CN116322134A - Organic electroluminescent device - Google Patents

Organic electroluminescent device Download PDF

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CN116322134A
CN116322134A CN202310107232.6A CN202310107232A CN116322134A CN 116322134 A CN116322134 A CN 116322134A CN 202310107232 A CN202310107232 A CN 202310107232A CN 116322134 A CN116322134 A CN 116322134A
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substituted
unsubstituted
different
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deuterium
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陆影
郭建华
孙月
刘小婷
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Changchun Hyperions Technology Co Ltd
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Changchun Hyperions Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/549—Organic PV cells

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  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides an organic electroluminescent device, and particularly relates to the technical field of organic electroluminescent. In order to solve the problems of low light extraction efficiency and the like of a cover layer material in the prior art, the invention provides an organic electroluminescent device, wherein the cover layer material of the device takes central benzene or N-heterocyclic benzene as a core, is connected with at least one benzo five-membered heterocycle and N-heterocyclic bridging group, has a strong rigid structure, has higher glass transition temperature and better thermal stability and is not easy to decompose at high temperature, and can effectively improve the light extraction effect, reduce the total reflection of light in the device and the generation of Joule heat when being applied to the organic electroluminescent device as a cover layer, thereby increasing the luminous efficiency and the service life of the device.

Description

Organic electroluminescent device
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescent device.
Background
An Organic Light-Emitting Diode (OLED) refers to a phenomenon in which an Organic semiconductor material and a Light-Emitting material emit Light by carrier injection and recombination under the driving of an applied electric field, and it can directly convert electric energy into Light energy. The light-emitting LED display device has the advantages of being ultrathin, full-cured, low in power consumption, self-luminous, high in response speed, wide in color gamut, good in temperature characteristic, flexible in display and the like, and is widely applied to the fields of information display and solid-state lighting.
In the OLED, under the action of an externally applied electric field, electrons from a cathode and holes from an anode enter an organic layer to carry out energy recombination and transfer the energy to an organic light-emitting compound, so that the organic light-emitting compound transits from a ground state to an excited state, and excited molecules return to the ground state from the excited state to release the energy in a light form, thereby forming a light-emitting phenomenon. An OLED is a sandwich-like sandwich structure, typically consisting of an anode, a cathode and an organic layer formed between the two electrodes. Currently, organic layers involved in OLEDs include hole injection layers, hole transport layers, hole blocking layers, light emitting layers, electron blocking layers, electron transport layers, electron injection layers, capping layers, and the like. Although OLED fabrication processes are continuously innovated and reformed, there are problems in commercialization of the OLED fabrication process for large-scale application due to the fact that the development of the organic light emitting materials is not perfect at the present stage.
For the coating material, most of the conventionally used coating materials are inorganic materials, so that certain disadvantages exist, on one hand, the evaporation temperature of the inorganic materials is higher, the device is deformed due to high temperature, so that the coating cannot be accurately evaporated, and on the other hand, the total reflection phenomenon of light in the device is increased due to the waveguide effect, and the extraction efficiency of the light in the device is reduced; in addition, the cathode of the OLED device is mostly metal with relatively active chemical properties, is extremely easy to erode in an environment containing oxygen, and particularly generates electrochemical corrosion in the air containing water vapor, so that the device is greatly damaged, and the service life of the device is reduced. In order to improve the light extraction efficiency of an organic light emitting device and to increase the lifetime of the device, it is important to develop a capping material having low absorption in the visible region, high refractive index, excellent film stability, and good durability.
Disclosure of Invention
The invention provides an organic electroluminescent device for solving the problem that the luminous efficiency and the service life of the organic electroluminescent device are influenced in the prior art.
Specifically, the invention provides an organic electroluminescent device, which comprises an anode, a cathode and an organic layer, wherein the organic layer comprises a covering layer, the covering layer has a structure shown in a formula I,
Figure BDA0004077534800000011
in formula I, the Ar 1 ～Ar 3 Is the same or different from each other, wherein at least one is selected from the group shown in a formula II, and the rest is the same or different from each other and is selected from any one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring groups;
Figure BDA0004077534800000021
in formula II, the L 0 Any one selected from the group consisting of the following groups and combinations thereof;
Figure BDA0004077534800000022
z is identical or different from each other and is selected from CH or N atoms, and at least one Z in each group is selected from N atoms; when Z is bonded to other groups, the Z is selected from C atoms;
the R is 1 Are the same or different from each other, and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
The a 1 Selected from 0, 1, 2 or 3, said a 2 Selected from 0, 1, 2, 3, 4 or 5; when two or more R's are present 1 When two or more R' s 1 Identical or different from each other, or adjacent two R' s 1 May be linked to each other to form a substituted or unsubstituted ring;
the x is 1 Selected from O, S, NR a Any one of them; the R is a Any one selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;
y, equal to or different from each other, is selected from CH or N atoms;
the R, R' are the same or different from each other and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
said m is selected from 0, 1, 2, 3 or 4; when two or more R's are present, two or more R's may be the same or different from each other, or adjacent two R's may be connected to each other to form a substituted or unsubstituted ring;
Said m' is selected from 0, 1 or 2;
the x are identical or different from each other and are selected from CH or N atoms, and when x is bonded with other groups, the x is selected from C atoms;
the R is 2 Any one selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
said n is selected from 0, 1, 2 or 3;
the L is 1 ～L 3 Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, bivalent substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group.
The beneficial effects are that: the compound of the formula I provided by the invention takes central benzene or N-heterocyclic benzene as a core, is connected with at least one benzo five-membered heterocycle and N-heterocyclic bridging group, has stronger rigidity, and forms a film layer with high compactness after the material is formed into a film, so that the film layer has higher stability; meanwhile, the compound shown in the formula I has higher glass transition temperature and better thermal stability, is not easy to decompose at high temperature, and can be used as a covering layer in an organic electroluminescent device, so that the light extraction effect can be effectively improved, the total reflection of light in the device can be reduced, the generation of Joule heat in the device can be reduced, and the luminous efficiency and the service life of the device can be improved.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes atoms in both its natural isotopic abundance and non-natural abundance.
In the present invention, "×" means a moiety attached to another substituent.
In the present invention, when the position of a substituent on a ring is not fixed, it means that it can be attached to any of the corresponding selectable positions of the ring. For example, the number of the cells to be processed,
Figure BDA0004077534800000031
can indicate->
Figure BDA0004077534800000032
Etc. And so on.
In this specification, when a substituent or linkage site is located across two or more rings, it is meant that it may be attached to either of the two or two rings, in particular to either of the respective selectable sites of the rings. For example, the number of the cells to be processed,
Figure BDA0004077534800000033
Can indicate->
Figure BDA0004077534800000034
Figure BDA0004077534800000035
Can indicate->
Figure BDA0004077534800000036
And so on.
Examples of the halogen atom according to the present invention may include fluorine, chlorine, bromine or iodine.
Alkyl according to the invention is understood to mean a monovalent radical obtained by removing one hydrogen atom from an alkane molecule, which may be a straight-chain alkyl radical or a branched alkyl radical, preferably having from 1 to 12 carbon atoms, more preferably having from 1 to 8 carbon atoms, particularly preferably having from 1 to 6 carbon atoms. Alkyl groups may be substituted or unsubstituted. Specific examples may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but are not limited thereto.
Alkenyl in the context of the present invention means a monovalent radical obtained by removing one hydrogen atom from an olefin molecule, which may be a straight-chain alkenyl or branched alkenyl radical, preferably having from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms, particularly preferably from 2 to 6 carbon atoms. Alkenyl groups may be substituted or unsubstituted. Specific examples may include vinyl, 1-propenyl, isopropenyl, butenyl, pentenyl, 3-methyl-1-butenyl, allyl, 1-phenylvinyl-1-yl, styryl, and the like, but are not limited thereto.
Cycloalkyl according to the invention is understood to mean a monovalent radical obtained by removal of one hydrogen atom from a cyclic alkane molecule, preferably from 3 to 12 carbon atoms, particularly preferably from 3 to 6 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted. The cycloalkyl group includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like.
Aryl as used herein refers to a monovalent group derived from an aromatic compound molecule by removal of one hydrogen atom from the aromatic nucleus carbon, which may be a monocyclic aryl, polycyclic aryl or fused ring aryl group, preferably having from 6 to 30 carbon atoms, more preferably from 6 to 18 carbon atoms, and most preferably from 6 to 12 carbon atoms. Aryl groups may be substituted or unsubstituted. The monocyclic aryl refers to aryl having only one aromatic ring in the molecule, for example, phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, for example, biphenyl, terphenyl, tetrabiphenyl, etc., but is not limited thereto; the condensed ring aryl group means an aryl group having two or more aromatic rings in the molecule and condensed with each other by sharing two adjacent carbon atoms, for example, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,
Figure BDA0004077534800000041
Phenyl, triphenylenyl, fluoranthenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, benzofluorenyl, 9' -spirobifluorenyl, and the like, but are not limited thereto.
