Organic electroluminescent compounds and their applications

Abstract

The present invention relates to the field of display technology, and more particularly to an organic electroluminescent compound and its application. The organic electroluminescent compound provided by the present invention has the following structure: #imgabs0# wherein R 1 ‑R 12 At least one of them has the structure shown below: #imgabs1#, which can enable an organic electroluminescent device containing the organic electroluminescent compound to have a lower driving voltage, higher current efficiency and longer life.

Description

Technical Field

[0001] The present invention relates to the field of display technology, and in particular to an organic electroluminescent compound and application thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs) convert electrical energy into light by applying electricity to organic electroluminescent materials. They are considered to be the most promising display and lighting technology and typically include an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of an organic light-emitting electronic device (organic EL) may include a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescence auxiliary layer, an electron blocking layer, a light-emitting layer (containing a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. The materials used in the organic layer can be divided into hole injection materials, hole transport materials, hole auxiliary materials, luminescence auxiliary materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, and the like depending on their functions. In an organic EL device, holes from the anode and electrons from the cathode are injected into the light-emitting layer by applying a voltage, and excitons with high energy are generated by the recombination of holes and electrons. The electrons of the organic electroluminescent material emit light by the energy when they move to an excited state and return to the ground state from the excited state.

[0003] However, the HOMO and LUMO energy levels of existing organic electroluminescent materials are poorly matched with adjacent energy levels, resulting in low stability and unbalanced carrier mobility. This causes organic electroluminescent devices containing these organic electroluminescent materials to have high driving voltages, low current efficiency, and short lifespans, severely limiting their application. Summary of the Invention

[0004] The present invention aims to overcome the problem that the HOMO and LUMO energy levels of existing organic electroluminescent materials have poor matching with adjacent energy levels, thereby resulting in low stability and unbalanced carrier mobility of the organic electroluminescent materials, and causing organic electroluminescent devices containing the organic electroluminescent materials to have high driving voltages, low current efficiency, and short lifespans, which seriously limit the applications of organic electroluminescent devices. The present invention further provides an organic electroluminescent compound and its applications.

[0005] Definitions of substituent terms in this invention:

[0006] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0007] As used herein, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0008] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a group derived from a monocyclic hydrocarbon or a polycyclic hydrocarbon having 1 to 30 ring main chain carbon atoms, and the cycloalkane may include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0009] In the present invention, aryl and arylene groups include monocyclic, polycyclic or condensed ring aromatic groups, and the rings may be interrupted by short non-aromatic units and may contain spiro structures. Aryl groups include but are not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, fluorenyl, spirobifluorenyl, etc., and arylene groups include but are not limited to phenylene, biphenylene, terphenylene, naphthylene, phenanthrenyl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0010] The heteroaryl and heteroarylene groups in the present invention include monocyclic, polycyclic or condensed ring heteroaryl groups, wherein the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen and sulfur. Heteroaryl groups include, but are not limited to, furyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzo thiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof; heteroarylene groups include but are not limited to furylene, phenylenethio, pyrroleene, thiophene ... yl, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, tetrazolylene, furazolylene, pyridylene, pyrazinylene, pyrimidylene, pyridazinylene, benzofuranylene, benzothiophenylene, isobenzofuranylene, dibenzofuranylene, dibenzothiophenylene, benzimidazolylene oxazolyl, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoxazolylene, isoindolyl, indolyl, indazolylene, benzothiadiazolylene, quinolinylene, isoquinolinylene, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, phenoxazinylene, phenothiazinylene, phenanthridinylene, benzodioxolylene, dihydroacridinylene, and derivatives thereof.

[0011] As used herein, the term "substituted" refers to a hydrogen atom in a compound being replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at that position can be replaced by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.

[0012] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium, and tritium.

[0013] In the present invention, the definition of the group defines the range of the number of carbon atoms, and the number of carbon atoms is any integer within the defined range. For example, a C6-C30 aromatic group represents an aromatic group, and the number of carbon atoms can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30.

