CN111689984A - Compound containing multi-heterocyclic structure and application thereof - Google Patents

Compound containing multi-heterocyclic structure and application thereof Download PDF

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CN111689984A
CN111689984A CN202010661812.6A CN202010661812A CN111689984A CN 111689984 A CN111689984 A CN 111689984A CN 202010661812 A CN202010661812 A CN 202010661812A CN 111689984 A CN111689984 A CN 111689984A
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CN111689984B (en
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梁现丽
李仲庆
范洪涛
段陆萌
杭德余
曹占广
班全志
陈婷
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Beijing Yanhua Jilian Optoelectronic Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons

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  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to the technical field of organic electroluminescent display, and particularly discloses an organic material containing a compound with a multi-heterocyclic structure, and also discloses an application of the organic material in an organic electroluminescent device. The compound containing the multi-heterocyclic structure is shown as a general formula (I), and can be applied to the field of organic electroluminescence and used as an electron transport material. The structural compound provided by the invention is applied to an OLED device, and the device has the advantages of low driving voltage and high luminous efficiency.

Description

Compound containing multi-heterocyclic structure and application thereof
Technical Field
The invention relates to the technical field of materials for organic electroluminescence, and particularly discloses a novel compound containing a multi-heterocyclic structure, and also discloses application of the compound in an organic electroluminescent device.
Background
The application of the organic electroluminescent (OLED) material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. With the development of multimedia information technology, the requirements for the performance of flat panel display devices are higher and higher. The main display technologies at present are plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). Compared with liquid crystal display devices, OLEDs do not need backlight sources, have wider viewing angles and low power consumption, and have response speed 1000 times that of the liquid crystal display devices, so the OLEDs have wider application prospects.
Since the first time high efficiency Organic Light Emitting Diodes (OLEDs) were reported, many researchers have been working on improving the performance of OLED devices. Organic charge transport materials are an important material for OLED devices. The organic charge transport material is an organic semiconductor material which can realize the controllable directional ordered movement of carriers under the action of an electric field when the carriers (electrons or holes) are injected, thereby carrying out charge transport. The organic charge transport material mainly transports holes and is called a hole type transport material, and the organic charge transport material mainly transports electrons and is called an electron type transport material or an electron transport material for short. Organic charge transport materials have been developed to date, in which hole transport materials are more diverse and have better performance, and electron transport materials are less diverse and have poorer performance. For example, the currently commonly used electron transport material Alq3 has low electron mobility, which results in higher operating voltage of the device and serious power consumption; part of electron transport materials such as LG201 triplet level is not high, and when a phosphorescent light emitting material is used as a light emitting layer, an exciton blocking layer needs to be added, otherwise the efficiency is reduced; still other materials, such as Bphen, tend to crystallize, resulting in reduced lifetimes. These problems with electron transport materials are bottlenecks that affect the development of organic electroluminescent display devices. Therefore, the development of new electron transport materials with better performance has important practical application value.
Disclosure of Invention
The invention aims to develop an electron transport material of an organic electroluminescent device, which is applied to an OLED device and has the advantages of low driving voltage and high luminous efficiency.
Specifically, in a first aspect, the present invention provides a compound containing a polyheterocyclic structure, having a structure represented by general formula (i):
Figure BDA0002578867620000021
wherein:
R1～R12is optionally selected from H, halogen atom, linear or branched alkyl, cycloalkyl, amino, alkylamino, substituted or unsubstituted C6～C40A monocyclic or polycyclic aromatic hydrocarbon group of (A), and R1～R12At least one of which is substituted or unsubstituted C6～C40Monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group of (a).
The halogen atom is F, Cl, Br or I.
Straight chain alkyl refers to the general formula CnH2n+1Straight chain alkyl of (E) -including but not limited to methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like.
Branched chain-containing alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, and the like.
Cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
Alkylamino refers to a group in which at least one H on the amino group is substituted with an alkyl group.
C6～C40The monocyclic aromatic hydrocarbon group or the polycyclic aromatic hydrocarbon group of (1), wherein the monocyclic aromatic hydrocarbon group is an aromatic hydrocarbon group containing one benzene ring; the polycyclic aromatic hydrocarbon group is polyphenyl aliphatic hydrocarbon group, biphenyl and biphenyl type polycyclic aromatic hydrocarbon group, spirobifluorene group or condensed ring aromatic hydrocarbon group.
Polycyclic aromatic hydrocarbon groups include, but are not limited to, groups comprising biphenyl, terphenyl, naphthalene, acenaphthene, dihydroacenaphthene, fluorene, spirobifluorene, phenanthrene, pyrene, fluoranthene, chrysene, benzo (a) anthracene, benzofluoranthene, triphenylene, benzopyrene, perylene, indenofluoranthene.