Heteroaryl according to the present invention refers to the generic term for groups in which one or more of the aromatic nucleus carbon atoms in the aryl group is replaced by a heteroatom, including but not limited to O, S, N, si or P atoms, preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 3 to 12 carbon atoms. The attachment site of the heteroaryl group may be on a ring-forming carbon atom or on a ring-forming heteroatom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a fused ring heteroaryl group. Heteroaryl groups may be substituted or unsubstituted. The monocyclic heteroaryl group includes, but is not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, and the like; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, etc., but is not limited thereto; the fused ring heteroaryl group includes quinolinyl, isoquinolinyl, benzoquinolinyl, benzoisoquinolinyl, quinazolinyl, quinoxalinyl, benzoquinazolinyl, benzoquinoxalinyl, phenanthroline, naphthyridinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, N-heterobenzoxazolyl, N-heterobenzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, dibenzooxazolyl, dibenzoimidazolyl, dibenzozolyl, carbazolyl, benzocarbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenoxazinyl, spirofluorene oxaanthracenyl, spirofluorene thioanthracenyl, and the like, but is not limited thereto.
The aliphatic ring according to the present invention is a cyclic hydrocarbon having aliphatic properties, and the molecule contains a closed carbon ring, preferably 3 to 30 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms, and still more preferably 3 to 7 carbon atoms. Which may form mono-or polycyclic hydrocarbons and may be fully unsaturated or partially unsaturated. The aliphatic ring may be substituted or unsubstituted. Specific examples may include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and the like. The plurality of monocyclic hydrocarbons may also be linked in a variety of ways: two rings in the molecule can share one carbon atom to form a spiro ring; the two carbon atoms on the ring can be connected by a carbon bridge to form a bridge ring; several rings may also be interconnected to form a cage-like structure.
The fused ring of an aromatic ring and an aliphatic ring in the present invention means a ring having one or more aromatic rings and having one or more aliphatic rings fused to each other by sharing two adjacent carbon atoms, the aromatic ring preferably has 6 to 30 carbon atoms, more preferably has 6 to 18 carbon atoms, most preferably has 6 to 12 carbon atoms, and the aliphatic ring preferably has 3 to 30 carbon atoms, more preferably has 3 to 18 carbon atoms, more preferably has 3 to 12 carbon atoms, and most preferably has 3 to 7 carbon atoms. The fused ring of the aromatic ring and the aliphatic ring may be substituted or unsubstituted. Examples include, but are not limited to, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, benzocyclobutene, benzocyclopentene, benzocyclohexene, benzocycloheptene, naphthocyclopropane, naphthocyclobutane, naphthocyclopentane, naphthocyclohexene, naphthocyclopentene, naphthocyclohexene, and the like.
The arylene group according to the present invention is a generic term for divalent groups remaining after two hydrogen atoms are removed from the aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, preferably having 6 to 30 carbon atoms, more preferably having 6 to 22 carbon atoms, still more preferably having 6 to 18 carbon atoms, and most preferably having 6 to 12 carbon atoms. Arylene groups may be substituted or unsubstituted. The polycyclic arylene group may be, but is not limited to, biphenylene, terphenylene, tetra-biphenylene, and the like. As the condensed ring arylene group, naphthylene, anthrylene, phenanthrylene, pyreylene, fluorenylene, spirofluorenylene, triphenylene, perylene, fluoranthrylene, and phenylene groups may be mentioned
Figure BDA0004077534800000051
A base, etc., but is not limited thereto.
The heteroarylene group according to the present invention means a group in which two hydrogen atoms are removed from the nuclear carbon of an aromatic heterocycle composed of carbon and a heteroatom, which may be one or more of N, O, S, si, P, a monocyclic heteroarylene group, a polycyclic heteroarylene group or a condensed ring heteroarylene group, preferably having 2 to 30 carbon atoms, more preferably having 2 to 22 carbon atoms, still more preferably having 2 to 20 carbon atoms, most preferably 3 to 12 carbon atoms, and the heteroarylene group may be substituted or unsubstituted. Examples may include, but are not limited to, a pyridylene, a pyrimidylene, a pyrazinylene, a pyridazinylene, a triazinylene, a thienyl, a pyrrolylene, a furanylene, a pyranylene, an oxazolylene, a thiazolylene, an imidazolylene, a benzoxazolylene, a benzothiazolylene, a benzimidazolylene, a carbazolylene, a benzocarbazolylene, an acridinylene, an oxaanthracylene, a thioxanthoylene, a phenazinylene, a phenothiazinylene, a phenoxazinylene, an indolylene, a quinolinylene, an isoquinolylene, a benzothienyl, a benzofuranylene, a dibenzofuranylene, a dibenzothiophenylene, a quinoxalinylene, a quinazolinylene, a naphthyridineylene, a purinylene, a phenanthroline, and the like.
The fused ring group of the divalent aromatic ring and the aliphatic ring in the present invention means that there are two linked positions, i.e., a divalent group, on the fused ring group of the aromatic ring and the aliphatic ring. In addition to the divalent groups, the above description of the condensed ring groups of the aromatic ring and the aliphatic ring may be applied.
"unsubstituted" in "substituted or unsubstituted" as used herein means that the hydrogen atom on the group is not substituted with any substituent; "substituted" means that at least one hydrogen atom on the group is replaced with a substituent, and the position of substitution is not limited. When a plurality of hydrogens are substituted with a plurality of substituents, the plurality of substituents may be the same or different.
The substituents mentioned in the "substituted or unsubstituted" in the present invention may be the same or different from each other and are selected from deuterium, cyano, nitro, trifluoromethyl, halogen atom, substituted or unsubstituted C1-C12 alkyl group, substituted or unsubstituted C2-C12 alkenyl group, substituted or unsubstituted C3-C12 cycloalkyl group, substituted or unsubstituted C2-C12 heterocycloalkyl group, substituted or unsubstituted C6-C30 aryl group, and,Any one of substituted or unsubstituted heteroaryl groups of C2 to C30, substituted or unsubstituted aromatic rings of C6 to C30 and condensed ring groups of aliphatic rings of C3 to C30, preferably deuterium, cyano, halogen atom, trifluoromethyl, alkyl groups of C1 to C12, cycloalkyl groups of C3 to C12, aryl groups of C6 to C30, heteroaryl groups of C2 to C30, specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, tolyl, penta-phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, triphenylenyl,
Figure BDA0004077534800000052
A group, perylene group, fluoranthryl group, fluorenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, spirofluorenyl group, carbazolyl group, 9-phenylcarbazolyl group, 9' -spirobifluorenyl group, benzocyclopropyl group, benzocyclobutanyl group, benzocyclobutenyl group, spirofluorenyl group, and combinations thereof benzocyclopentylalkyl, benzocyclohexenyl, benzocycloheptyl, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, benzocycloheptenyl, naphthocyclopentenyl, naphthocyclohexenyl, naphthocycloheptanyl, naphthocyclopentenyl, benzocyclohexenyl, naphtyl and naphtyl naphthalocyclohexenyl, naphthaloheptenyl, pyrrolyl, furanyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothiophenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, benzimidazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, phenothiazinyl, phenoxazinyl, acridinyl and the like, but is not limited thereto.
The term "link-forming ring" as used herein means that two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:
Figure BDA0004077534800000061
In the present invention, the ring formed by the connection may be an aromatic ring system, an aliphatic ring system or a ring system formed by the fusion of both, and the ring formed by the connection may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentaacene, cyclohexene, cyclohexane acene, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, naphthalene, phenanthrene or pyrene, but is not limited thereto.
The invention provides an organic electroluminescent device, which comprises an anode, a cathode and an organic layer, wherein the organic layer comprises a covering layer, the covering layer has a structure shown in a formula I,
Figure BDA0004077534800000062
in formula I, the Ar 1 ～Ar 3 Is the same or different from each other, wherein at least one is selected from the group shown in a formula II, and the rest is the same or different from each other and is selected from any one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring groups;
Figure BDA0004077534800000063
in formula II, the L 0 Any one selected from the group consisting of the following groups and combinations thereof;
Figure BDA0004077534800000064
z is identical or different from each other and is selected from CH or N atoms, and at least one Z in each group is selected from N atoms; when Z is bonded to other groups, the Z is selected from C atoms;
The R is 1 Are the same or different from each other and are selected from hydrogen, deuterium, cyano, trifluoromethyl,Any one of halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
the a 1 Selected from 0, 1, 2 or 3, said a 2 Selected from 0, 1, 2, 3, 4 or 5; when two or more R's are present 1 When two or more R' s 1 Identical or different from each other, or adjacent two R' s 1 May be linked to each other to form a substituted or unsubstituted ring;
the x is 1 Selected from O, S, NR a Any one of them; the R is a Any one selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;
y, equal to or different from each other, is selected from CH or N atoms;
the R, R' are the same or different from each other and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
Said m is selected from 0, 1, 2, 3 or 4; when two or more R's are present, two or more R's may be the same or different from each other, or adjacent two R's may be connected to each other to form a substituted or unsubstituted ring;
said m' is selected from 0, 1 or 2;
the x are identical or different from each other and are selected from CH or N atoms, and when x is bonded with other groups, the x is selected from C atoms;
the R is 2 Selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 arylAny one of a group, a substituted or unsubstituted C2 to C30 heteroaryl group;
said n is selected from 0, 1, 2 or 3;
the L is 1 ～L 3 Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, bivalent substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group.
Preferably, ar in formula I 1 -L 1 -*、Ar 2 -L 2 Ar & lt- & gt 3 -L 3 Groups are attached to each other in meta form on the central ring.
Preferably, x on the central ring in formula I is selected from CH and the central ring is selected from benzene rings.