[0014] The scheme adopted by the present invention is as follows:

[0015] The present invention provides an organic electroluminescent compound having the structure shown below:

[0016]

[0017] Among them, R 1 -R 12 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and substituted or unsubstituted C6-C30 arylamino;

[0018] R 13 、R 14 Each independently selected from deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C30 aryl;

[0019] Among them, R 1 -R 12 At least one has the following structure:

[0020]

[0021] X 1 Select N or CR X1 , X 2 Select N or CR X2 , X 3 Select N or CR X3 , X 4 Select N or CR X4 , X 5 Select N or CR X5 ;

[0022] R X1 -R X5 are each independently selected from hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, R X1 -R X5 Each exists independently, or two adjacent rings are connected to form Ring A, wherein Ring A is a substituted or unsubstituted C6-C30 aromatic ring, or a substituted or unsubstituted C3-C30 heteroaromatic ring;

[0023] L is selected from a connecting bond, a substituted or unsubstituted C6-C30 aromatic ring, or a substituted or unsubstituted C3-C30 heteroaromatic ring;

[0024] n is an integer from 0 to 5;

[0025] The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C5-C30 aryl, substituted C3-C30 heteroaryl, substituted C6-C30 aromatic amino, substituted C1-C20 alkyl, substituted C6-C30 aryl, substituted C6-C30 aromatic ring, and substituted C3-C30 heteroaromatic ring are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, and C3-C12 heteroaryl.

[0026] Preferably, L is selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, and a substituted or unsubstituted naphthylene group;

[0027] The substituents in the substituted phenylene, substituted biphenylene, substituted terphenylene and substituted naphthylene are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.

[0028] Optionally, n is 1, 2, 3, 4, or 5.

[0029] Preferably, R 1 -R 12 One of them has the structure represented by formula (a), and the others are hydrogen;

[0030] L is selected from phenylene, biphenylene, and naphthylene;

[0031] n is 0 or 1.

[0032] Preferably, X 1 -X 5 middle,

[0033] X 1 N, X 2 N, X 3 CR X3 , X 4 CR X4 , and X 5 CR X5 ;or

[0034] X 1 N, X 3 N, X 2 CR X2 , X 4 CR X4 , and X 5 CR X5 ;or

[0035] X 1 N, X 2 N, X 3 N, X 4 CR X4 , and X 5 CR X5 ;or

[0036] X 1 N, X 5 N, X 2 CR X2 , X 3 CR X3 , and X 4 CR X4 ;or

[0037] X 1 CR X1 , X 2 CR X2 , X 3 CR X3 , X 4 CR X4 , and X 5 CR X5 .

[0038] Preferably, R X1 -R X5 Each exists independently; or R X1 -R X5 Among them, two adjacent ones are connected to form ring A, and the others exist independently;

[0039] R X1 -R X5Each is independently selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0040] Ring A is a substituted or unsubstituted C6-C30 aromatic ring, or a substituted or unsubstituted C3-C30 heteroaromatic ring;

[0041] The substituents in the substituted C1-C30 alkyl, substituted C6-C30 aryl, substituted C3-C30 heteroaryl, substituted C6-C30 aromatic ring, and substituted C3-C30 heteroaromatic ring are selected from one or a combination of two of C5-C12 aryl and C3-C12 heteroaryl.

[0042] Preferably, R X2 -R X5 Each is independently selected from hydrogen, a substituted or unsubstituted A group, wherein the A group is selected from one of the following groups:

[0043] phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, pyrenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dinaphthothiophenyl, dinaphthofuranyl, benzophenanthrofuryl, dinaphthothiophenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, benzonaphthothiophenyl, phenyldibenzocarbazolyl, phenylbenzocarbazolyl, phenylcarbazolyl, dibenzocarbazolyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, and dimethylfluorenylphenyl;

[0044] The substituent of the substituted A group is selected from one or a combination of two of hydrogen, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, and C3-C12 heteroaryl.

[0045] Preferably, the formula (a) is selected from one of the following groups:

[0046]

[0047] Among them, R X2 -R X5 、R X15 、R X16 Each is independently selected from hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0048] The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from one or a combination of two of hydrogen, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, and C3-C12 heteroaryl.

[0049] in, Indicates a connection key.

[0050] Preferably, R X2 -R X5 、R X15 、R X16 Each is independently selected from hydrogen, a substituted or unsubstituted A group, wherein the A group is selected from one of the following groups:

[0051] phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, pyrenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dinaphthothiophenyl, dinaphthofuranyl, benzophenanthrofuryl, dinaphthothiophenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, benzonaphthothiophenyl, phenyldibenzocarbazolyl, phenylbenzocarbazolyl, phenylcarbazolyl, dibenzocarbazolyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, and dimethylfluorenylphenyl;

[0052] The substituent of the substituted A group is selected from one or a combination of two of hydrogen, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, and C3-C12 heteroaryl.

