyfluorophenyl, difluoropyridyl, nitrophenyl, dimethylthiazolyl, optionally substituted with CN or CF 3 By CN or CF 3 Substituted ethynyl, dimethylphosphinoxy, diphenylphosphinoxy, F, CF 3 ，OCF 3 ，SF 5 ，SO 2 CF 3 Cyano, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis (trifluoromethyl) phenyl, bis (trifluoromethoxy) phenyl, 4-cyanotetrafluorophenyl, by F, CN or CF 3 One or more substituted phenyl or biphenyl groups of (a), a tetrafluoropyridyl group, a pyrimidinyl group, a triazinyl group, a diphenylboryl group, a oxaboro-anthracenyl group, and combinations thereof.
8. The organic electroluminescent device as claimed in claim 7, wherein X and Y are
Figure FDA0003398928060000051
9. The organic electroluminescent device of any one of claims 1 to 8, wherein R is selected, identically or differently at each occurrence, from the group consisting of:
Figure FDA0003398928060000052
Figure FDA0003398928060000061
preferably, two R are the same in one first compound represented by formula 1;
Figure FDA0003398928060000062
represents a position where the R group is attached to a dehydrobenzodioxazole ring, a dehydrobenzodithiazole ring or a dehydrobenzodiselenazole ring in formula 1.
10. The organic electroluminescent device according to claim 9, wherein the first compound is selected from the group consisting of compound 1 to compound 1356; the compounds 1 to 1356 have the structures represented by formula 1-1:
Figure FDA0003398928060000063
wherein, two Z are the same, and the Z, X, Y, R respectively correspond to atoms or groups selected from the group shown in the following table:
Figure FDA0003398928060000071
Figure FDA0003398928060000081
Figure FDA0003398928060000091
Figure FDA0003398928060000101
Figure FDA0003398928060000111
Figure FDA0003398928060000121
Figure FDA0003398928060000131
Figure FDA0003398928060000141
Figure FDA0003398928060000151
Figure FDA0003398928060000161
Figure FDA0003398928060000171
Figure FDA0003398928060000181
Figure FDA0003398928060000191
Figure FDA0003398928060000201
11. the organic electroluminescent device according to any one of claims 1 to 10, wherein the second compound has a structure represented by any one of formulae 2-1 to 2-12:
Figure FDA0003398928060000202
X 1 to X 18 Selected from CR, identically or differently at each occurrence 1 ；
L 1 To L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring;
preferably, the second compound has a structure represented by formula 2-1, formula 2-2, formula 2-3, formula 2-4, formula 2-6, or formula 2-10.
12. The organic electroluminescent device as claimed in any one of claims 1 to 10, wherein, in formula 2, X 1 To X 18 At least one of which is N.
13. The organic electroluminescent device according to any one of claims 1 to 10, wherein the second compound has a structure represented by any one of formulae 2 to 13 to formulae 2 to 24:
Figure FDA0003398928060000211
Figure FDA0003398928060000221
X 1 to X 18 Selected from CR, identically or differently at each occurrence 1 Or N;
L 1 to L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atomsA substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring;
preferably, the second compound has a structure represented by formula 2-13, formula 2-14, formula 2-15, formula 2-16, formula 2-18, or formula 2-22.
14. The organic electroluminescent device of any one of claims 1 to 13, wherein L is 1 To L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 24 carbon atoms, or a combination thereof;
preferably, L 1 To L 3 Each occurrence being the same or different and is selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted silafluorenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted diglycylidene groupA benzofuranyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dibenzoselenophenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted spirobifluorenylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted pyrenylene group, or a combination thereof;
more preferably, L 1 To L 3 Each occurrence, the same or different, is selected from the group consisting of:
Figure FDA0003398928060000231
Figure FDA0003398928060000232
"" denotes a position bonded to the nitrogen in formula 2 in the L-1 to L-13, and a dotted line denotes X in formula 2 in the L-1 to L-13 1 To X 8 Any one of, Ar 1 Or Ar 2 The location of the connection.
15. The organic electroluminescent device as claimed in any one of claims 1 to 14, Ar 1 And Ar 2 Each occurrence, the same or different, has a structure represented by any one of formulas 3-1 to 3-4:
Figure FDA0003398928060000233
e is selected, identically or differently on each occurrence, from O, S, Se, C (R) 4 ) 2 ，Si(R 4 ) 2 Or Ge (R) 4 ) 2 ；
R 3 The same or different at each occurrence denotes mono-, poly-or unsubstituted;
R 3 and R 4 Each occurrence, the same or different, is selected from the group consisting of: hydrogenDeuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents R 3 ，R 4 Can optionally be linked to form a ring;
preferably, R 3 And R 4 Each occurrence, identically or differently, is selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, or a combination thereof;
dotted line represents said Ar 1 In the structure of (1) with the L 1 The location of the connection; the dotted line also represents said Ar 2 In the structure of (1) with the L 2 The location of the connection.
16. The organic electroluminescent device as claimed in claim 15, wherein Ar is Ar 1 And Ar 2 Each occurrence, identically or differently, is selected from the group consisting of G1 to G37:
Figure FDA0003398928060000241
Figure FDA0003398928060000251
R 4 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3-20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents R 4 Can optionally be linked to form a ring;