Preferably, 1, 2 or 3 x on the central ring in formula I are selected from N atoms, the remainder being selected from CH. More preferably, the center ring is selected from any one of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, and a triazine ring.
Preferably Ar 1 ～Ar 3 One of them is selected from the group represented by formula II, more preferably Ar 1 、Ar 2 Or Ar 3 Selected from the group represented by formula II.
Preferably Ar 1 ～Ar 3 Two of (a) are selected from the group represented by formula II, more preferably Ar 1 And Ar is a group 2 ，Ar 1 And Ar is a group 3 Or Ar 2 And Ar is a group 3 Selected from the group represented by formula II.
Preferably Ar 1 ～Ar 3 Are selected from the group shown in formula II.
Preferably, the L 0 Any one selected from the following groups;
Figure BDA0004077534800000081
z is identical or different from each other and is selected from CH or N atoms, and at least one Z in each group is selected from N atoms; when Z is bonded to other groups, the Z is selected from C atoms;
the R is 1 Identical or different from each other, selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, pyridinyl or pyrimidinyl;
The a 1 Selected from 0, 1, 2 or 3, said a 2 Selected from 0, 1, 2, 3, 4 or 5, said a 3 Selected from 0, 1, 2, 3 or 4, said a 4 Selected from 0, 1, 2, 3, 4, 5 or 6.
Preferably, the L 0 Any one selected from the following groups;
Figure BDA0004077534800000082
Figure BDA0004077534800000091
preferably, the said
Figure BDA0004077534800000092
Any one selected from the following groups;
Figure BDA0004077534800000093
the R, R' groups are identical or different from each other and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen or substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, pyridinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl or quinoxalinyl;
the m is 1 Selected from 0, 1, 2, 3 or 4, said m 2 Selected from 0, 1, 2 or 3, said m 3 Selected from 0, 1 or 2, said m 4 Selected from 0 or 1, when two or more R are present, two or more R are the same or different from each other, or two adjacent R may be linked to each other to form a substituted or unsubstituted ring;
the m 'is selected from 0, 1 or 2, and the m' is selected from 0 or 1.
Preferably, the said
Figure BDA0004077534800000094
Any one selected from the following groups;
Figure BDA0004077534800000095
Figure BDA0004077534800000101
the x is 1 Are identical or different from each other and are selected from O, S or NR a Any one of them;
the R is a Selected from hydrogen, deuterium or any one of the following groups substituted or unsubstituted by one or more deuterium, C1 to C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, triphenylyl, pyridinyl or pyrimidinyl;
said b 1 Selected from 0, 1, 2, 3, 4 or 5, said b 2 Selected from 0, 1, 2, 3 or 4, said b 3 Selected from 0, 1, 2, 3, 4, 5, 6 or 7.
Preferably, the Ar 1 ～Ar 3 Are identical or different from each other, at least one of them is selected from the group shown in formula II, and the others are identical or different from each other, and are selected from any of the groups shown in the followingOne of the two;
Figure BDA0004077534800000102
the R is 3 Are the same or different from each other, and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
The c 1 Selected from 0, 1, 2, 3, 4 or 5, said c 2 Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said c 3 Selected from 0, 1, 2, 3 or 4, said c 4 Selected from 0, 1, 2, 3, 4, 5 or 6; when two or more R's are present 3 When two or more R' s 3 Identical or different from each other, or adjacent two R' s 3 May be linked to each other to form a substituted or unsubstituted ring;
said Q is selected from O, S, C (R b )(R c )、N(R d ) Any one of them;
the R is b 、R c 、R d Are identical or different from each other and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R b 、R c Can be linked to each other to form a substituted or unsubstituted ring, or R b 、R c 、R d Can be combined with L 1 ～L 3 Any one of which is directly bonded;
the t are the same or different from each other and are selected from CH or N atoms, and 1, 2, 3 or 4 t are selected from N atoms in the formula III-4, and 1, 2, 3, 4, 5 or 6 t are selected from N atoms in the formula III-5; when t is bonded to other groups, said t is selected from a C atom;
said z 1 Selected from O, S or C (R) e ) The method comprises the steps of carrying out a first treatment on the surface of the Said z 2 Selected from C (R) f ) Or N;
the R is e 、R f Are the same or different from each other, and are selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl.
Preferably, said R 3 Identical to or different from each other, selected from hydrogen, deuterium or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, pyridinyl or pyrimidinyl.
Preferably, when two or more R's are present 3 When two or more R' s 3 Identical or different from each other, or adjacent two R' s 3 Can be connected with each other to form any one of a substituted or unsubstituted ternary ring, a quaternary ring, a five-membered ring, a six-membered ring, a benzene ring and a naphthalene ring.
Preferably, the Ar 1 ～Ar 3 Is the same or different from each other, wherein at least one is selected from the group shown in the formula II, and the rest is the same or different from each other and is selected from any one of the groups shown in the following;
Figure BDA0004077534800000111
Figure BDA0004077534800000121
the R is 4 Identical to or different from each other, selected from hydrogen, deuterium or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, ice-reducing A lamellar alkyl, phenyl, biphenyl, naphthyl, pyridinyl or pyrimidinyl group;
said d 1 Selected from 0, 1, 2, 3, 4 or 5, said d 2 Selected from 0, 1, 2, 3 or 4, said d 3 Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said d 4 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said d 5 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said d 6 Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said d 7 Selected from 0, 1, 2, 3, 4, 5 or 6, said d 8 Selected from 0, 1, 2 or 3;
the R is b 、R c 、R d Identical to or different from each other, selected from hydrogen, deuterium or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl, naphthalene, pyridinyl, or pyrimidinyl;
the L is a 、L b Are identical or different from each other, and are selected from any one of single bond, substituted or unsubstituted: phenylene, biphenylene, naphthylene, pyridylene or pyrimidinylene;
the ring A is selected from a spiro structure, and the spiro structure is selected from any one of the following groups:
Figure BDA0004077534800000122
The R is 5 Are the same or different from each other, and are selected from any one of hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl and naphthyl;
said e 1 Selected from 0, 1, 2, 3 or 4, said e 2 Selected from 0, 1, 2, 3, 4, 5 or 6, said e 3 Independently selected from 0, 1, 2, 34, 5, 6, 7 or 8, said e 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, said e 5 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, said e 6 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.
Preferably, the Ar 1 ～Ar 3 Is the same or different from each other, wherein at least one is selected from the group shown in the formula II, and the rest is the same or different from each other and is selected from any one of the groups shown in the following;
Figure BDA0004077534800000131
Figure BDA0004077534800000141
Figure BDA0004077534800000151
Figure BDA0004077534800000161
Figure BDA0004077534800000171
preferably, the L 1 ～L 3 Are the same or different from each other, and are selected from any one of single bonds or groups shown below;
Figure BDA0004077534800000172
the R is 6 Identical or different from each other, selected from hydrogen, deuterium or a C1-C12 alkyl group substituted or unsubstituted by one or more deuterium, a C3-C12 cycloalkyl group substituted or unsubstituted, a C6-C30 aryl group substituted or unsubstituted Any one of substituted or unsubstituted C2 to C30 heteroaryl groups;
the s is 1 Selected from 0, 1, 2, 3 or 4, said s 2 Selected from 0, 1, 2, 3, 4 or 5, said s 3 Selected from 0, 1, 2 or 3, said s 4 Selected from 0, 1 or 2, said s 5 Selected from 0, 1, 2, 3, 4, 5 or 6;
the R is x 、R y 、R z Are identical or different from each other and are selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R x 、R y May be linked to each other to form a substituted or unsubstituted ring;
the V's are the same or different from each other and are selected from CH or N atoms, and at least one V in each group is selected from N atoms; when V is bonded to other groups, said V is selected from a C atom;
the ring B is selected from the group consisting of substituted or unsubstituted C3-C7 aliphatic rings.
Preferably, the ring B is selected from any one of substituted or unsubstituted,
Figure BDA0004077534800000173
wherein "+" represents a cyclic attachment site; the dotted line represents a single bond or a double bond.
Preferably, the L 1 ～L 3 Are the same or different from each other, and are selected from any one of single bonds or groups shown below;
Figure BDA0004077534800000181
preferably, the cover layer is selected from any one of the following structures;
Figure BDA0004077534800000182
Figure BDA0004077534800000191
Figure BDA0004077534800000201
Figure BDA0004077534800000211
Figure BDA0004077534800000221
Figure BDA0004077534800000231
Figure BDA0004077534800000241
Figure BDA0004077534800000251
Figure BDA0004077534800000261
Figure BDA0004077534800000271
Figure BDA0004077534800000281
Figure BDA0004077534800000291
Figure BDA0004077534800000301
Figure BDA0004077534800000311
Figure BDA0004077534800000321
Figure BDA0004077534800000331
Figure BDA0004077534800000341
Figure BDA0004077534800000351
Figure BDA0004077534800000361
Figure BDA0004077534800000371
Figure BDA0004077534800000381
Figure BDA0004077534800000391
Figure BDA0004077534800000401
Figure BDA0004077534800000411
Figure BDA0004077534800000421
Figure BDA0004077534800000431
Figure BDA0004077534800000441
Figure BDA0004077534800000451
The specific structural forms of the compounds of formula I according to the present invention are listed above, but the present invention is not limited to these chemical structures, and substituents are included in the compounds of formula I based on the structures of formula I.