[0053] Preferably, R X2 -R X5 、R X15 、R X16 Each is independently selected from hydrogen, phenyl, biphenyl, naphthyl, phenanthrenyl, triphenylene, pyrenyl, benzonaphthothienyl, benzodimethylfluorenyl, dibenzofuranyl, triphenylfuranyl, and spirobifluorenyl.

[0054] Preferably, R 13 、R 14 Each independently selected from deuterium, C1-C6 alkyl;

[0055] Preferably, R 13 、R 14 Each is independently selected from deuterium, methyl, and ethyl.

[0056] When R 13 、R 14 When selected from deuterium, C1-C6 alkyl than R 13 、R 14When the aromatic group is selected from C3-C30, the HOMO and LUMO energy levels of the organic electroluminescent compound have a higher matching degree with the adjacent energy levels, thereby making the organic electroluminescent compound more stable and the carrier mobility more balanced, thereby making the organic electroluminescent device containing the organic electroluminescent compound have a lower driving voltage, higher current efficiency and longer life.

[0057] Preferably, the organic electroluminescent compound is selected from one of the following structures:

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065] The present invention also provides an organic electroluminescent material, comprising a first host material and a second host material, wherein the first host material comprises the organic electroluminescent compound described above, and the second host material comprises a compound having the structure of the following formula (2):

[0066]

[0067] Among them, Ar W1 、Ar W2 、Ar W3 are independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, Ar W1 、Ar W2 、Ar W3 They are not connected to each other or two adjacent ones are connected to form a ring;

[0068] L W1 、L W2 、L W3 Each is independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0069] The substituents in the substituted C6-C60 aryl group, substituted C3-C60 heteroaryl group, substituted C6-C30 arylene group, and substituted C3-C30 heteroarylene group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, and C3-C12 heteroaryl groups.

[0070] Preferably, L W1 、L W2 、L W3 Each is independently selected from a linker, a phenylene group, a biphenylene group, or a naphthylene group.

[0071] Preferably,

[0072] In formula (2), Ar W1 、Ar W2 、Ar W3 Each is independently selected from phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, anthracenyl, phenanthrenyl, triphenylene, pyridyl, and a group represented by formula (b-1):

[0073]

[0074] Wherein W is selected from O, S, CR W1 R W2 , and NR w , R w -L W R W3 ;

[0075] When Ar W1 、Ar W2 、Ar W3 When any one, two or three of the following are selected from formula (b-1), R in formula (b-1) 10’ -R 17’ 、R W1 、R W2 、R W3 Any one of them is chemically bonded to L W1 、L W2 or L W3 connect;

[0076] When formula (2) contains multiple groups of formula (b-1), the multiple groups of formula (b-1) are the same or different;

[0077] R 10’ -R 17’ 、R W1 、R W2 、R W3each independently selected from a linker, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C4-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryloxy;

[0078] R 10’ -R 17’ Each exists independently or two adjacent rings are connected to form ring B, and the ring B is a substituted or unsubstituted C6-C30 aromatic ring;

[0079] L W is selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0080] The substituents in the substituted C1-C30 alkyl, substituted C7-C30 aralkyl, substituted C6-C30 aryl, substituted C3-C30 heteroaryl, substituted C4-C30 heteroaralkyl, substituted C3-C30 cycloalkyl, substituted C3-C30 heterocycloalkyl, substituted C3-C30 cycloalkenyl, substituted C1-C30 alkoxy, substituted C6-C30 aryloxy, substituted C6-C30 arylene and substituted C3-C30 heteroarylene are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.

[0081] Optionally, the substituted C1-C30 alkyl group is a C1-C30 alkyl group in which one or more methylene groups are substituted with -O- and / or -S- in a non-adjacent O atom and / or S atom.

[0082] Preferably, formula (b-1) is selected from the structures shown in any one of the following:

[0083]

[0084] Among them, R 10’ -R 17’ each independently selected from hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, anthracenyl, phenanthrenyl, triphenylenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzonaphthofuranyl, and benzonaphthothiophenyl;

[0085] W is selected from O, S, CR W1 R W2 , and NR w , R w -L W R W3 ;

[0086] Among them, R W1 -R W2 are independently selected from hydrogen, deuterium, methyl, ethyl, and phenyl, or R W1 -R W2 Connected into spiro ring by chemical bonds;

[0087] R W3 a substituted or unsubstituted group selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, benzonaphthothiophene, dinaphthofuranyl, dinaphthothiophenyl, dibenzofuranphenyl, dibenzothiophenephenyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, and dimethylfluorenylphenyl;

[0088] L W is selected from a linker, a phenylene group, a biphenylene group, and a naphthylene group.

