CN111018854B

CN111018854B - Compound, organic electroluminescent device, and electronic device

Info

Publication number: CN111018854B
Application number: CN201911349119.9A
Authority: CN
Inventors: 陈志伟; 薛震; 王金平
Original assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Current assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Priority date: 2019-12-24
Filing date: 2019-12-24
Publication date: 2021-01-05
Anticipated expiration: 2039-12-24
Also published as: CN111018854A

Abstract

The present application belongs to the technical field of OLEDs and provides a compound having the structure of formula 1: wherein, X₁、X₂、X₃Is C or N, and X₁、X₂、X₃At least one is N; x₄、X₅、X₆Is C or N, and X₄、X₅、X₆Only one N; l is₁And L₂Each independently selected from the group consisting of a single bond, C1-C20 alkylene, C6-C30 arylene, C3-C30 heteroarylene, C3-C20 cycloalkylene; ar (Ar)₁And Ar₂Each independently selected from C1-C20 alkyl, C-C20 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, Si (R)₁R₂R₃). The present application provides phenanthrene-based fused ring compounds, the molecules of which have strong planar ductility. The strong plane ductility of the compound molecules can enhance the rigidity of the material and prolong the service life of the material. In addition, the molecular parent nucleus and the aryl substituent group easily form a large conjugated system, a plurality of nitrogen atom centers exist at the same time, the density of electron clouds in the molecule is increased, the electron mobility and the transition rate can be improved, and the organic electroluminescent device has high device efficiency. The application also provides an organic electroluminescent device and an electronic device.

Description

Compound, organic electroluminescent device, and electronic device

Technical Field

The application relates to the technical field of organic materials, in particular to a condensed ring compound, an organic electroluminescent device and an electronic device comprising the compound.

Background

An organic light-emitting diode (oled) is based on the principle that when an electric field is applied between a cathode and an anode, a hole on the anode side and an electron on the cathode side move to a light-emitting layer, and combine to form an exciton in the light-emitting layer, the exciton is in an excited state and releases energy outwards, and the process of releasing energy from the excited state to a ground state releases energy emits light outwards. Since Kodak corporation reports electroluminescence of organic molecules in 1987 and Cambridge university in England reports electroluminescence of polymers in 1990, various countries in the world have developed research and development. The material has the advantages of simple structure, high yield, low cost, active luminescence, high response speed, high fraction and the like, and has the performances of low driving voltage, full solid state, no vacuum, oscillation resistance, low temperature (-40 ℃) resistance and the like. In recent years, the OLED material has been widely used in the field of smart phones, is considered as a new technology that is most likely to replace liquid crystal displays in the future, and has attracted great attention.

In order to improve the brightness, efficiency and lifetime of organic electroluminescent devices, multilayer structures are commonly used in organic electroluminescent devices, which may include one or more of the following film layers: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an electron-blocking layer (EBL), an organic electroluminescent layer (EML), a hole-blocking layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL), etc. The film layers can improve the injection efficiency of carriers (holes and electrons) between interfaces of each layer and balance the capability of the carriers for transmitting between the layers, thereby improving the brightness and the efficiency of the organic electroluminescent device.

Efficient commercial organic light emitting diodes employ phosphors containing organometallic iridium complexes because they can trap both singlet and triplet excitons, thereby achieving 100% internal quantum efficiency. However, since the excited state exciton lifetime of the transition metal complex is relatively too long and concentration quenching effect of the light emitting material is easily generated, the unnecessary triplet-triplet (T1-T1) is quenched in the actual operation of the device, and in order to overcome this problem, researchers often incorporate triplet light emitting objects into organic host materials. Therefore, the research on the organic light emitting guest material is becoming a hot direction in the field of organic light emitting devices.

The information disclosed in the background section is only for enhancement of understanding of the background of the present disclosure and therefore it may contain information that does not constitute prior art that is known to a person of ordinary skill in the art.

Disclosure of Invention

The present application aims to provide a photoelectric material applied to an organic electroluminescent diode (OLED) and an application thereof in an electroluminescent device, so that the photoelectric material has the advantages of excellent photoelectric performance, high efficiency, low driving voltage and long service life.

In order to achieve the purpose, the following technical scheme is adopted in the application.

The present application provides a nitrogen heterocyclic compound having a structure represented by chemical formula 1:

wherein, X₁、X₂、X₃Is C or N, and X₁、X₂、X₃At least one is N;

X₄、X₅、X₆is C or N, and X₄、X₅、X₆One and only one is N;

L₁and L₂Each independently selected from a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms;

Ar₁and Ar₂Each independently selected from the following substituted or unsubstituted groups: alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 3 to 30 carbon atoms, Si (R)₁R₂R₃)；

R₁，R₂，R₃Each independently selected from the following substituted or unsubstituted groups: an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 30 carbon atoms.

The application provides a phenanthrene fused ring derivative as a parent nucleus, and a compound molecule has strong planarity. The strong plane ductility of the compound molecules can enhance the rigidity of the material and prolong the service life of the material. In addition, a large conjugated system is easily formed by the molecular parent nucleus and the aryl/heteroaryl, a plurality of nitrogen atom centers exist at the same time, the density of electron clouds in molecules is increased, the HOMO energy level can be further adjusted to a proper level, the electron mobility and the transition rate are further improved, and the organic electroluminescent device has high device efficiency.

The present application also provides organic electroluminescent devices and electronic devices comprising the compounds described herein.

Drawings

FIG. 1 is a general chemical formula of a compound of the present application;

FIG. 2 is a schematic structural view of one embodiment of an organic electroluminescent device of the present application;

fig. 3 is a schematic view of an electronic device employing the organic electroluminescent device of the present application.

Reference numerals:

100-an anode; 200-a cathode; 300-organic layer; 310-a hole injection layer; 320-a hole transport layer; 330-electron blocking layer; 340-an organic electroluminescent layer; 350-a hole blocking layer; 360-electron transport layer; 370-electron injection layer.

Detailed Description

Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a thorough understanding of embodiments of the application. One skilled in the relevant art will recognize, however, that the subject matter of the present application can be practiced without one or more of the specific details, or with other methods, materials, devices, etc. In other instances, well-known technical solutions have not been shown or described in detail to avoid obscuring aspects of the present application. The same reference numerals in the drawings denote the same or similar structures, and thus their detailed description will be omitted.

Furthermore, the drawings are merely schematic illustrations of the present application and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and thus their repetitive description will be omitted. The terms "a" and "the" are used to indicate the presence of one or more elements/components/etc.; the terms "comprising" and "having" are intended to be inclusive and mean that there may be additional elements/components/etc. other than the listed elements/components/etc.