As a preferred embodiment, in the general formula (I), R is as defined above1～R12Is optionally selected from H, substituted or unsubstituted C6～C40A monocyclic or polycyclic aromatic hydrocarbon group of (A), and R1～R12Not H at the same time; the polycyclic aromatic hydrocarbon group is any one of polyphenyl aliphatic hydrocarbon group, biphenyl polycyclic aromatic hydrocarbon group, spirobifluorene group and fused ring aromatic hydrocarbon group; said substituted C6～C40The monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon substituent of (a) is optionally selected from: halogen, straight-chain or branched-chain alkyl, cycloalkyl, polycyclic aryl, monocyclic aryl, heterocyclic aryl and heterocyclic aryl, wherein the number of the substituent groups is an integer selected from 1-7.
The polycyclic aryl groups can be biphenyl, phenanthryl, fluorenyl, anthracyl, fluoranthenyl, triphenylenyl, naphthyl, and the like.
The polycyclic arylo group may be phenanthro, anthraco, fluorantheno, triphenylo, naphtho, or the like.
Monocyclic aryl is phenyl.
Monocyclic aryl-and-heteroaryl is a phenyl group.
The heteroaryl group is a group having a heteroaryl ring, and may be a benzothienyl group, a benzofuranyl group, a pyridyl group, a pyrimidyl group, a thiazolyl group, or the like.
The heterocycloaryl group may be benzothieno, benzofuro, or the like.
As a preferred embodiment, in the general formula (I), R is as defined above1～R12Each independently selected from H, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzo (a) anthryl, substituted or unsubstituted benzo (b) fluoranthenyl, substituted or unsubstituted benzo (k) fluoranthenyl, substituted or unsubstituted benzo (a) pyrenyl, substituted or unsubstituted indenopluoroanthryl, substituted or unsubstituted perylenyl, with the proviso that R is1～R12Not H at the same time; the substituted substituent can be 1-3, and the substituent is selected from halogen and C1-5Linear or branched alkyl, C3-8Cycloalkyl, monocyclic aryl, monocyclic arylo, polycyclic aryl, polycyclic arylo of (a); the hydrogen on the substituent can be further substituted by 1-2 optional substituents as follows: c1-5Linear or branched alkyl, C3-8Cycloalkyl, phenyl.
As a preferred embodiment, in the general formula (I), R is as defined above1～R12Each independently selected from H, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted indenopfluoranthenyl, substituted or unsubstituted perylenyl, with the proviso that R is independently selected from the group consisting of1～R12Not H at the same time; the substituted substituent can be 1-3, and the substituent is selected from halogen and C1-5Linear or branched alkyl, C3-8Cycloalkyl, phenyl, biphenyl, naphthyl, naphtho, phenanthryl, benzo, triphenylene, fluoranthenyl; the hydrogen on the substituent may be further optionally substituted by 1 to 2Substituent group substitution: c1-5Linear or branched alkyl, C3-8Cycloalkyl, phenyl.
As a preferred embodiment, in the general formula (I), R is as defined above1～R12Each independently selected from H, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted indenopfluoranthenyl, substituted or unsubstituted perylenyl, with the proviso that R is independently selected from the group consisting of1～R12Not H at the same time; the substituted substituent can be 1-2, and the substituent is selected from C1-5Linear or branched alkyl, C3-6Cycloalkyl, phenyl, biphenyl, naphthyl, phenanthryl, benzo, triphenylene, naphtho, fluoranthenyl.
As a preferred embodiment, in the general formula (I), R is as defined above1～R12Each independently selected from H or the following groups:
Figure BDA0002578867620000031
Figure BDA0002578867620000041
and R is1～R12Not H at the same time. Wherein "" represents a linking site of a substituent to the parent nucleus.
As a preferred embodiment, in the general formula (I), R is as defined above1～R12At least one is selected from the group consisting of radicals other than H, preferably the R1～R12Wherein 1 to 5 groups are selected from groups other than H, and more preferably R1～R121 to 3 groups selected from the group other than H; when said R is1～R12When two or more groups other than H are selected, the groups other than H may be the same or different.
As a preferred embodiment, in the general formula (I), R is as defined above1～R12One of them is selected from groups other than H, and the others are all H; preferably R1Is a group other than H, and the others are all H; or, R2Is a group other than H, and the others are all H; or, R3Is a group other than H, and the others are all H; or, R6Is a group other than H, and the others are all H; or, R7Is a group other than H, and the others are all H; or, R9Is a group other than H, and the others are all H; or, R10Is a group other than H, and the others are all H; or, R11Is a group other than H, and the others are all H; more preferably, R2Is a group other than H, and the others are all H; or, R7Is a group other than H, and the others are all H; or, R10Is a group other than H, and the others are all H; or, R11The radicals other than H are all H.
As a preferred embodiment, in the general formula (I), R is as defined above1～R12Two of them are selected from groups other than H, and the others are both H; the R is1～R12The groups other than H selected in (1) may be the same or different. Preferably R1、R3Is a group other than H, and the others are all H; or, R6、R8Is a group other than H, and the others are all H; or, R9、R11Is a group other than H, and the others are all H; or, R2、R7Is a group other than H, and the others are all H; or, R7、R10Is a group other than H, and the others are all H; or, R2、R10Is a group other than H, and the others are all H; or, R3、R11Is a group other than H, and the others are all H; more preferably, R2、R7Is a group other than H, and the others are all H; or, R7、R10Is a group other than H, and the others are all H; or, R2、R10The radicals other than H are all H.