preferably, R 4 Each occurrence, the same or different, is selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a combination thereof;
more preferably, R 4 Each occurrence, identically or differently, is selected from hydrogen, deuterium, methyl, ethyl, isopropyl, fluorene,phenyl, biphenyl, naphthyl, or combinations thereof.
17. The organic electroluminescent device as claimed in any one of claims 1 to 16, wherein R is 1 Each occurrence, identically or differently, is selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, or a combination thereof;
preferably, R 1 Each occurrence is selected, identically or differently, from hydrogen, deuterium, fluoro, methyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, or combinations thereof.
18. The organic electroluminescent device of any one of claims 1 to 17, wherein the Ar in the second compound 1 And Ar 2 Are connected to form a ring;
preferably, L 1 And L 2 Is a single bond;
more preferably, the second compound has a structure represented by formulae 2 to 25:
Figure FDA0003398928060000252
X 1 to X 8 Selected from C, CR, the same or different at each occurrence 1 Or N;
X 9 to X 18 Selected from CR, identically or differently at each occurrence 1 Or N;
q is selected at each occurrence from C, Si or Ge;
t is selected, identically or differently on each occurrence, from CR 5 ’R 5 ', O, S or NR 5 ’；
R 5 The same or different at each occurrence denotes mono-, poly-or unsubstituted;
R 5 and R 5 ' each occurrence is the same or different and is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
L 3 each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
adjacent substituents R 1 ，R 5 And R 5 ' can optionally be linked to form a ring.
19. The organic electroluminescent device of any one of claims 1 to 18, wherein the second compound is selected from compound I-1 to compound I-273, compound II-1 to compound II-332, compound III-1 to compound III-273, compound IV-1 to compound IV-273, compound V-1 to compound V-273, compound VI-1 to compound VI-273, compound VII-1 to compound VII-273, compound VIII-1 to compound VIII-273, compound IX-1 to compound IX-273, or compound X-1 to compound X-273;
wherein, the compounds I-1 to I-273 have the structures represented by the formulae 2 to 13:
Figure FDA0003398928060000261
in formulae 2 to 13, X 1 To X 7 、X 9 To X 12 And X 15 To X 18 Are all CH, L 1 And L 2 Are all single bonds, and L 3 ，Ar 1 And Ar 2 Each corresponding to an atom or group selected from the following table:
Figure FDA0003398928060000262
Figure FDA0003398928060000271
Figure FDA0003398928060000281
Figure FDA0003398928060000291
the compounds II-1 to II-332 are shown below:
Figure FDA0003398928060000292
Figure FDA0003398928060000301
Figure FDA0003398928060000311
Figure FDA0003398928060000321
Figure FDA0003398928060000331
Figure FDA0003398928060000341
Figure FDA0003398928060000351
Figure FDA0003398928060000361
Figure FDA0003398928060000371
Figure FDA0003398928060000381
Figure FDA0003398928060000391
Figure FDA0003398928060000401
Figure FDA0003398928060000411
Figure FDA0003398928060000421
Figure FDA0003398928060000431
Figure FDA0003398928060000441
Figure FDA0003398928060000451
Figure FDA0003398928060000461
Figure FDA0003398928060000471
Figure FDA0003398928060000481
in the structures of the compound II-1 to the compound II-332, Ph represents a phenyl group;
wherein compounds III-1 through III-273 have structures represented by formulas 2-15:
Figure FDA0003398928060000482
in formulae 2 to 15, X 1 To X 5 、X 7 To X 12 And X 15 To X 18 Are all CH, L 1 And L 2 Are all single bonds, and L 3 ，Ar 1 And Ar 2 Each corresponding to an atom or group selected from the following table:
Figure FDA0003398928060000483
Figure FDA0003398928060000491
Figure FDA0003398928060000501
Figure FDA0003398928060000511
wherein the compounds IV-1 to IV-273 have the structures represented by the formulae 2 to 16:
Figure FDA0003398928060000512
in formulae 2 to 16, X 1 To X 4 、X 6 To X 12 And X 15 To X 18 Are all CH, L 1 And L 2 Are all single bonds, and L 3 ，Ar 1 And Ar 2 Each corresponding to an atom or group selected from the following table:
Figure FDA0003398928060000513
Figure FDA0003398928060000521
Figure FDA0003398928060000531
Figure FDA0003398928060000541
wherein the compound V-1 to the compound V-273 have a structure represented by formula 2-1:
Figure FDA0003398928060000542
in the formula 2-1, X 1 To X 7 、X 9 To X 18 Are all CH, L 1 And L 2 Are all single bonds, and L 3 ，Ar 1 And Ar 2 Each corresponding to an atom or group selected from the following table:
Figure FDA0003398928060000543
Figure FDA0003398928060000551
Figure FDA0003398928060000561
wherein compounds VI-1 through VI-273 have the structures represented by formula 2-2:
Figure FDA0003398928060000571
in the formula 2-2, X 1 To X 6 、X 8 To X 18 Are all CH, L 1 And L 2 Are all single bonds, and L 3 ，Ar 1 And Ar 2 Each corresponding to an atom or group selected from the following table:
Figure FDA0003398928060000572
Figure FDA0003398928060000581
Figure FDA0003398928060000591
wherein compounds VII-1 through VII-273 have structures represented by formulas 2-3:
Figure FDA0003398928060000601
in formula 2-3, X 1 To X 5 、X 7 To X 18 Are all CH, L 1 And L 2 Are all single bonds, and L 3 ，Ar 1 And Ar 2 Each corresponding to an atom or group selected from the following table:
Figure FDA0003398928060000602
Figure FDA0003398928060000611
Figure FDA0003398928060000621
wherein the compound VIII-1 to the compound VIII-273 have a structure represented by the formula 2-4:
Figure FDA0003398928060000631