The technical solution of the present application will be described in detail below.

One aspect of the present application provides a compound having a structure represented by chemical formula 1:

wherein the content of the first and second substances,

X₁、X₂、X₃is C or N, and X₁、X₂、X₃At least one is N;

X₄、X₅、X₆is C or N, and X₄、X₅、X₆One and only one is N;

Said L₁And L₂、Ar₁And Ar₂The substituents are the same or different and are each independently selected from deuterium, a halogen group, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an arylthio group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms and an arylsilyl group having 6 to 24 carbon atoms.

In the present application, L₁、L₂、Ar₁And Ar₂The number of carbon atoms of (b) means all the number of carbon atoms. For example, if L₁Selected from the group consisting of substituted arylene groups having 12 carbon atoms, all of the carbon atoms of the arylene group and the substituents thereon are 12.

In the present application, when a specific definition is not otherwise provided, "hetero" means that at least 1 hetero atom of B, N, O, S or P or the like is included in one functional group and the remaining atoms are carbon and hydrogen. An unsubstituted alkyl group can be a "saturated alkyl group" without any double or triple bonds.

In this application, the terms "optional" or "optionally" mean that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where the event or circumstance occurs or does not. For example, "a heterocyclic group optionally substituted with an alkyl" means that an alkyl may, but need not, be present, and the description includes the scenario where the heterocyclic group is substituted with an alkyl and the scenario where the heterocyclic group is not substituted with an alkyl. "optionally, Re and Rf which are bonded to the same atom may be bonded to each other to form a saturated or unsaturated 5-to 10-membered aliphatic ring" means that Re and Rf which are bonded to the same atom may be, but need not be, a ring, and includes a case where Re and Rf are bonded to each other to form a saturated or unsaturated 5-to 10-membered aliphatic ring, and also includes a case where Re and Rf are present independently of each other.

In the present application, the descriptions "… … is independently" and "… … is independently" and "… … is independently selected from" are interchangeable, and should be understood in a broad sense, which means that the specific items expressed between the same symbols do not affect each other in different groups, or that the specific items expressed between the same symbols do not affect each other in the same groups. For example,') "

Wherein each q is independently 0, 1,2 or 3, each R "is independently selected from hydrogen, deuterium, fluoro, chloro" and has the meaning: the formula Q-1 represents that Q substituent groups R ' are arranged on a benzene ring, each R ' can be the same or different, and the options of each R ' are not influenced mutually; the formula Q-2 represents that each benzene ring of biphenyl has Q substituent groups R ', the number Q of the substituent groups R' on the two benzene rings can be the same or different, each R 'can be the same or different, and the options of each R' are not influenced with each other.

In the present application, the term "substituted or unsubstituted" means either no substituent or substituted with one or more substituents. Such substituents include, but are not limited to, deuterium (D), halogen groups (F, Cl, Br), cyano, alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, aryloxy, arylthio, cycloalkyl, heterocycloalkyl.

In the present application, "alkyl" may include straight chain alkyl or branched alkyl. Alkyl groups may have 1 to 20 carbon atoms, and in the present application, numerical ranges such as "1 to 20" refer to each integer in the given range. For example, "1 to 20 carbon atoms" refers to an alkyl group that may include 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, or 20 carbon atoms. The alkyl group can also be a medium size alkyl group having 1 to 10 carbon atoms. The alkyl group may also be a lower alkyl group having 1 to 6 carbon atoms. Further, the alkyl group may be substituted or unsubstituted.

Preferably, the alkyl group is selected from alkyl groups having 1 to 10 carbon atoms, and specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl.

In the present application, "alkenyl" refers to a hydrocarbon group comprising one or more double bonds in a straight or branched hydrocarbon chain. Alkenyl groups may be unsubstituted or substituted. An alkenyl group can have 1 to 20 carbon atoms, and whenever appearing herein, a numerical range such as "1 to 20" refers to each integer in the given range. For example, "1 to 20 carbon atoms" refers to an alkenyl group that may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, or 20 carbon atoms. For example, the alkenyl group can be vinyl, butadiene, or 1,3, 5-hexatriene.

In the present application, cycloalkyl refers to a saturated hydrocarbon containing an alicyclic structure, including monocyclic and fused ring structures. Cycloalkyl groups may have 3-20 carbon atoms, and numerical ranges such as "3 to 20" refer to each integer in the given range. For example, "3 to 20 carbon atoms" refers to a cycloalkyl group that can include 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, or 20 carbon atoms. The cycloalkyl group may be a small ring, a normal ring or a large ring having 3 to 20 carbon atoms. Cycloalkyl groups can also be divided into monocyclic-only one ring, bicyclic-two rings, polycyclic-three or more rings. Cycloalkyl groups can also be divided into spiro rings, fused rings, and bridged rings, in which two rings share a common carbon atom, and more than two rings share a common carbon atom. In addition, cycloalkyl groups may be substituted or unsubstituted.

Preferably, the cycloalkyl group is selected from cycloalkyl groups having 3 to 10 carbon atoms, and specific examples include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and adamantane.

In the present application, aryl refers to an optional functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group, in other words, the aryl group may be a monocyclic aryl group, a fused ring aryl group, two or more monocyclic aryl groups connected by carbon-carbon bond conjugation, a monocyclic aryl group and a fused ring aryl group connected by carbon-carbon bond conjugation, two or more fused ring aryl groups connected by carbon-carbon bond conjugation. That is, two or more aromatic groups conjugated through a carbon-carbon bond may also be considered as an aryl group in the present application. Wherein the aryl group does not contain a heteroatom such as B, N, O, S or P. For example, biphenyl, terphenyl, and the like are aryl groups in this application. Examples of the aryl group may include phenyl, naphthyl, fluorenyl, anthracyl, phenanthryl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzo [9,10 ]]Phenanthryl, pyrenyl, benzofluoranthenyl, phenanthrenyl, pyrenyl, phenanthrenyl, pyrenyl,

a phenyl group, a fluorenyl group, and the like, without being limited thereto.

In this application, substituted aryl refers to an aryl group in which one or more hydrogen atoms are replaced with another group. For example, at least one hydrogen atom is substituted with deuterium atoms, F, Cl, I, CN, hydroxyl, amino, branched alkyl, straight chain alkyl, cycloalkyl, alkoxy, alkylamino, or other groups. It is understood that a substituted aryl group having 18 carbon atoms refers to an aryl group and the total number of carbon atoms in the substituents on the aryl group being 18. For example, 2, 3-dimethyl-6-phenylnaphthalene has a carbon number of 18, 9, 9-diphenylfluorenyl group of 25. Among them, biphenyl can be interpreted as an aryl group or a substituted phenyl group.