As a preferred embodiment, in the general formula (I), R is as defined above1～R12Three of (1) are selected from groups other than H, and the others are all H; the R is1～R12The groups other than H selected in (1) may be the same or different. Preferably R1～R4Wherein one is selected from the group consisting of radicals other than H, R5～R8Wherein one is selected from the group consisting of radicals other than H, R9～R12One of them is selected from the group other than H, and the others are all H; more preferably, R2、R7、R10Is selected from groups other than H, and all others are H.
As a preferred embodiment, the compound of formula (I) is selected from specific compounds represented by the following structural formula:
Figure BDA0002578867620000051
Figure BDA0002578867620000061
Figure BDA0002578867620000071
in a second aspect, the invention provides an application of the compound containing the multi-heterocyclic structure in preparing an organic electroluminescent device.
Preferably, the compound containing the multi-heterocyclic structure is used as an electron transport material in an organic electroluminescent device.
In a third aspect, the invention provides an organic electroluminescent device, which comprises an electron transport layer, wherein the electron transport layer contains the compound containing the multi-heterocyclic ring structure in the material.
Specifically, the invention provides an organic electroluminescent device, which sequentially comprises a transparent substrate, an anode layer, a hole injection layer, a hole transport layer, an electroluminescent layer, an electron transport layer, an electron injection layer and a cathode layer from bottom to top, wherein an electron transport material of the electron transport layer comprises the compound shown in the general formula (I), namely the compound containing a multi-heterocyclic structure.
In a preferred embodiment, the thickness of the electron transport layer may be 10 to 50nm, preferably 20 to 40 nm.
In a fourth aspect, the present invention provides a display device comprising the organic electroluminescent device.
In a fifth aspect, the present invention provides a lighting apparatus comprising the organic electroluminescent device.
The invention provides a novel OLED material, in particular to a compound containing a multi-heterocyclic structure as shown in a general formula (I), wherein the multi-heterocyclic structure is taken as a parent nucleus, and the parent nucleus structure has stronger electron-withdrawing capability and can be used as an electron transmission material; meanwhile, the film has good thermal stability and good film stability, and can be well applied to OLED devices; the compounds of this structure have suitable HOMO and LUMO energy levels and Eg; we have found that this is further achieved by introducing a neutral group R into the parent nucleus structure1～R12The electron transport performance of the material can be further improved by changing the mode of intermolecular stacking.
The compound containing the multi-heterocyclic structure as shown in the general formula (I) has better film stability and proper molecular energy level, and can be applied to the field of organic electroluminescence and used as an electron transport material. Experiments show that the compound disclosed by the invention has higher electron transport performance, is a stable and efficient electron transport material, can effectively reduce driving voltage, improves the luminous efficiency and the photoelectric performance of an OLED device, has very important practical application value, can be well applied to the field of organic electroluminescence, and can be used as an electron transport material for an electron transport layer of the OLED device.
The compound containing the multi-heterocyclic structure provided by the invention is used as an electron transport material of an electron transport layer, and the prepared OLED device has the advantages of low driving voltage and high luminous efficiency. The device can be applied in the fields of display and illumination.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples. The following examples are intended to illustrate the present invention, but are not intended to limit the scope of the present invention, and other equivalent changes or modifications made without departing from the spirit of the present invention are intended to be included within the scope of the appended claims.
According to the preparation method provided by the present invention, a person skilled in the art can use known common means to implement, such as further selecting a suitable catalyst and a suitable solvent, and determining a suitable reaction temperature, a suitable reaction time, a suitable material ratio, and the like, which are not particularly limited in the present invention. If not specifically stated, the starting materials for the preparation of solvents, catalysts, bases, etc. may be obtained by published commercial routes or by methods known in the art.
Synthesizing intermediate M1-M10
Synthesis of intermediate M1
Figure BDA0002578867620000081
The synthetic route is as follows:
Figure BDA0002578867620000082
the specific operation steps are as follows:
(1) adding 4-chloro-1-fluoro-2-nitrobenzene (17.5g, 0.1mol) and 2-bromo-4-chloroaniline (30.8g, 0.15mol) into a 2L three-necked bottle with mechanical stirring, protecting with argon, heating to 180 ℃, keeping the temperature for reaction for more than 30 hours, wherein the color of the reaction solution gradually becomes red in the reaction process, and finally gradually becomes deep red. After the reaction is finished, an organic phase is separated, extracted, dried, subjected to column chromatography, and subjected to spin-drying to obtain 30g of orange-red solid M-01 with the yield of 83%.