The invention provides a preparation method of a compound represented by a formula I, but the preparation method of the invention is not limited to the method, and a specific synthetic route is as follows: preparation of formula I:
1. when Ar is 1 -L 1 -*、Ar 2 -L 2 -*、Ar 3 -L 3 When the phases are identical to each other,
Figure BDA0004077534800000452
2. when Ar is 1 -L 1 -*、Ar 2 -L 2 When the phases are identical to each other,
Figure BDA0004077534800000461
3. when Ar is 1 -L 1 -*、Ar 2 -L 2 -*、Ar 3 -L 3 When the phases are different from each other,
Figure BDA0004077534800000462
preparation of formula II:
Figure BDA0004077534800000463
wherein X is a 、X b Are the same or different from each other and are selected from any one of Cl, br and I; ar (Ar) 1 ～Ar 3 、L 0 ～L 3 、x、x 1 、R、R’、R 2 The definition of Y, n, m, m' is the same as above; the sources of raw materials used in the preparation route can be commercial products or can be prepared by methods well known to those skilled in the art.
The organic electroluminescent device comprises an anode, a hole transmission area, a luminescent layer, an electron transmission area, a cathode, a cover layer and other functional layers. Each functional layer may be composed of a single layer, a double layer, or a multi-layer thin film, and each thin film may be composed of one material or two or more materials, however, the structure of the organic electroluminescent device is not limited thereto.
Preferably, the hole transport region according to the present invention includes at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.
Preferably, the hole transport layer according to the present invention comprises a first hole transport layer and/or a second hole transport layer.
Preferably, the electron transport region according to the present invention includes at least one of an electron injection layer, an electron transport layer, and a hole blocking layer.
Preferably, the electron transport layer according to the present invention comprises a first electron transport layer and/or a second electron transport layer.
Preferably, the cover layer of the present invention comprises any one or more of the compounds of formula I of the present invention.
Preferably, the cover layer according to the present invention comprises a first cover layer and/or a second cover layer, wherein the first cover layer and/or the second cover layer comprises any one or more of the compounds of formula I according to the present invention.
The organic electroluminescent device of the present invention is generally formed on a substrate. The substrate may be a substrate made of glass, plastic, polymer film, silicon, or the like, as long as it is not changed when an electrode is formed or an organic layer is formed.
The anode material according to the present invention preferably uses a material having a high function to improve hole injection efficiency. Anode materials useful in the present invention are selected from the following: indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and tin oxide (SnO) 2 ) Zinc oxide (ZnO) or any combination thereof, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof. The anode may have a single-layer structure or a multi-layer structure including two or more layers, for example, the anode may have a single-layer structure of Al or a three-layer structure of ITO/Ag/ITO, but is not limited thereto.
The hole injection layer material of the present invention is preferably a material having a suitable HOMO value to facilitate hole injection and transport. Can be selected from any one or more of the following structures: metalloporphyrins, oligothiophenes, arylamine derivatives, hexanitrile hexaazabenzophenanthrene compounds, phthalocyanine compounds, polycyano conjugated organic materials, quinacridone compounds, anthraquinone compounds, and conductive polymers based on polyaniline and polythiophene, etc., but are not limited thereto.
The hole transport layer material according to the present invention is preferably a material having high hole mobility. Can be selected from any one or more of the following structures: carbazole derivatives, triarylamine derivatives, biphenyldiamine derivatives, fluorene derivatives, stilbene derivatives, hexanitrile hexaazabenzophenanthrene compounds, quinacridone compounds, anthraquinone compounds, polyaniline, polythiophene, polyvinylcarbazole, and the like. Examples of the hole transport layer material include, but are not limited to, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), N '-tetrakis (3-methylphenyl) -3,3' -dimethylbiphenyl diamine (HMTPD), and the like.
The luminescent layer material comprises a host material AND a doping material, AND the luminescent layer host material can be selected from 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4 '-tris (carbazole-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (alpha-AND), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4',1": 4',1 '-tetrabenzoyl ] -4, 4' -diamine group (4 PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), AND the like. In addition to the above materials and combinations thereof, the light emitting layer host material may include other known materials suitable for a light emitting layer, and the like, but is not limited thereto. The light-emitting layer doping material of the present invention is classified into a blue light-emitting material, a green light-emitting material, and a red light-emitting material. The light emitting layer doping material may be selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyren-1-amine) (DPAP-DPPA), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4 '-bis [4- (diphenylamino) styryl ] biphenyl (BDAVBi), 4' -bis [4- (di-p-tolylamino) styryl ] biphenyl (DPAVBi), bis (2-hydroxyphenylpyridine) beryllium (Bepp 2), bis (4, 6-difluorophenylpyridine-C2, N) picolinic iridium (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy) 3), bis (2-phenylpyridine) iridium (Ir (ppy) 2 (acac)), 9, 10-bis [ N- (p-tolyl) anilino ] anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylpyridine-C2, N ] iridium (Ir) (p-phenylpyridine) iridium (p-phenylene) iridium (p-phenylene) 2), tris (p-phenylpyridine) iridium (Ir (p-phenylene) iridium (Ir) 2 (Ir (p-p) iridium) (Ir (q) (Ir) 3), iridium (Ir).
The doping ratio of the host material and the guest material in the light-emitting layer according to the present invention is determined according to the materials used. The amount of the dopant is preferably 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, still more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.
The hole blocking layer material is preferably a material capable of effectively blocking hole transport and enabling excitons to be recombined in a light emitting layer rather than an electron transport layer, and can be selected from any one or more of the following structures besides the nitrogen-containing heterocyclic derivatives provided by the invention: phenanthroline derivatives, rare earth derivatives, imidazole derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, azabenzene derivatives, anthrone derivatives, and the like, but are not limited thereto.
The electron transport layer material of the present invention is preferably a material having high electron mobility. Can be selected from any one or more of the following structures: 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), tris (8-hydroxyquinoline) aluminum (III) (Alq 3), 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-t-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like, but are not limited thereto.
The electron injection layer material of the present invention is preferably a material having a small potential barrier difference from a material of an adjacent organic layer, and specific examples may include: alkali metal compounds (for example, lithium oxide, lithium fluoride, cesium carbonate, cesium fluoride, 8-hydroxyquinoline cesium, 8-hydroxyquinoline aluminum), organic metal salts (metal acetate, metal benzoate, or metal stearate), molybdenum trioxide, metal aluminum, and the like, but are not limited thereto.
The cathode material according to the present invention preferably uses a material having a low work function that can promote electron injection into the organic layer to lower the electron injection barrier. Can be selected from any one or more of the following materials: ag. Mg, cu, al, pt, pd, au, ni, nd, ir, cr, li, ca, liF/Ca, liF/Al, mo, ti, compounds including them or mixtures thereof (e.g., mixtures of Ag and Mg), but are not limited thereto.
The cover layer is provided outside one or more of the anode and the cathode, thereby reducing total reflection loss of light and improving light extraction efficiency. Can be selected from any one or more of the following structures: arylamine derivatives, biscarbazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, triazole derivatives, benzofuran derivatives, diamine derivatives, porphyrin derivatives, phthalocyanine derivatives, alq 3 TPBi or mixtures thereof, but are not limited thereto. Preferred are compounds of formula I according to the invention.
The thickness of each organic layer of the organic electroluminescent device is not particularly limited, and may be any thickness commonly used in the art.
The organic electroluminescent device according to the present invention can be manufactured by sequentially laminating the above-described structures. The production method may be a known method such as a wet film forming method or a dry film forming method. Specific examples of the wet film forming method include: various coating methods such as spin coating, dipping, casting, and ink jet are specific examples of dry film forming methods: vacuum deposition, sputtering, plasma, ion plating, and the like, but is not limited thereto.
The organic light-emitting device can be widely applied to the fields of panel display, illumination light sources, flexible OLED, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, indication boards, signal lamps and the like.
The present invention is explained more fully by the following examples, but is not intended to be limited thereby. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue burden.
Preparation and characterization of the Compounds
Description of the starting materials, reagents and characterization equipment:
the source of the raw materials used in the following examples is not particularly limited and may be commercially available products or prepared by a preparation method well known to those skilled in the art.
The mass spectrum uses a Wotes G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer in UK, chloroform as a solvent;
the elemental analysis uses a Vario EL cube type organic elemental analyzer of Elementar, germany, and the mass of the sample is 5-10 mg;
synthesis example 1: preparation of intermediate M-1:
Figure BDA0004077534800000481
preparation of intermediate M1-1:
under the protection of nitrogen, the raw materials m-1 (34.64 g,180.00 mmol), the bisboronic acid pinacol ester (50.79 g,200.00 mmol) and K are reacted 2 CO 3 (74.63g，540.00mmol)、Pd(PPh 3 ) 4 (6.24 g,5.40 mmol) was added to DMF (850 mL), the mixture of the above reactants was heated under reflux for 6h, after the reaction was completed, the reaction mixture was cooled to room temperature, distilled water was added, extracted with dichloromethane, left to stand for separation, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by distillation under reduced pressure, and the obtained solid was recrystallized from ethyl acetate and dried to give intermediate M1-1 (37.94 g, 88%); HPLC purity ∈ 98.81%. Mass spectrum m/z:239.0871 (theory: 239.0884).