In the present application, the fluorenyl group may be substituted and two substituents may be combined with each other to form a spiro structure, and specific examples include, but are not limited to, the following structures:

in the present application, the heteroaryl group may be a heteroaryl group including at least one of B, O, N, P, Si and S as a heteroatom. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group, in other words, the heteroaryl group may be a single aromatic ring system or a plurality of aromatic ring systems connected by carbon-carbon bonds in a conjugated manner, and any one of the aromatic ring systems is an aromatic monocyclic ring or an aromatic fused ring. For example, heteroaryl groups can include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, N-arylcarbazolyl, N-heteroarylcarbazolyl, N-alkylcarbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuryl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzosilyl, dibenzofuryl, phenyl-substituted dibenzofuryl, Dibenzofuranyl-substituted phenyl groups, and the like, without being limited thereto. Wherein, thienyl, furyl, phenanthroline and the like are heteroaryl of a single aromatic ring system, and N-aryl carbazolyl, N-heteroaryl carbazolyl, phenyl-substituted dibenzofuryl and the like are heteroaryl of a plurality of aromatic ring systems connected by carbon-carbon bond conjugation.

In this application, the explanation for aryl applies to arylene and the explanation for heteroaryl applies equally to heteroarylene.

In the present application, the halogen may be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.

In one embodiment of the compounds described herein, L₁And L₂Are independently selected fromThe compound is selected from single bond, substituted or unsubstituted arylene with 6-25 ring carbon atoms and substituted or unsubstituted heteroarylene with 3-24 ring carbon atoms.

In some embodiments, the compound of formula 1 described herein is selected from the following compounds:

in some embodiments of the compounds described herein, L₁And L₂Each independently selected from the group consisting of a single bond or the following group, but not limited thereto:

wherein the content of the first and second substances,

represents a chemical bond of a compound represented by the formula,

Z₁to Z₂₁Independently selected from hydrogen, deuterium, halogen, cyano, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, alkoxy having 1 to 6 carbon atoms, aryloxy having 6 to 18 carbon atoms, arylthio having 6 to 18 carbon atoms, aryl having 6 to 20 carbon atoms, heteroaryl having 3 to 20 carbon atoms, cycloalkyl having 3 to 10 carbon atoms;

z is selected from C (R)₄R₅)，N(R₆)，O，S，Si(R₄R₅)，Se；

R₄，R₅The same or different, each is independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aryl group having 3 to 10 carbon atoms, or substituted or unsubstituted aryl group having two or more carbon atomsHeteroaryl of 3 to 20; alternatively, the first and second electrodes may be,

optionally, R₄，R₅Are linked to each other to form a saturated or unsaturated cyclic group;

x is selected from the following substituted or unsubstituted groups: alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms, arylene having 6 to 20 carbon atoms, heteroarylene having 3 to 30 carbon atoms;

R₆selected from the following substituted or unsubstituted groups: alkyl with 1-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, aryl with 6-20 carbon atoms and heteroarylene with 3-20 carbon atoms;

X₁to X₁₀Each independently selected from C or N, and at least one is N;

X₁₁to X₁₅Each independently selected from C or N, and at least one is N;

X₁₆to X₂₃Each independently selected from C or N, and at least one is N;

X₂₄to X₂₇Are each independently selected from C (R)₄R₅)，N(R₆)，O，S，Si(R₄R₅)，Se；

X₂₈，X₂₉Each independently selected from C or N, and at least one is N;

n₁，n₃，n₄，n₆，n₇，n₈，n₉，n₁₅，n₁₇，n₁₉each independently selected from 1,2, 3 or 4;

n₂，n₁₄，n₁₆，n₂₀each independently selected from 1,2, 3,4, 5 or 6;

n₅，n₁₂，n₁₈each independently selected from 1,2, 3,4, 5, 6, 7 or 8;

n₁₃selected from 1,2, 3,4 or 5;

n₁₀，n₁₁each independently selected from 1,2 or 3;

n₂₁selected from 1,2, 3,4, 5, 6 or 7.

In some embodiments of the compounds described herein, R₄，R₅Are independent of each other and are not directly connected; or R₄，R₅Directly attached, and the atoms commonly attached to form a ring, which may be saturated (e.g., five-membered ring, six-membered ring, adamantane, etc.) or unsaturated. That is, R₄，R₅The substituents may be independent of each other or may be linked to each other to form a cyclic group, and specific examples of the cyclic group that may be formed include, but are not limited to: cyclopropane, cyclobutane, cyclopentane, cyclohexane, and adamantane.

In some embodiments of the compounds described herein, Ar₁And Ar₂Each independently selected from the following substituted or unsubstituted groups: an aryl group having 6 to 25 ring-forming carbon atoms and a heteroaryl group having 5 to 18 ring-forming carbon atoms.

In some embodiments of the compounds described herein, Ar₁And Ar₂Each independently selected from the group consisting of, but not limited to:

wherein the content of the first and second substances,

represents a chemical bond of a compound represented by the formula,

T₁to T₁₇Independently selected from hydrogen, deuterium, halogen, cyano, alkyl with 1-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, haloalkyl with 1-10 carbon atoms, alkoxy with 1-6 carbon atoms, aryloxy with 6-18 carbon atoms, arylthio with 6-18 carbon atoms, aryl with 6-20 carbon atoms, heteroaryl with 3-20 carbon atoms, trialkylsilyl with 3-12 carbon atoms and C6-An arylsilyl group of 24;

t is selected from C (R)₇R₈)，N(R₉)，O，S，Si(R₇R₈)，Se；

R₇，R₈The same or different, each is independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms; alternatively, the first and second electrodes may be,

optionally, R₇，R₈Are linked to each other to form a saturated or unsaturated cyclic group;

w is selected from the following substituted or unsubstituted groups: alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms, arylene having 6 to 20 carbon atoms, heteroarylene having 3 to 20 carbon atoms;

R₉selected from the following substituted or unsubstituted groups: alkylene having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, arylene having 6 to 20 carbon atoms, heteroarylene having 3 to 20 carbon atoms;

W₁，W₂each independently selected from C or N, and at least one is N;

W₃to W₇Each independently selected from C or N, and at least one is N;

W₈to W₁₅Each independently selected from C or N, and at least one is N;

W₁₆，W₁₇each independently selected from C (R)₇R₈)，N(R₉)，O，S，Si(R₇R₈)，Se；

e₁，e₁₁，e₁₄，e₁₅，e₁₇Each independently selected from 1,2, 3,4 or 5;

e₁₆selected from 1,2 or 3;

e₂，e₉each independently selected from 1,2, 3,4, 5, 6 or 7;

e₃，e₄，e₅are respectively provided withIndependently selected from 1,2, 3,4, 5, 6, 7, 8 or 9;

e₆selected from 1,2, 3,4, 5, 6, 7 or 8;

e₇，e₁₀，e₁₂，e₁₃each independently selected from 1,2, 3 or 4;

e₈selected from 1,2, 3,4, 5 or 6.