(2) In a 1L three-necked flask equipped with a mechanical stirrer, M-01(36.0g, 0.1mol), sodium sulfide nonahydrate (96g, 0.4mol), ethanol (200mL), and water (100mL) were added, and the mixture was heated to reflux under nitrogen protection, and the reaction was terminated after refluxing for 3 hours. Separating organic phase, extracting, drying, column chromatography and spin-drying solvent to obtain 26.5g white solid M-02 with yield of 80%.
(3) In a 1L three-necked flask with mechanical stirring, adding M-02(33.0g, 0.1mol) and 300mL of acetone for complete dissolution, adding a solution of KOH (11.2g,0.2mol) dissolved in water (50mL), slowly dropwise adding 2-bromo-4-chlorobenzoyl chloride (25.2g, 0.1mol) into the reaction flask, gradually precipitating solids in the reaction flask, reacting at normal temperature for 2 hours after the dropwise adding is finished, and finishing the reaction. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 43.8g of white solid M-03 with the yield of 79%.
(4) Adding M-03(54.8g, 0.1mol) and 200mL of glycol ether into a 1L three-necked flask, gradually heating to reflux under the protection of nitrogen, gradually dissolving the solid, magnetically stirring, keeping the temperature and reacting for 3 hours, and finishing the reaction. The organic phase was separated, extracted, dried, column chromatographed, and the solvent was spin-dried to give 40g of M-04 as a pale red solid in 76% yield.
(5) Under the protection of nitrogen, M-04(53.0g, 0.1mol) and THF 800mL are added into a 2L three-necked flask, the mixture is cooled to-78 ℃, n-butyllithium (100mL, 0.25mol) is slowly added dropwise under stirring for about 30mins, 50mL of THF is used for flushing a dropping funnel after dropping, and the temperature is kept for 1.5 hours after dropping to obtain a reaction solution of M-05. Slowly dropwise adding sulfur dichloride (16mL, 0.25mol) into a low-temperature system at-78 ℃, then flushing a dropping funnel with a small amount of THF, preserving the temperature for 1 hour after the addition is finished, slowly heating to room temperature, stirring at room temperature for reacting for 4 hours, and finishing the reaction. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 26.6g of intermediate M1 as a white solid with the yield of 66%.
Product MS (m/e): 401.96, respectively; elemental analysis (C)19H9Cl3N2S): theoretical value C: 56.53%, H: 2.25%, N: 6.94 percent; found value C: 56.32%, H: 2.11%, N: 6.82 percent.
Synthesis of intermediate M2
Figure BDA0002578867620000091
Referring to the synthesis of intermediate M1, the starting material was synthesized
Figure BDA0002578867620000092
Is replaced by
Figure BDA0002578867620000093
And selecting a proper material ratio, and obtaining an intermediate M2 by the same synthesis method of the intermediate M1 and other raw materials and steps.
Product MS (m/e): 367.99, respectively; elemental analysis (C)19H10Cl2N2S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.55%, H: 2.61%, N: 7.45 percent.
Synthesis of intermediate M3
Figure BDA0002578867620000101
Referring to the synthesis of intermediate M1, the starting material was
Figure BDA0002578867620000102
Are used separately
Figure BDA0002578867620000103
And (3) replacing, selecting a proper material ratio, and obtaining the intermediate M3 by using other raw materials and steps which are the same as the synthesis method of the intermediate M1.
Product MS (m/e): 367.99, respectively; elemental analysis (C)19H10Cl2N2S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.55%, H: 2.61%, N: 7.48 percent.
Synthesis of intermediate M4
Figure BDA0002578867620000104
Referring to the synthesis of intermediate M1, the starting material was
Figure BDA0002578867620000105
Are used separately
Figure BDA0002578867620000106
And (3) replacing, selecting a proper material ratio, and obtaining the intermediate M4 by using other raw materials and steps which are the same as the synthesis method of the intermediate M1.
Product MS (m/e): 367.99, respectively; elemental analysis (C)19H10Cl2N2S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.56%, H: 2.60%, N: 7.44 percent.
Synthesis of intermediate M5
Figure BDA0002578867620000111
Referring to the synthesis of intermediate M1, the starting material was
Figure BDA0002578867620000112
Are used separately
Figure BDA0002578867620000113
And (3) replacing, selecting a proper material ratio, and obtaining the intermediate M5 by using other raw materials and steps which are the same as the synthesis method of the intermediate M1.
Product MS (m/e): 367.99, respectively; elemental analysis (C)19H10Cl2N2S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.55%, H: 2.61%, N: 7.45 percent.
Synthesis of intermediate M6
Figure BDA0002578867620000114
Referring to the synthesis of intermediate M1, the starting material was
Figure BDA0002578867620000115
Are used separately
Figure BDA0002578867620000116
And (3) replacing, selecting a proper material ratio, and obtaining the intermediate M6 by using other raw materials and steps which are the same as the synthesis method of the intermediate M1.
Product MS (m/e): 334.03, respectively; elemental analysis (C)19H11ClN2S): theoretical value C: 68.16%, H: 3.31%, N: 8.37 percent; found value C: 68.01%, H: 3.16%, N: 8.25 percent.