in the formulae 2-4, X 1 To X 4 、X 6 To X 18 Are all CH, L 1 And L 2 Are all single bonds, and L 3 ，Ar 1 And Ar 2 Each corresponding to an atom or group selected from the following table:
Figure FDA0003398928060000632
Figure FDA0003398928060000641
Figure FDA0003398928060000651
wherein compound IX-1 through compound IX-273 have structures represented by formulas 2-6:
Figure FDA0003398928060000661
in the formulae 2 to 6, X 1 To X 6 、X 8 To X 18 Are all CH, L 1 And L 2 Are all single bonds, and L 3 ，Ar 1 And Ar 2 Each corresponding to an atom or group selected from the following table:
Figure FDA0003398928060000662
Figure FDA0003398928060000671
Figure FDA0003398928060000681
wherein the compound X-1 to the compound X-273 have a structure represented by formula 2-10:
Figure FDA0003398928060000691
in the formula 2-10, X 1 To X 6 、X 8 To X 18 Are all CH, L 1 And L 2 Are all single bonds, and L 3 ，Ar 1 And Ar 2 Each corresponding to an atom or group selected from the following table:
Figure FDA0003398928060000692
Figure FDA0003398928060000701
Figure FDA0003398928060000711
20. the organic electroluminescent device of any one of claims 1 to 19, wherein the first organic layer is a hole injection layer, and the hole injection layer is in contact with an anode.
21. The organic electroluminescent device of any one of claims 1 to 20, wherein the organic electroluminescent device further comprises at least one light-emitting layer; preferably, the at least one light emitting layer comprises at least one host material and at least one dopant material;
more preferably, the maximum emission wavelength of the organic electroluminescent device is between 300 and 1200 nm.
22. The organic electroluminescent device of claim 21, wherein the organic electroluminescent device further comprises a second organic layer disposed between the first organic layer and the at least one light emitting layer;
preferably, the second organic layer comprises a compound comprising any one or more of the following chemical building blocks selected from the group consisting of: triarylamines, carbazoles, fluorenes, spirobifluorenes, thiophenes, furans, phenyls, oligophenylethylenes, oligofluorenes, and combinations thereof;
more preferably, the one compound in the second organic layer is the second compound.
23. The organic electroluminescent device of claim 22, wherein the organic electroluminescent device further comprises a third organic layer disposed between the second organic layer and the light emitting layer;
preferably, the third organic layer comprises another compound comprising any one or more chemical building blocks selected from the group consisting of: triarylamines, carbazoles, fluorenes, spirobifluorenes, thiophenes, furans, phenyls, oligophenylenes, oligofluorenes, and combinations thereof;
more preferably, the other compound in the third organic layer is the second compound.
24. The organic electroluminescent device of claim 22, wherein the first organic layer has a thickness between 0.1nm and 40nm and the second organic layer has a thickness between 0.1nm and 300 nm.
25. A display assembly comprising the organic electroluminescent device of any one of claims 1 to 24.
26. A combination of compounds comprising a first compound and a second compound, wherein the first compound has a structure represented by formula 1:
Figure FDA0003398928060000721
in the case of the formula 1, the compound,
x and Y are, identically or differently on each occurrence, selected from NR ', CR "R'", O, S or Se;
Z 1 and Z 2 Identically or differently on each occurrence is selected from O, S or Se;
r, R ', R "and R'" are, identically or differently at each occurrence, selected from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF 5 A boryl group, a sulfinyl group, a sulfonyl group, a phosphinyloxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, and combinations thereof;
each R may be the same or different and at least one of R, R ', R "and R'" is a group having at least one electron withdrawing group;
adjacent substituents in formula 1 can optionally be linked to form a ring;
the second compound has a structure represented by formula 2:
Figure FDA0003398928060000731
in the formula 2, the first and second groups,
X 1 to X 8 Selected from C, CR, the same or different at each occurrence 1 Or N; x 9 To X 18 Selected from CR, identically or differently at each occurrence 1 Or N;
q is selected from C, Si or Ge;
L 1 to L 3 Each occurrence, the same or different, is selected from a single bond, a substituted or unsubstituted arylene having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene having 3 to 30 carbon atoms, or a combination thereof;
Ar 1 and Ar 2 Each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R 1 each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl group having 6 to 20 carbon atomsAn arylsilyl group, a substituted or unsubstituted alkylgermyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents L 1 ，L 2 ，L 3 ，R 1 ，Ar 1 And Ar 2 Can optionally be linked to form a ring.
CN202111488167.3A 2021-02-06 2021-12-08 Organic electroluminescent device Pending CN114914372A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US17/649,874 US20220359832A1 (en) 2021-02-06 2022-02-03 Organic electroluminescent device
JP2022016627A JP7432950B2 (en) 2021-02-06 2022-02-04 organic electroluminescent device
DE102022102796.1A DE102022102796B4 (en) 2021-02-06 2022-02-07 Organic electroluminescent device, display arrangement comprising the same and connection combination
KR1020220015428A KR20220113876A (en) 2021-02-06 2022-02-07 Organic electroluminescent device
JP2023123641A JP2023153909A (en) 2021-02-06 2023-07-28 Organic electroluminescent element