In some embodiments of the compounds described herein, R₇，R₈Are independent of each other and are not directly connected; or R₄，R₅Directly attached, and the atoms commonly attached to form a ring, which may be saturated (e.g., five-membered ring, six-membered ring, adamantane, etc.) or unsaturated. That is, R₇，R₈The substituents may be independent of each other or may be linked to each other to form a cyclic group, and specific examples of the cyclic group that may be formed include, but are not limited to: cyclopropane, cyclobutane, cyclopentane, cyclohexane, and adamantane.

the compound according to the present application, wherein the compound is selected from any one of the following compounds, but not limited thereto:

another aspect of the present application provides an organic electroluminescent device comprising an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode, wherein a guest material of the light-emitting layer is selected from one or more of the compounds described herein.

In the organic electroluminescent device described herein, the organic electroluminescent device may further include one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron injection layer, or an electron transport layer. According to the combination of different organic layers and the compounds contained in each organic layer, the corresponding compounds with different organic layers and high matching degree are selected to improve the photoelectric properties of the compounds.

The present application also provides an organic electroluminescent device comprising an anode, a cathode, an organic layer between the anode and the cathode, wherein the organic layer comprises the compound.

Optionally, the organic layer comprises a light emitting layer comprising the compound.

Optionally, the light emitting layer includes a host material and a guest material, the guest material including the compound.

Optionally, the organic electroluminescent device is a blue light device.

For example, as shown in fig. 2, the organic electroluminescent device includes an anode 100 and a cathode 200 oppositely disposed, and an organic layer 300 disposed between the anode 100 and the cathode 200; the organic layer 300 comprises a compound provided herein.

Alternatively, the compounds provided herein may be used to form at least one organic film layer in the organic layer 300 to improve the lifetime characteristics, efficiency characteristics, and reduce the driving voltage of the organic electroluminescent device; in some embodiments, the mass production stability of the organic electroluminescent device can also be improved.

Optionally, the organic layer 300 includes an electron transport layer 360, the electron transport layer 360 comprising a compound provided herein. The electron transport layer 360 may be composed of the nitrogen-containing compound provided herein, or may be composed of the compound provided herein and other materials.

In one embodiment of the present application, as shown in fig. 1, the organic electroluminescent device may include an anode 100, a hole injection layer 310, a hole transport layer 320, an electron blocking layer 330, an organic light emitting layer 340, a hole blocking layer 350, an electron transport layer 360, an electron injection layer 370, and a cathode 200, which are sequentially stacked. The compound provided by the application can be applied to an electron transport layer 360 and a hole blocking layer 350 of an organic electroluminescent device, and can effectively improve the electron transport property of the organic electroluminescent device. Here, the hole characteristics mean that holes formed in the anode 100 are easily injected into the organic electroluminescent layer 340 and are transported in the organic electroluminescent layer 340 according to conduction characteristics of the HOMO level.

Optionally, the anode 100 comprises an anode material, which is preferably a material with a large work function that facilitates hole injection into the organic layer. Specific examples of the anode material include: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combined metals and oxides such as ZnO: Al or SnO2: Sb; or a conductive polymer such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDT), polypyrrole and polyaniline, but not limited thereto. Preferably, a transparent electrode including Indium Tin Oxide (ITO) as an anode is included.

Alternatively, the organic light emitting layer 340 may be composed of a single light emitting material, and may also include a host material and a guest material. Alternatively, the organic light emitting layer 340 may be composed of a host material and a guest material, and a hole injected into the organic light emitting layer 340 and an electron injected into the organic light emitting layer 340 may be combined in the organic light emitting layer 340 to form an exciton, which transfers energy to the host material, and the host material transfers energy to the guest material, so that the guest material can emit light.

The host material of the organic light emitting layer 340 may be a metal chelate compound, a bisstyryl derivative, an aromatic amine derivative, a dibenzofuran derivative, or other types of materials, which is not particularly limited in the present application. In one embodiment of the present application, the host material of the organic light emitting layer 340 may be α, β -ADN.

The guest material of the organic light emitting layer 340 may be a compound having a condensed aryl ring or a derivative thereof, a compound having a heteroaryl ring or a derivative thereof, an aromatic amine derivative, or other materials, which is not particularly limited in the present application. The compounds of the present application may be used as guest materials for light-emitting layer 340.

The electron transport layer 360 may have a single-layer structure or a multi-layer structure, and may include one or more electron transport materials, and the electron transport materials may be selected from benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials, which is not particularly limited in this application. For example, in one embodiment of the present application, the electron transport layer 360 may be composed of DBimiBphen and LiQ.

Optionally, the cathode 200 comprises a cathode material, which is a material with a small work function that facilitates electron injection into the organic layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or a multilayer material such as LiF/Al, Liq/Al, LiO₂Al, LiF/Ca, LiF/Al and BaF₂But not limited thereto,/Ca. Preferably, a metal electrode comprising aluminum is included as a cathode.

Optionally, as shown in fig. 2, a hole injection layer 310 may be further disposed between the anode 100 and the hole transport layer 320 to enhance the ability to inject holes into the hole transport layer 320. The hole injection layer 310 may be made of benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives, or other materials, which are not limited in this application. In one embodiment of the present application, the hole injection layer 310 may be composed of m-MTDATA.

Optionally, as shown in fig. 1, an electron injection layer 370 may be further disposed between the cathode 200 and the electron transport layer 360 to enhance the ability to inject electrons into the electron transport layer 360. The electron injection layer 370 may include an inorganic material such as an alkali metal sulfide or an alkali metal halide, or may include a complex of an alkali metal and an organic material. In one embodiment of the present application, the electron injection layer 370 may include LiQ.

The electronic device comprises any one of the electronic elements described in the electronic element embodiment. Since the electronic device has any one of the electronic elements described in the electronic element embodiments, the electronic device has the same beneficial effects, and the details of the electronic device are not repeated herein.

For example, as shown in fig. 3, the present application provides an electronic device 400, wherein the electronic device 400 includes any one of the organic electroluminescent devices described in the organic electroluminescent device embodiments. The electronic device 400 may be a display device, a lighting device, an optical communication device, or other types of electronic devices, and may include, but is not limited to, a computer screen, a mobile phone screen, a television, electronic paper, an emergency light, an optical module, and the like. Since the electronic device 400 has any one of the organic electroluminescent devices described in the organic electroluminescent device embodiments, the same advantages are obtained, and details are not repeated herein.