Synthesis of intermediate M7
Figure BDA0002578867620000121
Referring to the synthesis of intermediate M1, the starting material was
Figure BDA0002578867620000122
Are used separately
Figure BDA0002578867620000123
And (3) replacing, selecting a proper material ratio, and obtaining the intermediate M7 by using other raw materials and steps which are the same as the synthesis method of the intermediate M1.
Product MS (m/e): 334.03, respectively; elemental analysis (C)19H11ClN2S): theoretical value C: 68.16%, H: 3.31%, N: 8.37 percent; found value C: 68.02%, H: 3.11%, N: 8.26 percent.
Synthesis of intermediate M8
Figure BDA0002578867620000124
Referring to the synthesis of intermediate M1, the starting material was
Figure BDA0002578867620000125
Are used separately
Figure BDA0002578867620000126
Figure BDA0002578867620000127
And (3) replacing, selecting a proper material ratio, and obtaining the intermediate M8 by using other raw materials and steps which are the same as the synthesis method of the intermediate M1.
Product MS (m/e): 334.03, respectively; elemental analysis (C)19H11ClN2S): theoretical value C: 68.16%, H: 3.31%, N: 8.37 percent; found value C: 68.02%, H: 3.11%, N: 8.26 percent.
Synthesis of intermediate M9
Figure BDA0002578867620000128
The synthetic route is as follows:
Figure BDA0002578867620000131
the specific operation steps are as follows:
(1) synthesis of intermediate M9-04:
by using
Figure BDA0002578867620000132
Respectively replace
Figure BDA0002578867620000133
Figure BDA0002578867620000134
Selecting a proper material ratio, and obtaining M9-04 firstly, wherein other raw materials and steps are the same as the synthesis method of the intermediate M1.
(2) Synthesis of intermediate M9:
in N2Under protection, M9-04(58.8g,0.1mol) and 500ml of anhydrous THF were added into a 2L three-necked flask, the reaction system was cooled to-78 ℃ with stirring by a liquid nitrogen ethanol bath, 70ml of a 1.6M hexane solution of n-butyllithium (0.11mol) was slowly added at this temperature, after completion of the dropwise addition, the temperature was maintained at this temperature for 15 minutes, sublimed sulfur powder (3.2g,0.1mol) was then added, after completion of the addition, the reaction system was stirred at-78 ℃ for 1 hour, and then the reaction system was slowly heated to-20 ℃ and kept at this temperature for 30 minutes. The reaction was then cooled further to-78 ℃ and CuCl (10g, 0.1mol) was added, the temperature was held at this temperature for 30 minutes, then the cold bath was removed, the reaction was allowed to warm to room temperature naturally, stirred for 2h, then the reaction was heated to reflux and reacted for 2 h. Cooling to room temperature, slowly addingAdding saturated ammonium chloride solution, adding 250ml of ethyl acetate, separating organic phase, extracting aqueous phase with ethyl acetate for 3 times, combining organic phase, drying anhydrous magnesium chloride, spin-drying solvent, and separating by column chromatography to obtain intermediate M9, 19.4g altogether, white solid with yield of about 47%.
Product MS (m/e): 411.94, respectively; elemental analysis (C)19H10BrClN2S): theoretical value C: 55.16%, H: 2.44%, N: 6.77 percent; found value C: 55.02%, H: 2.21%, N: 6.59 percent.
Synthesis of intermediate M10
Figure BDA0002578867620000141
By using
Figure BDA0002578867620000142
Respectively replace
Figure BDA0002578867620000143
And selecting a proper material ratio, and obtaining an intermediate M10 by the same synthesis method of the intermediate M9 and other raw materials and steps.
Product MS (m/e): 411.94, respectively; elemental analysis (C)19H10BrClN2S): theoretical value C: 55.16%, H: 2.44%, N: 6.77 percent; found value C: 55.01%, H: 2.22%, N: 6.54 percent.
Example 1
Figure BDA0002578867620000144
The synthetic route is as follows:
Figure BDA0002578867620000145
the synthesis of the compound I-1 comprises the following specific steps:
A1L three-necked flask was taken, and magnetic stirring was carried out, after nitrogen substitution, M1(40.2g, 0.1mol), phenylboronic acid (36.6g, 0.3mol), cesium carbonate (117g, 0.36mol) and dioxane (400 ml) were sequentially added, and stirring was started. After nitrogen replacement again, (2.2g, 11mmol) tri-tert-butylphosphine and (4.1g, 4.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting pH to neutral, separating organic phase, extracting, drying, performing column chromatography, and spin-drying solvent to obtain 40.1g pale yellow solid with yield of about 76%.
Product MS (m/e): 528.17, respectively; elemental analysis (C)37H24N2S): theoretical value C: 8.06%, H: 4.58%, N: 5.30 percent; found value C: 7.85%, H: 4.41%, N: 5.16 percent.
Example 2
Figure BDA0002578867620000151
The synthetic route is as follows:
Figure BDA0002578867620000152
synthesis of Compound I-8, substituting M1, 3, 4-dimethylphenylboronic acid with M2, selecting appropriate material ratios, and the other raw materials and procedures were the same as in example 1, giving 40.1g of a pale yellow solid with a yield of about 79%.