Preparation of intermediate M2-1:
under the protection of nitrogen, raw material n-1 (31.52 g,160.00 mmol), intermediate M1-1 (35.93 g,150.00 mmol) and K are mixed 2 CO 3 (41.46g，300.00mmol)、Pd(PPh 3 ) 4 (3.47 g,3.00 mmol) was added to 570mL toluene, 190mL ethanol, 190mL water, the mixture of the above reactants was heated to reflux for 5h, after the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was purified with toluene/ethanol=4: 1 recrystallisation and drying to give intermediate M2-1 (28.25 g, 82%); HPLC purity. Mass spectrum m/z:229.0284 (theory: 229.0294).
Preparation of intermediate M-1:
intermediate M2-1 (27.56 g,120.00 mmol) was taken under nitrogen protectionPinacol ester (33.52 g,132.00 mmol), K 2 CO 3 (49.75g，360.00mmol)、Pd(PPh 3 ) 4 (4.16 g,3.60 mmol) was added to DMF (560 mL), the mixture of the above reactants was heated under reflux for 3.5h, after the reaction was completed, the reaction mixture was cooled to room temperature, distilled water was added, extracted with dichloromethane, left to stand for separation, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by distillation under reduced pressure, and the obtained solid was recrystallized from ethyl acetate and dried to give intermediate M-1 (33.15 g, 86%); HPLC purity ∈ 98.83%. Mass spectrum m/z:321.1545 (theory: 321.1536).
The intermediate M can be prepared by correspondingly replacing the raw materials according to the preparation method of the intermediate M-1 in the synthesis example 1, wherein the raw materials are shown in the following table:
Figure BDA0004077534800000491
Figure BDA0004077534800000501
Figure BDA0004077534800000511
Synthesis example 2: preparation of Compound 1:
Figure BDA0004077534800000512
under the protection of nitrogen, g-1 (9.44 g,30.00 mmol), M-1 (30.51 g,95.00 mmol) K 2 CO 3 (14.51 g,105.00 mmol) was added to 240ml tetrahydrofuran and 60ml distilled water, pd (PPh) was added with stirring 3 ) 4 (0.52 g,0.45 mmol) and refluxing the mixture of the above reactants for 5h, cooling to room temperature after the reaction, adding distilled water, extracting with dichloromethane, standing for separating, collecting the organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating by distillation under reduced pressureThe filtrate was cooled to crystallize, suction-filtered, and the obtained solid was recrystallized from toluene to give compound 1 (15.00 g, 76%), with HPLC purity ≡ 99.97%. Mass spectrum m/z:657.2069 (theory: 657.2052). Theoretical element content (%) C 45 H 27 N 3 O 3 : c,82.18; h,4.14; n,6.39. Measured element content (%): c,82.21; h,4.11; n,6.43.
Synthesis example 3: preparation of Compound 89:
Figure BDA0004077534800000521
preparation of intermediate I-89:
under nitrogen, g-89 (11.29 g,50.00 mmol), A-89 (12.40 g,50.00 mmol), KOAc (9.81 g,100.00 mmol) were added to 400ml tetrahydrofuran and 100ml distilled water, pd (dppf) Cl with stirring 2 (0.37 g,0.50 mmol) of the above-mentioned mixed solution of the reactants was heated and refluxed for 3 hours, after the reaction was completed, cooled to room temperature, distilled water was added, extracted with methylene chloride, left to stand for separation, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, concentrated by distillation under reduced pressure to give a filtrate, cooled and crystallized, suction-filtered, and the obtained solid was recrystallized from ethyl acetate to give intermediate I-89 (13.97 g, 80%), with HPLC purity of 99.84%. Mass spectrum m/z:348.0465 (theory: 348.0473).
Preparation of Compound 89:
i-89 (10.48 g,30.00 mmol), M-1 (20.23 g,63.00 mmol), K were purged with nitrogen 2 CO 3 (10.37 g,75.00 mmol) was added to 240ml tetrahydrofuran and 60ml distilled water, and Pd (PPh) was added with stirring 3 ) 4 (0.35 g,0.30 mmol) of the above-mentioned mixed solution of the reactants was heated and refluxed for 4.5 hours, after the completion of the reaction, cooled to room temperature, distilled water was added, extracted with methylene chloride, left to stand for separation, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, concentrated by distillation under reduced pressure to give a filtrate, cooled and crystallized, suction-filtered, and the obtained solid was recrystallized from toluene to give compound 89 (15.60 g, 78%), with an HPLC purity of > 99.92%. Mass spectrum m/z:666.2322 (theory: 666.2307). Theoretical element content (%)C 48 H 30 N 2 O 2 : c,86.46; h,4.54; n,4.20. Measured element content (%): c,86.50; h,4.59; n,4.17.
Synthesis example 4: preparation of compound 96:
Figure BDA0004077534800000522
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-96 and M-1 was replaced with equimolar M-96, compound 96 (13.81 g) was obtained with an HPLC purity of ≡ 99.95%. Mass spectrum m/z:597.2424 (theory: 597.2434). Theoretical element content (%) C 42 H 19 D 7 N 2 O 2 : c,84.40; h,5.56; n,4.69. Measured element content (%): c,84.37; h,5.59; n,4.73.
Synthesis example 5: preparation of Compound 97:
Figure BDA0004077534800000531
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-97 and M-1 was replaced with equimolar M-97, compound 97 (14.60 g) was obtained with an HPLC purity of ≡ 99.97%. Mass spectrum m/z:648.2538 (theory: 648.2525). Theoretical element content (%) C 44 H 32 N 4 O 2 : c,81.46; h,4.97; n,8.64. Measured element content (%): c,81.50; h,4.94; n,8.66.
Synthesis example 6: preparation of compound 98:
Figure BDA0004077534800000532
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-98 and M-1 was replaced with equimolar M-98, compound 98 (15.91 g) was obtained with an HPLC purity of ≡ 99.91%. Mass spectrum m/z:716.2450 (theory: 716.2464). Theoretical element content (%)C 52 H 32 N 2 O 2 : c,87.13; h,4.50; n,3.91. Measured element content (%): c,87.09; h,4.47; n,3.96.
Synthesis example 7: preparation of compound 110:
Figure BDA0004077534800000533
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-110 and M-1 was replaced with equimolar M-110, compound 110 (15.48 g) was obtained with an HPLC purity of ≡ 99.94%. Mass spectrum m/z:716.2479 (theory: 716.2464). Theoretical element content (%) C 52 H 32 N 2 O 2 : c,87.13; h,4.50; n,3.91. Measured element content (%): c,87.16; h,4.55; n,3.88.
Synthesis example 8: preparation of compound 124:
Figure BDA0004077534800000541
preparation of intermediate I-124:
under nitrogen, g-124 (25.39 g,80.00 mmol), A-124 (16.57 g,80.00 mmol), KOAc (15.70 g,160.00 mmol) were added to 640ml tetrahydrofuran and 160ml distilled water, pd (dppf) Cl with stirring 2 (0.59 g,0.80 mmol) the mixture of the above reactants was heated and refluxed for 3.5 hours, after the reaction was completed, cooled to room temperature, distilled water was added, extracted with methylene chloride, left to stand for separation, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, concentrated by distillation under reduced pressure to give filtrate, cooled and crystallized, suction-filtered, and the obtained solid was recrystallized from ethyl acetate to give intermediate I-124 (22.29 g, 79%) with an HPLC purity of 99.83%. Mass spectrum m/z:351.0366 (theory: 351.0376).
Preparation of intermediate II-124:
i-124 (17.64 g,50.00 mmol), M-1 (16.06 g,50.00 mmol), KOAc (9.81 g,100 mmol) were added to 400ml tetrahydrofuran and 100ml distilled water under nitrogen blanket, stirredPd (OAc) was added under stirring 2 (0.11 g,0.50 mmol) of the above-mentioned mixed solution of the reactants was heated and refluxed for 3 hours, after the reaction was completed, cooled to room temperature, distilled water was added, extracted with methylene chloride, left to stand for separation, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, concentrated by distillation under reduced pressure to give a filtrate, cooled and crystallized, suction-filtered, and the obtained solid was recrystallized from ethyl acetate to give intermediate II-124 (17.75 g, 76%) having an HPLC purity of 99.87%. Mass spectrum m/z:466.1782 (theory: 466.1798).
Preparation of compound 124:
under nitrogen, II-124 (14.01 g,30.00 mmol), M-124 (11.13 g,33.00 mmol), K 2 CO 3 (8.29 g,60.00 mmol) was added to 240ml tetrahydrofuran and 60ml distilled water, pd (PPh) was added with stirring 3 ) 4 (0.35 g,0.30 mmol) and the mixture of the above reactants was heated under reflux for 4h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by reduced pressure distillation, cooling for crystallization, suction filtering, and recrystallizing the obtained solid with toluene to obtain a compound 124 (13.48 g, 70%), wherein the HPLC purity is not less than 99.98%. Mass spectrum m/z:641.2496 (theory: 641.2487). Theoretical element content (%) C 44 H 19 D 9 N 2 OS: c,82.34; h,5.81; n,4.36. Measured element content (%): c,82.31; h,5.77; n,4.38.
Synthesis example 9: preparation of compound 160:
Figure BDA0004077534800000542
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-160 and M-1 was replaced with equimolar M-160, compound 160 (17.44 g) was obtained with an HPLC purity of ≡ 99.93%. Mass spectrum m/z:818.2947 (theory: 818.2933). Theoretical element content (%) C 60 H 38 N 2 O 2 : c,88.00; h,4.68; n,3.42. Measured element content (%): c,88.03; h,4.72; n,3.38.