Hereinafter, the present application will be described in further detail with reference to examples. However, the following examples are merely illustrative of the present application and do not limit the present application.

For the convenience of understanding of the present application, the following raw materials and intermediates correspond to the numbers of the compounds to be prepared, and for example, "raw material 2 a", "raw material 2 b" and "raw material 2 c" respectively refer to raw material Ia, raw material Ib and raw material Ic specifically selected for preparing the compound 2; "starting material 18 a", "starting material 18 b", "intermediate 18 d", "starting material 18 c" and "intermediate 18 e" respectively refer to starting material Ia, starting material Ib, intermediate Id, starting material Ic and intermediate Ie, which are specifically selected for the preparation of compound 18.

Synthesis of Compound intermediate starting Material (taking 4a as an example)

(1) After nitrogen replacement is carried out in a three-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a constant pressure dropping funnel, the raw materials of p-dibromobenzene (200mmol) and 500.0ml of THF are sequentially added, stirring is started, the temperature is reduced to-85 to-90 ℃, 2mol/L n-butyllithium (210mmol) is dropped, the temperature in the dropping process is kept at-85 to-90 ℃, heat preservation is carried out for 1h after dropping is finished, and the solution of the raw materials of 4a-1(200mmol) and 140.0ml of THF is dropped. After the dropwise addition, the temperature is kept for 0.5h, and the temperature is naturally raised to room temperature for reaction for 3 h. Pouring the reaction solution into 10% ammonium chloride aqueous solution, extracting with 320.0ml toluene, separating, extracting the water phase with 320.0ml toluene for 1 time, combining the organic phase, washing with 260.0ml water for 2 times, separating, adding 12g anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating the organic phase (minus 0.08-0.09 MPa, 55-65 ℃) until the organic phase cannot be discharged, adding 150.0ml petroleum ether, stirring for 0.5h, filtering, leaching the filter cake with petroleum ether to obtain an intermediate 4a-2(150mmol), and obtaining the yield of 75%.

(2) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, sequentially adding the intermediate 4a-2(150mmol), p-toluenesulfonic acid (200mmol) and 560.0ml of toluene, heating to 100-105 ℃, and carrying out heat preservation reaction for 7 hours. Adding 200.0ml of water, separating, extracting a water phase by 300.0ml of toluene, combining organic phases, adding 300.0ml of water, washing for 2 times, separating, adding 10g of anhydrous sodium sulfate into the organic phase, stirring, drying, filtering, concentrating the organic phase (minus 0.08 to minus 0.09MPa, 55-65 ℃) until the organic phase cannot be obtained, adding 100.0ml of ethanol, stirring, separating out a large amount of solid, filtering, leaching a filter cake by using ethanol, and obtaining 4a-3(130mmol) with the yield of 86.6%.

(3) Adding 4a-3(125mmol) and cesium carbonate in sequence under the protection of nitrogen in a three-port reaction flask with a mechanical stirrer, a thermometer and a condenser pipe(200mmol), Tricyclohexylphosphine tetrafluoroborate (12.5mmol), Pd (OAc)₂(2.5mmol), 621.1ml of N, N-dimethylacetamide, stirring, heating to 130-140 ℃, reacting for 15h, pouring the reaction solution into 200.0ml of water, stirring and adding 400.0ml of dichloroethane, standing, separating, extracting the aqueous phase with 200.0ml of 2 times of dichloroethane, combining the organic phases, washing the organic phase with 300.0ml of water for 2 times, drying with 15g of anhydrous sodium sulfate, filtering, passing the filtrate through a (80-120) mesh silica gel column, concentrating the column-passing solution (50-70 ℃, minus 0.09-minus 0.08MPa) until the solution cannot be separated out, adding 200.00L of N-heptane under stirring, filtering, and using 1g of the obtained solid crude product: recrystallization from 3.2ml of ethyl acetate gave compound 4a (90mmol) in 46.7% overall yield.

The following compounds were synthesized according to the method of 4a, except that the starting material 4a-1 was replaced with the corresponding one, and the starting materials used and the compounds prepared accordingly are shown in table 1 below.

TABLE 1

Synthesis of compound intermediate class d (taking 4d as an example):

after nitrogen replacement in a three-neck reaction flask equipped with a mechanical stirrer, a thermometer and a constant pressure dropping funnel, 220mL of dichloroethane, 150mmol of benzene and 160mmol of anhydrous aluminum trichloride are sequentially added, the temperature is reduced to 10-15 ℃, and a 4-d (145mmol) dichloroethane (220mL) solution is added dropwise. After the dropwise addition, naturally heating to room temperature for reaction for 3h, slowly pouring the reaction solution into 62.5mL of frozen concentrated hydrochloric acid while stirring, stirring until the system completely changes color, adding 220mL of water and 110mL of dichloroethane, stirring until the system is clear, separating the liquid, extracting the aqueous phase with 220mL of 2 dichloroethane, combining the organic phases, washing the organic phase with 220mL of 2, drying the organic phase with 10g of anhydrous sodium sulfate, filtering, concentrating the organic phase to be dry under the conditions of (35-40 ℃ and-0.04-0.06 MPa), and adding dichloromethane: after the product was concentrated to dryness, 1g:3mL of ethyl acetate was added and stirred to dissolve, and a solid was precipitated by standing at room temperature and filtered to obtain 4d (105mmol) with a yield of 72.4%.

The following compounds were synthesized according to the method of 4d, except that the starting materials 4-d were replaced by the corresponding starting materials, and the starting materials used and the compounds prepared accordingly are shown in table 2 below.

TABLE 2

Example 1

Synthesis of Compound 4

(1) Adding raw material 4a (100mmol), raw material 4b (100mmol), potassium carbonate (200mmol), palladium (1mmol) of tetratriphenylphosphine, 280.0ml of toluene, 56.0ml of ethanol and 56.0ml of water into a three-mouth reaction bottle provided with a mechanical stirrer, a thermometer and a condenser after nitrogen replacement, starting stirring, heating to 65-70 ℃, carrying out heat preservation reaction for 8 hours, adding 112.0ml of water into the reaction solution under stirring, standing for liquid separation, extracting the aqueous phase for 1 time by using 140.0ml of toluene, carrying out liquid separation, combining organic phases, and washing for 2 times by using 112.0ml of water. Adding 5g of anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating the organic phase (-0.08-0.09 MPa, 55-65 ℃) until the organic phase cannot be discharged, adding 140.0ml of ethanol under stirring, and filtering to obtain an intermediate, 4c (93mmol), wherein the yield is 93%.