Product MS (m/e): 508.20, respectively; elemental analysis (C)35H286N2S): theoretical value C: 82.64%, H: 5.55%, N: 5.51 percent; found value C: 82.39%, H: 5.37%, N: 5.42 percent.
Example 3
Figure BDA0002578867620000153
The synthetic route is as follows:
Figure BDA0002578867620000154
synthesis of Compound I-10, substituting M1 with M3, and substituting phenylboronic acid with 4-cyclopentylphenylboronic acid, selecting appropriate material ratios, and the other raw materials and procedures were the same as in example 1, to obtain 47.61g of a pale yellow solid with a yield of about 81%.
Product MS (m/e): 588.26, respectively; elemental analysis (C)41H36N2S): theoretical value C: 83.63%, H: 6.16%, N: 4.76 percent; found value C: 83.41%, H: 6.01%, N: 4.42 percent.
Example 4
Figure BDA0002578867620000161
The synthetic route is as follows:
Figure BDA0002578867620000162
synthesis of Compound I-14, substituting M1 with M4 and phenylboronic acid with phenylboronic acid, selecting appropriate material ratios, and other raw materials and procedures were the same as in example 1, to give 42.9g of a pale yellow solid with a yield of about 71%.
Product MS (m/e): 604.20, respectively; elemental analysis (C)43H28N2S): theoretical value C: 85.40%, H: 4.67%, N: 4.63 percent; found value C: 85.15%, H: 4.42%, N: 4.39 percent.
Example 5
Figure BDA0002578867620000163
The synthetic route is as follows:
Figure BDA0002578867620000164
synthesis of Compound I-24, substituting M1 with M5 and phenylboronic acid with 2-naphthalene boronic acid, selecting appropriate material ratios, and the other raw materials and procedures were the same as in example 1, to give 46.9g of a pale yellow solid with a yield of about 85%.
Product MS (m/e): 552.17, respectively; elemental analysis (C)39H24N2S): theoretical value C: 84.75%, H: 4.38%, N: 5.07 percent; found value C:84.51％，H：4.14％，N：4.87％。
example 6
Figure BDA0002578867620000171
The synthetic route is as follows:
Figure BDA0002578867620000172
synthesis of Compound I-34 with M6 instead of M1 and triphenylen-2-yl boronic acid instead of phenylboronic acid, the appropriate ratios of materials were chosen and the other starting materials and procedures were the same as in example 1 to give 42.6g of a pale yellow solid with a yield of about 81%.
Product MS (m/e): 526.15, respectively; elemental analysis (C)37H22N2S): theoretical value C: 84.38%, H: 4.21%, N: 5.32 percent; found value C: 84.12%, H: 4.01%, N: 5.05 percent.
Example 7
Figure BDA0002578867620000173
The synthetic route is as follows:
Figure BDA0002578867620000174
synthesis of Compound I-41, M7 was used in place of M1, 9, 9' -spirobifluorene-2-boronic acid in place of phenylboronic acid, and the other raw materials and procedures were the same as in example 1, with selection of an appropriate material ratio, to give 52.2g of a pale yellow solid with a yield of about 85%.
Product MS (m/e): 614.18, respectively; elemental analysis (C)44H26N2S): theoretical value C: 85.97%, H: 4.26%, N: 4.56 percent; found value C: 85.72%, H: 4.03%, N: 4.26 percent.
Example 8
Figure BDA0002578867620000181
The synthetic route is as follows:
Figure BDA0002578867620000182
synthesis of Compound I-43, M8 was used in place of M1 and indeno [1,2,3-cd ] fluoranthen-5-ylboronic acid was used in place of phenylboronic acid, and the appropriate ratios of materials were chosen, and the other materials and procedures were the same as in example 1, giving 43.1g of a pale yellow solid with a yield of about 75%.
Product MS (m/e): 574.15, respectively; elemental analysis (C)41H22N2S): theoretical value C: 85.69%, H: 3.86%, N: 4.87 percent; found value C: 85.43%, H: 3.65%, N: 4.61 percent.
Example 9
Figure BDA0002578867620000183
The synthetic route is as follows:
Figure BDA0002578867620000184
the synthesis of the compound I-49 comprises the following specific steps:
into a 1L three-necked flask, M9(41.2g, 0.1mol), 4-isopropylphenylboronic acid (16.4g, 0.1mol), sodium carbonate (21.2g,0.2mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and Pd (PPh) was added after the reaction system was purged with nitrogen3)4(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating mode, the ethyl acetate is pulped, and 36.2g of light yellow solid I-49-1 is obtained through filtration, and the yield is about 80%.
Then, a 1L three-necked flask was taken, magnetic stirring was carried out, and after nitrogen substitution, I-49-1(45.2g, 0.1mol), biphenylboronic acid (19.8g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane (400 ml) were sequentially added, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 43.3g pale yellow solid I-49 with yield of about 76%.