Synthesis example 10: preparation of compound 168:
Figure BDA0004077534800000551
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-168 and M-1 was replaced with equimolar M-168, compound 168 (16.05 g) was obtained with an HPLC purity of ≡ 99.96%. Mass spectrum m/z:742.2355 (theory: 742.2369). Theoretical element content (%) C 52 H 30 N 4 O 2 : c,84.08; h,4.07; n,7.54. Measured element content (%): c,84.10; h,4.11; n,7.50.
Synthesis example 11: preparation of compound 173:
Figure BDA0004077534800000552
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-173 and M-1 was replaced with equimolar M-173, compound 173 (14.85 g) was obtained with an HPLC purity of ≡ 99.92%. Mass spectrum m/z:668.2228 (theory: 668.2212). Theoretical element content (%) C 46 H 28 N 4 O 2 : c,82.62; h,4.22; n,8.38. Measured element content (%): c,82.57; h,4.25; n,8.40.
Synthesis example 12: preparation of compound 180:
Figure BDA0004077534800000553
according to the same manner as that of Synthesis example 3 except that g-89 was replaced with equimolar g-180 and A-89 was replaced with equimolar A-180, compound 180 (15.07 g) was obtained with an HPLC purity of ≡ 99.91%. Mass spectrum m/z:727.3289 (theory: 727.3278). Theoretical element content (%) C 52 H 37 D 3 N 2 O 2 : c,85.80; h,5.95; n,3.85. Measured element content (%): c,85.78; h,5.98; n,3.89.
Synthesis example 13: preparation of Compound 187:
Figure BDA0004077534800000554
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-187 and M-1 was replaced with equimolar M-187, compound 187 (15.69 g) was obtained with an HPLC purity of ≡ 99.92%. Mass spectrum m/z:768.2516 (theory: 768.2525). Theoretical element content (%) C 54 H 32 N 4 O 2 : c,84.36; h,4.20; n,7.29. Measured element content (%): c,84.40; h,4.17; n,7.31.
Synthesis example 14: preparation of compound 223:
Figure BDA0004077534800000561
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-96 and M-1 was replaced with equimolar A-223, compound 223 (15.41 g) was obtained with an HPLC purity of ≡ 99.97%. Mass spectrum m/z:675.2550 (theory: 675.2562). Theoretical element content (%) C 51 H 33 NO: c,90.64; h,4.92; n,2.07. Measured element content (%): c,90.66; h,4.89; n,2.11.
Synthesis example 15: preparation of compound 276:
Figure BDA0004077534800000562
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-276 and M-1 was replaced with equimolar A-276, compound 276 (14.83 g) was obtained with an HPLC purity of ≡ 99.94%. Mass spectrum m/z:641.2185 (theory: 641.2177). Theoretical element content (%) C 47 H 31 NS: c,87.95; h,4.87; n,2.18. Measured element content (%): c,87.91; h,4.90; n,2.20.
Synthesis example 16: preparation of compound 288:
Figure BDA0004077534800000563
according to the same manner as that of Synthesis example 8 except that A-124 was replaced with equimolar A-288, M-1 was replaced with equimolar B-288 and M-124 was replaced with equimolar M-288, compound 288 (13.73 g) was obtained with an HPLC purity of ≡ 99.93%. Mass spectrum m/z:635.3141 (theory: 635.3126). Theoretical element content (%) C 47 H 33 D 4 NO: c,88.78; h,6.50; n,2.20. Measured element content (%): c,88.81; h,6.46; n,2.15.
Synthesis example 17: preparation of Compound 291:
Figure BDA0004077534800000571
according to a production method similar to that of Synthesis example 8, A-124 was replaced with equimolar A-291, M-1 was replaced with equimolar B-291, and M-124 was replaced with equimolar M-291, whereby Compound 291 (13.56 g) was obtained, and HPLC purity was ≡ 99.91%. Mass spectrum m/z:645.2798 (theory: 645.2780). Theoretical element content (%) C 46 H 35 N 3 O: c,85.55; h,5.46; n,6.51. Measured element content (%): c,85.58; h,5.50; n,6.49.
Synthesis example 18: preparation of compound 330:
Figure BDA0004077534800000572
according to the same manner as that of Synthesis example 8 except that A-124 was replaced with equimolar A-223, M-1 was replaced with equimolar B-330 and M-124 was replaced with equimolar M-1, compound 330 (15.11 g) was obtained with an HPLC purity of ≡ 99.94%. Mass spectrum m/z:689.2341 (theory: 689.2355). Theoretical element content (%) C 51 H 31 NO 2 : c,88.80; h,4.53; n,2.03. Measured element content (%): c,88.77;H,4.49；N,2.08。
synthesis example 19: preparation of compound 476:
Figure BDA0004077534800000573
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-1 and M-1 was replaced with equimolar A-476, compound 476 (14.99 g) was obtained with an HPLC purity of ≡ 99.98%. Mass spectrum m/z:703.2130 (theory: 703.2147). Theoretical element content (%) C 51 H 29 NO 3 : c,87.04; h,4.15; n,1.99. Measured element content (%): c,87.08; h,4.12; n,1.94.
Synthesis example 20: preparation of Compound 499:
Figure BDA0004077534800000581
according to the same manner as that of Synthesis example 3, g-89 was replaced with equimolar g-499, A-89 was replaced with equimolar M-499, and M-1 was replaced with equimolar A-499, to give Compound 499 (17.37 g), and HPLC purity was > 99.95%. Mass spectrum m/z:863.2076 (theory: 863.2065). Theoretical element content (%) C 59 H 33 N 3 OS 2 : c,82.01; h,3.85; n,4.86. Measured element content (%): c,82.04; h,3.81; n,4.90.
Synthesis example 21: preparation of compound 508:
Figure BDA0004077534800000582
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-508 and M-1 was replaced with equimolar A-508, compound 508 (17.63 g) was obtained with an HPLC purity of ≡ 99.91%. Mass spectrum m/z:903.3268 (theory: 903.3250). Theoretical element content (%) C 67 H 41 N 3 O: c,89.01; h,4.57; n,4.65. Measured element content (%):C,89.03；H,4.60；N,4.61。
synthesis example 22: preparation of compound 516:
Figure BDA0004077534800000583
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-516 and M-1 was replaced with equimolar M-124, compound 516 (15.48 g) was obtained with an HPLC purity of ≡ 99.93%. Mass spectrum m/z:706.1331 (theory: 706.1320). Theoretical element content (%) C 44 H 26 N 4 S 3 : c,74.76; h,3.71; n,7.93. Measured element content (%): c,74.78; h,3.68; n,7.89.
Synthesis example 23: preparation of compound 538:
Figure BDA0004077534800000591
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-223 and M-1 was replaced with equimolar M-538, compound 538 (15.73 g) was obtained with an HPLC purity of ≡ 99.96%. Mass spectrum m/z:698.1832 (theory: 698.1850). Theoretical element content (%) C 48 H 30 N 2 S 2 : c,82.49; h,4.33; n,4.01. Measured element content (%): c,82.51; h,4.30; n,4.05.
Synthesis example 24: preparation of compound 552:
Figure BDA0004077534800000592
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-552 and M-1 was replaced with equimolar M-552, compound 552 (17.28 g) was obtained with an HPLC purity of ≡ 99.92%. Mass spectrum m/z:822.2150 (theory: 822.2163). Theoretical element content (%) C 58 H 34 N 2 S 2 : c,84.64; h,4.16; n,3.40. Measured element content (%)：C,84.67；H,4.20；N,3.36。
Synthesis example 25: preparation of compound 580:
Figure BDA0004077534800000593
according to the same manner as that of Synthesis example 8 except that A-124 was replaced with equimolar A-580, M-1 was replaced with equimolar B-580 and M-124 was replaced with equimolar M-580, compound 580 (14.48 g) was obtained with an HPLC purity of ≡ 99.94%. Mass spectrum m/z:679.2091 (theory: 679.2082). Theoretical element content (%) C 48 H 29 N 3 S: c,84.80; h,4.30; n,6.18. Measured element content (%): c,84.77; h,4.34; n,6.20.
Synthesis example 26: preparation of compound 587:
Figure BDA0004077534800000594
according to the same manner as that of Synthesis example 8 except that A-124 was replaced with equimolar A-587, M-1 was replaced with equimolar B-587 and M-124 was replaced with equimolar M-587, compound 587 (16.48 g) was obtained, and HPLC purity was. Mass spectrum m/z:807.2945 (theory: 807.2960). Theoretical element content (%) C 60 H 41 NS: c,89.18; h,5.11; n,1.73. Measured element content (%): c,89.21; h,5.07; n,1.76.
Synthesis example 27: preparation of compound 588:
Figure BDA0004077534800000601
according to the same manner as that of Synthesis example 3, g-89 was replaced with equimolar g-588, A-89 was replaced with equimolar A-588, and M-1 was replaced with equimolar M-538, to obtain compound 588 (15.78 g), which had an HPLC purity of 99.95%. Mass spectrum m/z:710.1864 (theory: 710.1850). Theoretical element content (%) C 49 H 30 N 2 S 2 : c,82.79; h,4.25; n,3.94. Measured element content (%): c,82.82; h,4.29; n,3.92.