(2) After nitrogen replacement is carried out in a three-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a constant pressure dropping funnel, the intermediate 4c (80mmol) and 220.0ml THF are sequentially added, stirring is started, the temperature is reduced to-85 to-90 ℃, 2mol/L n-butyl lithium (96mmol) is dropwise added, the temperature in the dropwise adding process is kept at-85 to-90 ℃, the temperature is kept for 0.5h after the dropwise adding is finished, and the solution of 4d (80mmol) and 70.0ml THF is dropwise added. After the dropwise addition, the temperature is kept for 0.5h, and the temperature is naturally raised to room temperature for reaction for 3 h. Pouring the reaction solution into 0.5mol/L diluted hydrochloric acid, extracting with 160.0ml toluene, separating, extracting the water phase with 160.0ml toluene for 1 time, combining the organic phases, washing with 120.0ml water for 2 times, separating, adding 5g anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating the organic phase until the organic phase cannot be discharged (0.08 to-0.09 MPa, 55 to 65 ℃), adding 100.0ml petroleum ether, stirring for 0.5h, filtering, leaching the filter cake with petroleum ether to obtain an intermediate 4e (65mmol), wherein the yield is 81.25%.

(3) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, adding the intermediate 4e (50mmol), p-toluenesulfonic acid (10mmol) and 460.0ml of toluene in sequence, heating to 100-105 ℃, and carrying out heat preservation reaction for 5 hours. Adding 200.0ml of water, separating, extracting the water phase with 230.0ml of toluene, combining organic phases, adding 200.0ml of water, washing for 2 times, separating, adding 5g of anhydrous sodium sulfate into the organic phase, stirring and drying, filtering, concentrating the organic phase (minus 0.08-minus 0.09MPa, 55-65 ℃) until the organic phase cannot be discharged, adding 15ml of toluene and 45ml of ethanol, heating and dissolving, cooling to 25 ℃, stirring and separating out a large amount of solids, filtering, leaching a filter cake with ethanol to obtain 4f (46mmol), wherein the yield is 92%.

(4) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer and a thermometer, sequentially adding an intermediate 4f (40mmol), 180.0ml of dichloromethane and boron trifluoride diethyl etherate (40mmol), cooling to-5-0 ℃, adding DDQ (120mmol) in 4 batches, controlling the temperature to-5-0 ℃, preserving heat for 2 hours, adding 100.0ml of water, separating, extracting the water phase with 100.0ml of dichloromethane, separating, combining organic phases, washing with 100.0ml of water for 2 times, separating, adding 5g of anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating the organic phase to (-0.06-0.075 MPa, 35-40 ℃) to 30ml of solvent, cooling to 25 ℃, stirring to separate out a large amount of solids, filtering to obtain 4g (33mmol) of the intermediate, wherein the yield is 82.5%.

(5) The device is provided with a mechanical stirring device and a thermometer, under the protection of nitrogen in a condenser tube three-port reaction bottle, 4g (30mmol) of an intermediate, 4H (30mmol) of a raw material, potassium carbonate (60mmol), palladium acetate (0.3mmol), s-phos (0.6mmol), 120.0ml of toluene, 30.0ml of ethanol and 30.0ml of water are added, stirring is started, the temperature is increased to 65-70 ℃, reaction is kept for 8H, 30.0ml of water is added into a reaction solution under stirring, standing and liquid separation are carried out, an aqueous phase is extracted by 80.0ml of toluene, liquid separation is carried out, organic phases are combined, 100.0ml of water is added for washing for 2 times, liquid separation is carried out, 5g of anhydrous sodium sulfate is added into the organic phases for drying, a silica gel column is passed, the organic phases are concentrated to be not discharged, 50.0ml of ethanol is added under stirring, filtering is carried out, a solid is leached by 20.0ml of ethanol, and compound 4(23.6mmol) is obtained, the yield is 78.6%, the total yield is 45.07%, and the M/z.]⁺。

Example 2

Synthesis of Compound 38

(1) Adding the raw material 38a (100mmol), the raw material 38b (100mmol), potassium carbonate (200mmol), palladium (1mmol) of tetratriphenylphosphine, 280.0ml of toluene, 56.0ml of ethanol and 56.0ml of water into a three-mouth reaction bottle provided with a mechanical stirrer, a thermometer and a condenser after nitrogen replacement, starting stirring, heating to 65-70 ℃, carrying out heat preservation reaction for 12 hours, adding 112.0ml of water into the reaction solution under stirring, standing for liquid separation, extracting the aqueous phase for 1 time by using 140.0ml of toluene, carrying out liquid separation, combining organic phases, and washing for 2 times by using 112.0ml of water. Adding 5g of anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating the organic phase (minus 0.08 to minus 0.09MPa, 55 to 65 ℃) until the organic phase cannot be discharged, adding 160.0ml of ethanol while stirring, filtering, and leaching with 20.0ml of ethanol to obtain an intermediate 38c (88mmol), wherein the yield is 88%.

(2) After nitrogen replacement is carried out in a three-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a constant pressure dropping funnel, the intermediate 38c (80mmol) and 220.0ml THF are sequentially added, stirring is started, the temperature is reduced to-85 to-90 ℃, 2mol/L n-butyl lithium (96mmol) is dropwise added, the temperature in the dropwise adding process is kept at-85 to-90 ℃, heat preservation is carried out for 1h after the dropwise adding is finished, and the solution of the raw material 38d (80mmol) +60.0ml THF is dropwise added. After the dropwise addition, the temperature is kept for 1h, and the temperature is naturally raised to room temperature for reaction for 5 h. Pouring the reaction solution into 0.5mol/L diluted hydrochloric acid, extracting with 160.0ml toluene, separating, extracting the water phase with 160.0ml toluene for 1 time, combining the organic phases, washing with 120.0ml water for 2 times, separating, adding 5g anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating the organic phase to the temperature of minus 0.08 to minus 0.09MPa, 55 to 65 ℃, adding 120.0ml petroleum ether, stirring for 0.5h, filtering, leaching the filter cake with 30.0ml petroleum ether, obtaining an intermediate 38e (60mmol), and obtaining the yield of 75%.