Product MS (m/e): 570.21, respectively; elemental analysis (C)40H30N2S): theoretical value C: 84.18%, H: 5.30%, N: 4.91 percent; found value C: 83.92%, H: 5.11%, N: 4.69 percent.
Example 10
Figure BDA0002578867620000191
The synthetic route is as follows:
Figure BDA0002578867620000192
synthesis of Compound I-50 with M10 instead of M9, (4-phenylnaphthalen-1-yl) boronic acid instead of 4-isopropylphenylboronic acid, [1,1':3',1 "-terphenyl ] -5' -ylboronic acid instead of biphenylboronic acid, the appropriate material ratios were chosen and the other raw materials and procedures were the same as in example 9 to give I-50 as a pale yellow solid, 52.6g, in about 72% yield.
Product MS (m/e): 730.24, respectively; elemental analysis (C)53H34N2S): theoretical value C: 87.09%, H: 4.69%, N: 3.83 percent; found value C: 86.87%, H: 4.43%, N: 3.61 percent.
According to the synthesis schemes of the above examples 1 to 10, other compounds in I-1 to I-52 can be synthesized by simply replacing the corresponding raw materials without changing any substantial operation.
Example 11
The embodiment provides a group of OLED green light devices, and the device structure is as follows: ITO/HATCN (1nm)/HT01(40nm)/NPB (30nm)/EML (30 nm)/any of the compounds (30nm)/LiF (1nm)/Al provided in examples 1 to 10, the preparation process comprising:
(1) carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (the volume ratio is 1: 1), baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form HATCN as a first hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a second hole injection layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 40 nm; then, evaporating and plating a layer of NPB (N-propyl bromide) on the hole injection layer film to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 30 nm; wherein the structural formulas of HATCN, HT01 and NPB are as follows:
Figure BDA0002578867620000201
(3) vacuum evaporating EML (electron emission layer) on the hole transport layer to serve as a light emitting layer of the device, wherein the EML comprises a main material and a dye material, placing the main material serving as the light emitting layer in a chamber of a vacuum vapor deposition device by using a multi-source co-evaporation method, and adding Ir (ppy) serving as a dopant3Placing in another chamber of vacuum vapor deposition equipment, adjusting evaporation rate of CBP as main material to 0.1nm/s, and adjusting Ir (ppy) as dye material3The concentration of (2) is 10%, and the total film thickness of evaporation plating is 30 nm; wherein CBP, Ir (ppy)3The structural formula of (A) is as follows:
Figure BDA0002578867620000202
(4) taking any one of the compounds provided in the embodiments 1 to 10 as an electron transport material of an electron transport layer of a device for evaporation, wherein the evaporation rate is 0.1nm/s, and the total thickness of the evaporation film is 30 nm;
(5) sequentially vacuum evaporating LiF with the thickness of 1nm on the electron transport layer to serve as an electron injection layer of the device, continuously evaporating a layer of Al on the electron injection layer to serve as a cathode of the device, and evaporating the film with the thickness of 150 nm; obtaining a series of OLED-1-OLED-10 devices provided by the invention.
According to the same procedure as above, only the electron transport material in the step (4) was replaced with a comparative compound, the structural formula of which is shown below, to obtain a comparative device OLED-11.
Figure BDA0002578867620000203
The performance of the obtained devices OLED-1 to OLED-11 is detected, and the detection results are shown in Table 1.
TABLE 1
Figure BDA0002578867620000211
As can be seen from the results in the table above, the current efficiency of the devices OLED-1 to OLED-10 prepared by using the compound provided by the invention is higher, and the working voltage is lower than that of the device OLED-11 using the comparative compound Bphen as an electron transport material under the same brightness condition. As described above, the organic material represented by the general formula (I) provided by the invention is a novel electron transport material with good performance.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A compound containing a polyheterocyclic structure, having a structure represented by general formula (i):
Figure FDA0002578867610000011
wherein:
R1～R12is selected from H, halogen atom, straight chain or branched chain alkyl, cycloalkyl, amino and alkaneAmino, substituted or unsubstituted C6～C40A monocyclic or polycyclic aromatic hydrocarbon group of (A), and R1～R12At least one of which is substituted or unsubstituted C6～C40Monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group of (a).
2. A compound of claim 1, wherein R is1～R12Is optionally selected from H, substituted or unsubstituted C6～C40A monocyclic or polycyclic aromatic hydrocarbon group of (A), and R1～R12Not H at the same time; the polycyclic aromatic hydrocarbon group is any one of polyphenyl aliphatic hydrocarbon group, biphenyl polycyclic aromatic hydrocarbon group, spirobifluorene group and fused ring aromatic hydrocarbon group; said substituted C6～C40The substituents of the monocyclic or polycyclic aromatic hydrocarbon group of (a) are optionally selected from: halogen, straight-chain or branched-chain alkyl, cycloalkyl, polycyclic aryl, monocyclic aryl, heterocyclic aryl and heterocyclic aryl, wherein the number of the substituent groups is an integer selected from 1-7.