Synthesis example 28: preparation of compound 615:
Figure BDA0004077534800000602
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-124 and M-1 was replaced with equimolar A-223, compound 615 (15.57 g) was obtained with an HPLC purity of ≡ 99.96%. Mass spectrum m/z:691.2350 (theory: 691.2334). Theoretical element content (%) C 51 H 33 NS: c,88.53; h,4.81; n,2.02. Measured element content (%): c,88.50; h,4.79; n,2.06.
Synthesis example 29: preparation of Compound 621:
Figure BDA0004077534800000603
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-621 and M-1 was replaced with equimolar A-621, compound 621 (14.53 g) was obtained with an HPLC purity of ≡ 99.91%. Mass spectrum m/z:672.2588 (theory: 672.2599). Theoretical element content (%) C 48 H 36 N 2 S: c,85.68; h,5.39; n,4.16. Measured element content (%): c,85.71; h,5.43; n,4.11.
Synthesis example 30: preparation of compound 626:
Figure BDA0004077534800000611
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-626 and M-1 was replaced with equimolar A-626, compound 626 (13.49 g) was obtained with an HPLC purity of ≡ 99.93%. Mass spectrum m/z:615.2039 (theory: 615.2021). Theoretical element content (%) C 45 H 29 NS: c,87.77; h,4.75; n,2.27. Actual measurement elementContent (%) of element: c,87.80; h,4.71; n,2.32.
Synthesis example 31: preparation of compound 659:
Figure BDA0004077534800000612
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-659 and M-1 was replaced with equimolar M-538, compound 659 (15.40 g) was obtained with an HPLC purity of ≡ 99.98%. Mass spectrum m/z:712.1656 (theory: 712.1643). Theoretical element content (%) C 48 H 28 N 2 OS 2 : c,80.87; h,3.96; n,3.93. Measured element content (%): c,80.90; h,3.91; n,3.89.
Synthesis example 32: preparation of compound 669:
Figure BDA0004077534800000613
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar A-669 and M-1 was replaced with equimolar M-669, compound 669 (15.05 g) was obtained with an HPLC purity of ≡99.96%. Mass spectrum m/z:716.1434 (theory: 716.1453). Theoretical element content (%) C 44 H 24 N 6 OS 2 : c,73.72; h,3.37; n,11.72. Measured element content (%): c,73.69; h,3.40; n,11.76.
Synthesis example 33: preparation of compound 670:
Figure BDA0004077534800000621
according to the same manner as that of Synthesis example 3 except that g-89 was replaced with equimolar g-670 and A-89 was replaced with equimolar A-670, compound 670 (14.93 g) was obtained with an HPLC purity of ≡ 99.93%. Mass spectrum m/z:681.2063 (theory: 681.2052). Theoretical element content (%) C 47 H 27 N 3 O 3 ：C,82.80；H,3.99；N,6.16。Measured element content (%): c,82.76; h,3.97; n,6.21.
Synthesis example 34: preparation of compound 677:
Figure BDA0004077534800000622
according to a production method similar to that of Synthesis example 3, A-89 was replaced with equimolar A-677 and M-1 was replaced with equimolar M-538 to obtain Compound 677 (14.91 g), with an HPLC purity of ≡ 99.94%. Mass spectrum m/z:662.1471 (theory: 662.1487). Theoretical element content (%) C 44 H 26 N 2 OS 2 : c,79.73; h,3.95; n,4.23. Measured element content (%): c,79.69; h,3.98; n,4.18.
Synthesis example 35: preparation of compound 709:
Figure BDA0004077534800000623
according to the same manner as that of Synthesis example 3 except that g-89 was replaced with equimolar g-709, A-89 was replaced with equimolar M-709, and M-1 was replaced with equimolar A-709, compound 709 (16.06 g) was obtained, and HPLC purity was ≡ 99.97%. Mass spectrum m/z:775.2142 (theory: 775.2152). Theoretical element content (%) C 52 H 29 DN 4 O 2 S: c,80.50; h,4.03; n,7.22. Measured element content (%): c,80.47; h,4.07; n,7.18.
Synthesis example 36: preparation of compound 727:
Figure BDA0004077534800000631
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-124 and M-1 was replaced with equimolar B-330, compound 727 (15.33 g) was obtained with an HPLC purity of ≡ 99.92%. Mass spectrum m/z:719.1936 (theory: 719.1919). Theoretical element content (%) C 51 H 29 NO 2 S：C,85.09; h,4.06; n,1.95. Measured element content (%): c,85.11; h,4.02; n,1.98.
Synthesis example 37: preparation of compound 734:
Figure BDA0004077534800000632
according to the same manner as that of Synthesis example 3 except that A-89 was replaced with equimolar M-734 and M-1 was replaced with equimolar A-734, compound 734 (15.34 g) was obtained with an HPLC purity of ≡ 99.95%. Mass spectrum m/z:751.1451 (theory: 751.1462). Theoretical element content (%) C 51 H 29 NS 3 : c,81.46; h,3.89; n,1.86. Measured element content (%): c,81.48; h,3.93; n,1.81.
Synthesis example 38: preparation of compound 778:
Figure BDA0004077534800000633
according to a production method similar to that of Synthesis example 8, g-124 was replaced with equimolar g-778, A-124 was replaced with equimolar A-778, M-1 was replaced with equimolar B-778, and M-124 was replaced with equimolar M-778, whereby Compound 778 (17.39 g) was obtained, and HPLC purity was ∈ 99.90%. Mass spectrum m/z:864.3517 (theory: 864.3504). Theoretical element content (%) C 66 H 44 N 2 : c,91.63; h,5.13; n,3.24. Measured element content (%): c,91.60; h,5.09; n,3.25.
Device example 1
Firstly, the ITO/Ag/ITO substrate is washed 3 times in distilled water, ultrasonic washing is carried out for 15 minutes, after the distilled water washing is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially washed by ultrasonic waves, and then the substrate is dried at 120 ℃.
Evaporating HI-1:P-1=93:3 (doping mass ratio) with the thickness of 35nm on the cleaned ITO/Ag/ITO substrate by adopting a vacuum evaporation method to serve as a hole injection layer material; evaporating HT-1 with the thickness of 80nm on the hole injection layer as a hole transport layer material; evaporating RH-1:RD-1=98:2 (mass ratio) on the hole transport layer as a light emitting layer, wherein the evaporating thickness is 40nm; evaporating HB-1 on the light-emitting layer as a hole blocking layer material, wherein the evaporating thickness is 40nm;
evaporating ET-1 and Liq (doping mass ratio is 1:1) on the hole blocking layer to serve as electron transport layer materials, wherein the evaporating thickness is 30nm; evaporating LiF as an electron injection layer on the electron transport layer, wherein the evaporating thickness is 1.0nm; then, mg is evaporated on the electron injection layer, wherein Ag=1:9 (the mass ratio is 1:1) is used as a cathode, and the evaporation thickness is 11nm; then, compound 1 was evaporated on the cathode as a coating layer to an evaporation thickness of 70nm, thereby preparing an organic electroluminescent device.
Figure BDA0004077534800000641
Device examples 2 to 37
An organic electroluminescent device was produced by the same production method as in device example 1, except that compound 1 in device example 1 was replaced with compound 89, compound 96, compound 97, compound 98, compound 110, compound 124, compound 160, compound 168, compound 173, compound 180, compound 187, compound 223, compound 276, compound 288, compound 291, compound 330, compound 476, compound 499, compound 508, compound 516, compound 538, compound 552, compound 580, compound 587, compound 588, compound 615, compound 621, compound 626, compound 659, compound 669, compound 670, compound 677, compound 709, compound 727, compound 734 and compound 778 according to the present invention.
Comparative device examples 1 to 2
An organic electroluminescent device was manufactured by the same manufacturing method as device example 1, except that the compound 1 in device example 1 was replaced with the comparative compound 1 or the comparative compound 2, respectively, as the capping layer.
Test software, a computer, a K2400 digital source list manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research, U.S. are combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature.
Examples 1 to 37 of the inventive devices, and comparative examples 1 to 2 gave the results of the light emission characteristics of the organic electroluminescent devices shown in table 1 below.
Figure BDA0004077534800000642
Figure BDA0004077534800000651
As can be seen from the data results of table 1, the application of the capping layer compound of the present invention to an organic electroluminescent device as a capping layer material can effectively improve the light extraction efficiency of the device, reduce the total reflection phenomenon of light inside the device, and increase the luminous efficiency and the service life of the organic electroluminescent device, compared with comparative device examples 1-2.
It should be noted that while the invention has been particularly described with reference to individual embodiments, those skilled in the art may make various modifications in form or detail without departing from the principles of the invention, which modifications are also within the scope of the invention.