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110165072 2021-02-06
CN2021101650721 2021-02-06

Publications (1)

Publication Number Publication Date
CN114914372A true CN114914372A (en) 2022-08-16

Family

ID=82763231

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111488167.3A Pending CN114914372A (en) 2021-02-06 2021-12-08 Organic electroluminescent device

Country Status (1)

Country Link
CN (1) CN114914372A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115490704A (en) * 2021-11-25 2022-12-20 北京夏禾科技有限公司 Organic electroluminescent materials and devices
CN116589365A (en) * 2023-04-07 2023-08-15 南京高光半导体材料有限公司 Amino compound and organic electroluminescent device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115490704A (en) * 2021-11-25 2022-12-20 北京夏禾科技有限公司 Organic electroluminescent materials and devices
CN115490704B (en) * 2021-11-25 2023-10-31 北京夏禾科技有限公司 Organic electroluminescent material and device
CN116589365A (en) * 2023-04-07 2023-08-15 南京高光半导体材料有限公司 Amino compound and organic electroluminescent device

Similar Documents

Publication Publication Date Title
CN112778283A (en) Organic electroluminescent material and device thereof
CN115073501A (en) Organic electroluminescent material and device thereof
CN114605473A (en) Phosphorescent organic metal complex and device thereof
CN113968875A (en) Electroluminescent material and device
CN114914372A (en) Organic electroluminescent device
JP2023153909A (en) Organic electroluminescent element
CN114057797A (en) Metal complex, electroluminescent device and application thereof
CN114516890A (en) Organic electroluminescent material and device thereof
CN114524850A (en) Organic electroluminescent material and device thereof
CN114835718A (en) Organic electroluminescent material and device thereof
CN114256430A (en) Electroluminescent device
CN115403628A (en) Organic electroluminescent material and device thereof
CN114613924A (en) Electroluminescent device
CN114075208A (en) Electroluminescent material and device
US20240065100A1 (en) Organic electroluminescent device
US20230309394A1 (en) Organic electroluminescent device
CN115666151A (en) Novel organic electroluminescent device
CN115734641A (en) Organic electroluminescent device
CN115915885A (en) Organic electroluminescent device
CN115472756A (en) Organic electroluminescent device
CN113809243A (en) Organic electroluminescent device
CN113809242A (en) Organic electroluminescent device
CN114628601A (en) Organic electroluminescent device
CN115942851A (en) Organic electroluminescent device
CN114591341A (en) Electroluminescent material and device 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