3. A compound according to claim 1 or 2, wherein R is1～R12Each independently selected from H, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzo (a) anthryl, substituted or unsubstituted benzo (b) fluoranthenyl, substituted or unsubstituted benzo (k) fluoranthenyl, substituted or unsubstituted benzo (a) pyrenyl, substituted or unsubstituted indenopluoroanthryl, substituted or unsubstituted perylenyl, with the proviso that R is1～R12Not H at the same time; the substituted substituent can be 1-3, and the substituent is selected from halogen and C1-5Linear or branched alkyl, C3-8Cycloalkyl, monocyclic aryl, monocyclic arylo, polycyclic aryl, polycyclic arylo(ii) a The hydrogen on the substituent can be further substituted by 1-2 optional substituents as follows: c1-5Linear or branched alkyl, C3-8Cycloalkyl, phenyl of (a);
preferably, said R is1～R12Each independently selected from H, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted indenopfluoranthenyl, substituted or unsubstituted perylenyl, with the proviso that R is independently selected from the group consisting of1～R12Not H at the same time; the substituted substituent can be 1-3, and the substituent is selected from halogen and C1-5Linear or branched alkyl, C3-8Cycloalkyl, phenyl, biphenyl, naphthyl, naphtho, phenanthryl, benzo, triphenylene, fluoranthenyl; the hydrogen on the substituent can be further substituted by 1-2 optional substituents as follows: c1-5Linear or branched alkyl, C3-8Cycloalkyl, phenyl of (a);
more preferably, said R1～R12Each independently selected from H, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted indenopfluoranthenyl, substituted or unsubstituted perylenyl, with the proviso that R is independently selected from the group consisting of1～R12Not H at the same time; the substituted substituent can be 1-2, and the substituent is selected from C1-5Linear or branched alkyl, C3-6Cycloalkyl, phenyl, biphenyl, naphthyl, phenanthryl, benzo, triphenylene, naphtho, fluoranthenyl.
4. The method according to any one of claims 1 to 3Wherein R is as defined above1～R12Each independently selected from H or the following groups:
Figure FDA0002578867610000021
Figure FDA0002578867610000031
and R is1～R12Not H at the same time.
5. A compound according to claim 3 or 4, wherein R is1～R12At least one is selected from the group consisting of radicals other than H, preferably the R1～R12Wherein 1 to 5 groups are selected from groups other than H, and more preferably R1～R121 to 3 groups selected from the group other than H; when said R is1～R12When two or more groups other than H are selected, the groups other than H may be the same or different;
preferably, said R is1～R12One of them is selected from groups other than H, and the others are all H; preferably R1Is a group other than H, and the others are all H; or, R2Is a group other than H, and the others are all H; or, R3Is a group other than H, and the others are all H; or, R6Is a group other than H, and the others are all H; or, R7Is a group other than H, and the others are all H; or, R9Is a group other than H, and the others are all H; or, R10Is a group other than H, and the others are all H; or, R11Is a group other than H, and the others are all H; more preferably, R2Is a group other than H, and the others are all H; or, R7Is a group other than H, and the others are all H; or, R10Is a group other than H, and the others are all H; or, R11Is a group other than H, and the others are all H;
or, said R1～R12Two of themSelected from the group consisting of groups other than H, all others being H; preferably R1、R3Is a group other than H, and the others are all H; or, R6、R8Is a group other than H, and the others are all H; or, R9、R11Is a group other than H, and the others are all H; or, R2、R7Is a group other than H, and the others are all H; or, R7、R10Is a group other than H, and the others are all H; or, R2、R10Is a group other than H, and the others are all H; or, R3、R11Is a group other than H, and the others are all H; more preferably, R2、R7Is a group other than H, and the others are all H; or, R7、R10Is a group other than H, and the others are all H; or, R2、R10Is a group other than H, and the others are all H;
or, said R1～R12Three of (1) are selected from groups other than H, and the others are all H; preferably R1～R4Wherein one is selected from the group consisting of radicals other than H, R5～R8Wherein one is selected from the group consisting of radicals other than H, R9～R12One of them is selected from the group other than H, and the others are all H; more preferably, R2、R7、R10Is selected from groups other than H, and all others are H.
6. The compound of any one of claims 1 to 5, wherein the compound is selected from the group consisting of compounds represented by the following structural formulae:
Figure FDA0002578867610000041
Figure FDA0002578867610000051
Figure FDA0002578867610000061
7. use of a compound containing a polyheterocyclic structure according to any one of claims 1 to 6 in the preparation of an organic electroluminescent device;
preferably, the compound containing the multi-heterocyclic structure is used as an electron transport material in an organic electroluminescent device.
8. An organic electroluminescent device, comprising an electron transport layer, wherein the electron transport layer comprises a compound containing a polyheterocyclic structure according to any one of claims 1 to 6.
9. A display device comprising the organic electroluminescent element according to claim 8.
10. A lighting device comprising the organic electroluminescent element according to claim 8.
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