Claims (10)

1. An organic electroluminescent device comprises an anode, a cathode and an organic layer, wherein the organic layer comprises a covering layer, and the organic electroluminescent device is characterized in that the covering layer has a structure shown in a formula I;
Figure FDA0004077534790000011
in formula I, the Ar 1 ～Ar 3 Are identical or different from each other, at least one of which is selected from the group represented by formula IIThe rest groups are the same or different from each other and are selected from any one of substituted or unsubstituted aryl groups of C6-C30, substituted or unsubstituted heteroaryl groups of C2-C30, substituted or unsubstituted aromatic rings of C6-C30 and condensed ring groups of aliphatic rings of C3-C30;
Figure FDA0004077534790000012
in formula II, the L 0 Any one selected from the group consisting of the following groups and combinations thereof;
Figure FDA0004077534790000013
z is identical or different from each other and is selected from CH or N atoms, and at least one Z in each group is selected from N atoms; when Z is bonded to other groups, the Z is selected from C atoms;
the R is 1 Are the same or different from each other, and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
The a 1 Selected from 0, 1, 2 or 3, said a 2 Selected from 0, 1, 2, 3, 4 or 5; when two or more R's are present 1 When two or more R' s 1 Identical or different from each other, or adjacent two R' s 1 May be linked to each other to form a substituted or unsubstituted ring;
the x is 1 Selected from O, S, NR a Any one of them; the R is a Any one selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;
y, equal to or different from each other, is selected from CH or N atoms;
the R, R' are the same or different from each other and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
said m is selected from 0, 1, 2, 3 or 4; when two or more R's are present, two or more R's may be the same or different from each other, or adjacent two R's may be connected to each other to form a substituted or unsubstituted ring;
Said m' is selected from 0, 1 or 2;
the x are identical or different from each other and are selected from CH or N atoms, and when x is bonded with other groups, the x is selected from C atoms;
the R is 2 Any one selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
said n is selected from 0, 1, 2 or 3;
the L is 1 ～L 3 Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, bivalent substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group.
2. An organic electroluminescent device as claimed in claim 1, wherein the L 0 Any one selected from the following groups;
Figure FDA0004077534790000021
z is identical or different from each other and is selected from CH or N atoms, and at least one Z in each group is selected from N atoms; when Z is bonded to other groups, the Z is selected from C atoms;
the R is 1 Identical or different from each other, selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, pyridinyl or pyrimidinyl;
The a 1 Selected from 0, 1, 2 or 3, said a 2 Selected from 0, 1, 2, 3, 4 or 5, said a 3 Selected from 0, 1, 2, 3 or 4, said a 4 Selected from 0, 1, 2, 3, 4, 5 or 6.
3. An organic electroluminescent device as claimed in claim 1, wherein the L 0 Any one selected from the following groups;
Figure FDA0004077534790000022
Figure FDA0004077534790000031
4. an organic electroluminescent device as claimed in claim 1, wherein the
Figure FDA0004077534790000032
Any one selected from the following groups;
Figure FDA0004077534790000033
the R, R' groups are identical or different from each other and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen or substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, pyridinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl or quinoxalinyl;
the m is 1 Selected from 0, 1, 2, 3 or 4, said m 2 Selected from 0, 1, 2 or 3, said m 3 Selected from 0, 1 or 2, said m 4 Selected from 0 or 1, when two or more R are present, two or more R are the same or different from each other, or two adjacent R may be linked to each other to form a substituted or unsubstituted ring;
The m 'is selected from 0, 1 or 2, and the m' is selected from 0 or 1.
5. An organic electroluminescent device as claimed in claim 1, wherein the
Figure FDA0004077534790000041
Any one selected from the following groups;
Figure FDA0004077534790000042
the x is 1 Are identical or different from each other and are selected from O, S or NR a Any one of them;
the R is a Selected from hydrogen, deuterium or any one of the following groups substituted or unsubstituted by one or more deuterium, C1 to C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, triphenylyl, pyridinyl or pyrimidinyl;
said b 1 Selected from 0, 1, 2, 3, 4 or 5, said b 2 Selected from 0, 1, 2, 3 or 4, said b 3 Selected from 0, 1, 2, 3, 4, 5, 6 or 7.
6. An organic electroluminescent device as claimed in claim 1, wherein Ar 1 ～Ar 3 Is the same or different from each other, wherein at least one is selected from the group shown in the formula II, and the rest is the same or different from each other and is selected from any one of the groups shown in the following;
Figure FDA0004077534790000051
the R is 3 Are the same or different from each other, and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
The c 1 Selected from 0, 1, 2, 3, 4 or 5, said c 2 Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said c 3 Selected from 0, 1, 2, 3 or 4, said c 4 Selected from 0, 1, 2, 3, 4, 5 or 6; when two or more R's are present 3 When two or more R' s 3 Identical or different from each other, or adjacent two R' s 3 May be linked to each other to form a substituted or unsubstituted ring;
said Q is selected from O, S, C (R b )(R c )、N(R d ) Any one of them;
the R is b 、R c 、R d Are identical or different from each other and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R b 、R c Can be linked to each other to form a substituted or unsubstituted ring, or R b 、R c 、R d Can be combined with L 1 ～L 3 Any one of them directlyBonding;
the t are the same or different from each other and are selected from CH or N atoms, and 1, 2, 3 or 4 t are selected from N atoms in the formula III-4, and 1, 2, 3, 4, 5 or 6 t are selected from N atoms in the formula III-5; when t is bonded to other groups, said t is selected from a C atom;
said z 1 Selected from O, S or N (R) e ) The method comprises the steps of carrying out a first treatment on the surface of the Said z 2 Selected from C (R) f ) Or an N atom;
the R is e 、R f Are the same or different from each other, and are selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl.
7. An organic electroluminescent device as claimed in claim 1, wherein Ar 1 ～Ar 3 Is the same or different from each other, wherein at least one is selected from the group shown in the formula II, and the rest is the same or different from each other and is selected from any one of the groups shown in the following;
Figure FDA0004077534790000052
Figure FDA0004077534790000061
the R is 4 Identical to or different from each other, selected from hydrogen, deuterium or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl, naphthalene, pyridinyl, or pyrimidinyl;
said d 1 Selected from 0, 1, 2, 3, 4 or 5, said d 2 Selected from 0, 1, 2, 3Or 4, said d 3 Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said d 4 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said d 5 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said d 6 Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said d 7 Selected from 0, 1, 2, 3, 4, 5 or 6, said d 8 Selected from 0, 1, 2 or 3;
the R is b 、R c 、R d Identical to or different from each other, selected from hydrogen, deuterium or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl, naphthalene, pyridinyl, or pyrimidinyl;
the L is a 、L b Are identical or different from each other, and are selected from any one of single bond, substituted or unsubstituted: phenylene, biphenylene, naphthylene, pyridylene or pyrimidinylene;
the ring A is selected from a spiro structure, and the spiro structure is selected from any one of the following groups:
Figure FDA0004077534790000071
the R is 5 Are the same or different from each other, and are selected from any one of hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl and naphthyl;
Said e 1 Selected from 0, 1, 2, 3 or 4, said e 2 Selected from 0, 1, 2, 3, 4, 5 or 6, said e 3 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said e 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, said e 5 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12,said e 6 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.
8. An organic electroluminescent device as claimed in claim 1, wherein Ar 1 ～Ar 3 Is the same or different from each other, wherein at least one is selected from the group shown in the formula II, and the rest is the same or different from each other and is selected from any one of the groups shown in the following;
Figure FDA0004077534790000072
Figure FDA0004077534790000081
Figure FDA0004077534790000091
Figure FDA0004077534790000101
Figure FDA0004077534790000111
9. an organic electroluminescent device as claimed in claim 1, wherein the L 1 ～L 3 Are the same or different from each other, and are selected from any one of single bonds or groups shown below;
Figure FDA0004077534790000112
the R is 6 Identical or different from each other, optionallyAny one of hydrogen, deuterium or C1-C12 alkyl substituted or unsubstituted by one or more deuterium, C3-C12 cycloalkyl substituted or unsubstituted, C6-C30 aryl substituted or unsubstituted, and C2-C30 heteroaryl substituted or unsubstituted;
the s is 1 Selected from 0, 1, 2, 3 or 4, said s 2 Selected from 0, 1, 2, 3, 4 or 5, said s 3 Selected from 0, 1, 2 or 3, said s 4 Selected from 0, 1 or 2, said s 5 Selected from 0, 1, 2, 3, 4, 5 or 6;
the R is x 、R y 、R z Are identical or different from each other and are selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R x 、R y May be linked to each other to form a substituted or unsubstituted ring;
the V's are the same or different from each other and are selected from CH or N atoms, and at least one V in each group is selected from N atoms; when V is bonded to other groups, said V is selected from a C atom;
the ring B is selected from the group consisting of substituted or unsubstituted C3-C7 aliphatic rings.
10. An organic electroluminescent device according to claim 1, wherein the cover layer is selected from any one of the following structures;
Figure FDA0004077534790000121
Figure FDA0004077534790000131
Figure FDA0004077534790000141
Figure FDA0004077534790000151
Figure FDA0004077534790000161
Figure FDA0004077534790000171
Figure FDA0004077534790000181
Figure FDA0004077534790000191
Figure FDA0004077534790000201
Figure FDA0004077534790000211
Figure FDA0004077534790000221
Figure FDA0004077534790000231
Figure FDA0004077534790000241
Figure FDA0004077534790000251
Figure FDA0004077534790000261
Figure FDA0004077534790000271
Figure FDA0004077534790000281
Figure FDA0004077534790000291
Figure FDA0004077534790000301
Figure FDA0004077534790000311
Figure FDA0004077534790000321
Figure FDA0004077534790000331
Figure FDA0004077534790000341
Figure FDA0004077534790000351
Figure FDA0004077534790000361
Figure FDA0004077534790000371
Figure FDA0004077534790000381
CN202310107232.6A 2023-02-13 2023-02-13 Organic electroluminescent device Pending CN116322134A (en)

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