(3) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, adding the intermediate 38e (50mmol), p-toluenesulfonic acid (10mmol) and 460.0ml of toluene in sequence, heating to 100-105 ℃, and carrying out heat preservation reaction for 3 hours. Adding 200.0ml of water, stirring, standing, separating liquid, extracting a water phase by 230.0ml of toluene, combining organic phases, washing by 200.0ml of water each time for 2 times, adding 5g of anhydrous sodium sulfate into the organic phase after liquid separation, stirring, drying, filtering, concentrating the organic phase (-0.08 to-0.09 MPa, 55-65 ℃) until the organic phase cannot be discharged, adding 16ml of toluene and 48ml of ethanol, heating, dissolving, cooling to 25 ℃, stirring to separate out a large amount of solids, filtering, leaching a filter cake by 30.0ml of ethanol to obtain 38f (42mmol), wherein the yield is 84%.

(4) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirring thermometer, sequentially adding an intermediate 38f (40mmol), 180.0ml of dichloromethane and boron trifluoride diethyl etherate (40mmol), cooling to-5-0 ℃, adding DDQ (120mmol) in 4 batches, controlling the temperature to-5-0 ℃, preserving heat for 4 hours, adding 100.0ml of water, stirring, standing for liquid separation, extracting the water phase with 100.0ml of dichloromethane, liquid separation, combining organic phases, washing with 100.0ml of water for 2 times, liquid separation, adding 5g of anhydrous sodium sulfate into the organic phases for drying, filtering, cooling to 25 ℃ when the organic phases are concentrated to 22ml of solvent (-0.06-0.075 MPa, 35-40 ℃) to obtain a large amount of solid, and filtering to obtain 38g (32mmol) of the intermediate with the yield of 82%.

(5) Adding 38g (30mmol) of intermediate, 38h (30mmol) of potassium carbonate (60mmol) of raw materials, 0.3mmol of palladium acetate, 0.6mmol of s-phos, 120.0ml of toluene, 30.0ml of ethanol and 30.0ml of water into a three-port reaction bottle with a mechanical stirrer, a thermometer and a condenser under the protection of nitrogen, starting stirring, heating to 65-70 ℃, carrying out heat preservation reaction for 6h, adding 30.0ml of water into the reaction liquid under stirring, standing for liquid separation, extracting the water phase with 80.0ml of toluene, carrying out liquid separation, combining organic phases, washing with 100.0ml of water for 2 times each time, carrying out liquid separation, adding 5g of anhydrous sodium sulfate into the organic phases for drying, passing through a silica gel column, adding 50.0ml of ethanol under stirring, filtering, leaching the solid with 20.0ml of ethanol, obtaining 38(21mmol), wherein the yield is 70%, and the total yield is 31.82%. 719.2[ M + H ] M/z]⁺。

Example 3

Synthesis of Compound 103

(1) Adding a raw material 103a (100mmol), a raw material 103b (100mmol), potassium carbonate (200mmol), palladium (1mmol) of tetratriphenylphosphine, 280.0ml of toluene, 56.0ml of ethanol and 56.0ml of water into a three-mouth reaction bottle provided with a mechanical stirrer, a thermometer and a condenser after nitrogen replacement, starting stirring, heating to 65-70 ℃, carrying out heat preservation reaction for 6 hours, adding 112.0ml of water into a reaction solution under stirring, standing for liquid separation, extracting an aqueous phase for 1 time by using 140.0ml of toluene, carrying out liquid separation, combining organic phases, and washing for 2 times by using 112.0ml of water. Adding 5g of anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating the organic phase (-0.08-0.09 MPa, 55-65 ℃) until the organic phase cannot be discharged, adding 140.0ml of ethanol under stirring, and filtering to obtain an intermediate 103c (94mmol), wherein the yield is 94%.

(2) After nitrogen replacement is carried out in a three-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a constant pressure dropping funnel, the intermediate 103c (80mmol) and 220.0ml THF are sequentially added, stirring is started, the temperature is reduced to-85 to-90 ℃, 2mol/L n-butyl lithium (96mmol) is dropwise added, the temperature in the dropwise adding process is kept at-85 to-90 ℃, heat preservation is carried out for 1h after the dropwise adding is finished, and the solution of the raw material 103d (80mmol) +70.0ml THF is dropwise added. After the dropwise addition, the temperature is kept for 0.5h, and the temperature is naturally raised to room temperature for reaction for 2 h. Pouring the reaction solution into 0.5mol/L diluted hydrochloric acid, extracting with 160.0ml toluene, separating, extracting the water phase with 160.0ml toluene for 1 time, combining the organic phases, washing with 120.0ml water for 2 times, separating, adding 8g anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating the organic phase until the organic phase is not discharged (0.08 to-0.09 MPa, 55 to 65 ℃), adding 130.0ml petroleum ether, stirring for 0.5h, filtering, leaching the filter cake with 30.0ml petroleum ether, obtaining an intermediate 103e (68mmol), wherein the yield is 85%.

(3) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, the intermediate 103e (50mmol), p-toluenesulfonic acid (10mmol) and 460.0ml of toluene are sequentially added, the temperature is raised to 100-105 ℃, and the reaction is carried out for 7 hours under heat preservation. Adding 200.0ml of water under stirring, separating liquid, extracting a water phase by 230.0ml of toluene, combining organic phases, adding 200.0ml of water, washing for 2 times, separating liquid, adding 5g of anhydrous sodium sulfate into the organic phases, stirring and drying, filtering, concentrating the organic phases (minus 0.08 to minus 0.09MPa, 55-65 ℃) until the organic phases cannot be discharged, adding 15ml of toluene and 45ml of ethanol, heating and dissolving, cooling to 25 ℃, stirring and separating out a large amount of solids, filtering, leaching a filter cake by 15.0ml of ethanol to obtain 103f (40mmol), wherein the yield is 80%.

(4) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer and a thermometer, sequentially adding an intermediate 103f (40mmol), 180.0ml of dichloromethane and boron trifluoride diethyl etherate (40mmol), cooling to-5-0 ℃, adding DDQ (120mmol) in 4 batches, keeping the temperature at-5-0 ℃, preserving the temperature for 5h, adding 100.0ml of water, separating, extracting the water phase with 100.0ml of dichloromethane, separating, combining organic phases, washing with 100.0ml of water for 2 times, separating, adding 5g of anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating the organic phase to (-0.06-0.075 MPa, 35-40 ℃) to 18ml of solvent, cooling to 25 ℃, stirring to separate out a large amount of solids, and filtering to obtain an intermediate 103g (33mmol) with the yield of 82.5%.

(5) Adding 103g (30mmol) of intermediate, 103h (30mmol) of potassium carbonate (60mmol) as raw materials, 0.3mmol of palladium acetate, 0.6mmol of s-phos, 120.0ml of toluene, 30.0ml of ethanol and 30.0ml of water into a three-port reaction bottle with a mechanical stirrer, a thermometer and a condenser under the protection of nitrogen, starting stirring, heating to 65-70 ℃, carrying out heat preservation reaction for 10h, adding 30.0ml of water into reaction liquid under stirring, standing for liquid separation, extracting water phase with 80.0ml of toluene, carrying out liquid separation, combining organic phases, adding 100.0ml of water for washing for 2 times, carrying out liquid separation, adding 5g of anhydrous sodium sulfate into the organic phases for drying, passing through a silica gel column, concentrating the organic phase at (-0.08-0.09 MPa, 55-65 ℃) until the organic phase cannot be discharged,50.0ml ethanol was added with stirring, filtered and the solid was rinsed with 20.0ml ethanol to give compound 103(22mmol) in 73.3% yield and 38.65% overall yield. 621.4[ M + H ] M/z]⁺。

Examples 4 to 13

The following compounds were synthesized in the same manner as in example 1, except that the starting materials 4a, 4b, 4d and 4h in example 1 were replaced with the corresponding starting materials, and the used starting materials and the compounds prepared accordingly, and the mass spectrum data are specifically shown in Table 3.

TABLE 3

The following application examples 1 to 13 are used to illustrate the application of the compound of the present application in a light emitting layer in an organic electroluminescent device.

Application example 1

A method of manufacturing an organic light emitting device, comprising the steps of:

(1) firstly, distilled water and methanol are sequentially used for ultrasonic cleaning

Drying a glass bottom plate of an Indium Tin Oxide (ITO) electrode;

(2) cleaning the anode base plate for 5 minutes by using oxygen plasma, and then loading the cleaned anode base plate into vacuum deposition equipment;

(3) the compound 2-TNATA (CAS: 185690-41-9) was vacuum deposited onto an ITO electrode

A hole injection layer 310 of a thickness and vacuum depositing NPB (N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine) on the hole injection layer

A hole transport layer 320 of thickness. TCTA (structure shown as formula A) is evaporated on the hole transport layer to form

Electron blocking layer 330 of thickness. Then, the host luminescent material alpha, beta-ADN (with the structure shown as the formula B) and the compound 4 are taken as objects to be co-deposited on the electron barrier layer according to the film thickness ratio of 100:3 to form

A light emitting layer 340 of a thickness;

(4) will be provided with

Vacuum deposition of a thickness of DPVBi (CAS: 142289-08-5) forms a hole blocking layer 350 over the light emitting layer;

(5) mixing DBimiBphen (structure shown as formula C) and LiQ (structure shown as formula D) at a weight ratio of 1:1, and vacuum-depositing on the hole blocking layer to form

Electron transport layer 360 of thickness. Then, LiQ (8-hydroxyquinoline-lithium) was evaporated on the electron transport layer to form

An electron injection layer 370 with a thickness of 1: 9, and magnesium (Mg) and silver (Ag) are mixed at a vapor deposition rate, and vacuum-deposited on the electron injection layer to form

A cathode of a thickness of

Forming a capping layer (CPL), thereby completing the organic light emitterAnd (4) manufacturing the piece.

Comparative examples 1 to 3

In comparative examples 1 to 3, organic electroluminescent devices were fabricated in the same manner as in example 1, except that compound a, compound B, and compound C, which have the following structural formulae, were used as the guest of the light-emitting layer instead of compound 1, respectively:

application examples 2 to 13

An organic electroluminescent device was produced in the same manner as in application example 1, except that in application examples 2 to 13, compounds shown in table 4 below were used as guest materials instead of compound 4, respectively, to produce organic electroluminescent devices.

For the organic electroluminescent device prepared as above, at 15mA/cm²The electron luminescence characteristics were analyzed under the conditions of (1), and the results are shown in Table 4.

Table 4 performance test results of organic electroluminescent device

The driving voltage of the organic electroluminescent device prepared by applying the examples 1 to 13 is 3.9 to 4.4V, the average value of the driving voltage of the organic electroluminescent device is reduced by 6 to 16 percent compared with the driving voltage of the organic electroluminescent device of the comparative proportion, the luminous efficiency of the organic electroluminescent device is 5.9 to 6.8Cd/A, the luminous efficiency of the organic electroluminescent device of the comparative proportion is improved by 13 to 30 percent, the external quantum efficiency is 12.1 to 13.4 percent, and the external quantum efficiency of the comparative proportion is improved by 17 to 30 percent. Compared with the comparative example, the T95 service life of the organic electroluminescent device is improved by at least 10%.

It can be seen that the organic electroluminescent devices prepared in application examples 1 to 13 have lower driving voltage, higher luminous efficiency, higher external quantum efficiency and brightness, compared to the device of the comparative example. Compared with the compound A and the compound B, the condensed ring compound parent nucleus, the aryl and heteroaryl substituent groups adopted by the compound are easy to form a large conjugated system, a plurality of nitrogen atom centers exist at the same time, the density of electron clouds in molecules is increased, the HOMO energy level can be further adjusted to a proper level, the electron mobility and the transition rate are further improved, and the organic electroluminescent device has high device efficiency. The performance of the organic electroluminescent device can be remarkably improved when the organic electroluminescent device is used for a light emitting layer of the organic electroluminescent device.

In the present application, the organic electroluminescent device may be used in an organic light-emitting electronic device, wherein the electronic device may be a display screen of a mobile phone, a computer display screen, a television display screen, a display screen of a smart watch, a display screen of an organic electroluminescent device of a smart car, a display screen of a VR or AR helmet, a display screen of various smart devices, and the like. Fig. 3 is a schematic view of an electronic device according to an embodiment of the present application. In fig. 3, 400 denotes a display panel of a cellular phone including an organic electroluminescent device.

Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.

Claims

1. A compound having a structure represented by chemical formula 1:

wherein the content of the first and second substances,

X₁、X₂、X₃is C or N, and X₁、X₂、X₃At least one is N;

X₄、X₅、X₆is C or N, and X₄、X₅、X₆One and only one is N;

L₁and L₂Each independently selected from a single bond or from the group consisting of:

Ar₁and Ar₂Each independently selected from the group consisting of:

2. the compound of claim 1, wherein the compound is selected from any one of the following compounds:

3. an organic electroluminescent device comprising an anode, a cathode and an organic layer disposed between the cathode and the anode;

the organic layer comprises the compound of claim 1 or 2.

4. The organic electroluminescent device according to claim 3, wherein the organic layer comprises a light-emitting layer comprising a host material and a guest material comprising the compound according to claim 1 or 2.

5. The organic electroluminescent device according to claim 3 or 4, wherein the organic electroluminescent device is a blue light device.

6. An electronic device comprising the organic electroluminescent element as claimed in any one of claims 3 to 5.