[0089] Preferably, the formula (b-1) is selected from substituted or unsubstituted D groups:

[0090] Wherein the D group is selected from one of the following groups:

[0091]

[0092] in Represents the connection key, which is understandable. For example, the connecting bond Lc can be connected to any carbon atom of C1-C6 in ring E and ring F.

[0093] wherein the substituents of the substituted D group are each independently selected from deuterium, halogen, cyano, nitro, unsubstituted or R'-substituted C1-C4 straight or branched alkyl, unsubstituted or R'-substituted C6-C20 aryl, and unsubstituted or R'-substituted C3-C20 heteroaryl;

[0094] R' is selected from deuterium, halogen, cyano or nitro;

[0095] Preferably, the C6-C20 aryl group is selected from one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, naphthyl-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl or spirobifluorenyl;

[0096] Preferably, the C3-C20 heteroaryl group is selected from pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzocarbazolyl or dibenzocarbazolyl;

[0097] Preferably, the C1-C4 straight-chain or branched alkyl group is selected from methyl, ethyl, propyl, tert-butyl, cyclohexyl or adamantyl.

[0098] Preferably, Ar W1 、Ar W2 、Ar W3 Each is independently selected from phenyl, naphthyl, dibenzofuranyl, spirobifluorenyl, phenylcarbazolyl, benzodimethylfluorenyl, and dibenzocarbazolyl.

[0099] Preferably, the compound of formula (3) is selected from one of the following compounds:

[0100]

[0101]

[0102]

[0103] Preferably, the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) is 1:9-9:1;

[0104] Preferably, the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) is 2:8-8:2;

[0105] More preferably, the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) is 3:7-7:3;

[0106] More preferably, the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) is 4:6-6:4.

[0107] The present invention provides the use of the above-mentioned organic electroluminescent material in the preparation of optical devices.

[0108] The present invention provides an organic electroluminescent device, comprising an anode and a cathode, and an organic layer arranged between the anode and the cathode, wherein the organic layer comprises the above-mentioned organic electroluminescent compound or the above-mentioned organic electroluminescent material. Preferably, the light-emitting layer in the organic layer comprises the above-mentioned organic electroluminescent compound or the above-mentioned organic electroluminescent material.

[0109] Preferably, the organic layer comprises a light-emitting layer, and the material of the light-emitting layer comprises a host material and a guest material; the host material comprises the above-mentioned organic electroluminescent compound or the above-mentioned organic electroluminescent material;

[0110] Preferably, the guest material comprises a phosphorescent dopant or a thermally activated delayed fluorescence compound;

[0111] Preferably, the phosphorescent dopant comprises a transition metal complex;

[0112] The present invention provides an organic electroluminescent device, which includes the organic electroluminescent device as described above.

[0113] In an embodiment of an organic electroluminescent device of the present invention, the organic layer is composed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer stacked in sequence. The organic electroluminescent device also includes a substrate, which is located on the surface of the anode facing away from the cathode.

[0114] Optionally, an electron blocking layer is further included between the hole transport layer and the light-emitting layer.

[0115] Optionally, the organic electroluminescent compound represented by formula (1) is contained in one of the hole injection layer, the hole transport layer, the electron blocking layer, the electron injection layer, the electron transport layer, the light-emitting layer, or in an organic layer formed by a combination of part or all of the hole injection layer, the hole transport layer, the electron blocking layer, the electron injection layer, the electron transport layer and the light-emitting layer.

[0116] In the present invention, the organic electroluminescent compound represented by formula (1) can be prepared by the following synthetic route:

[0117] 1. When n is 0,

[0118] (1) Compound Nn-A reacts with compound Nn-B to obtain intermediate Nn-1:

[0119]

[0120] Wherein Hal represents halogen;

[0121] (2) Suzuki coupling reaction

[0122]

[0123] Bpin is a pinacol borate group.

[0124] (3) Suzuki coupling reaction

[0125]

[0126] Hal 1 Represents halogen.

[0127] Beneficial effects of the present invention:

[0128] 1. The present invention provides an organic electroluminescent compound, based on the structure of formula (1), limiting R 1 -R 14 and further define R 1 -R 12 At least one of the structures is selected from the structure represented by formula (a), and the two structures cooperate with each other to achieve a high degree of matching between the HOMO and LUMO energy levels of the organic electroluminescent compound and the adjacent energy levels, so that the organic electroluminescent compound obtains higher stability and more balanced carrier mobility, thereby enabling the organic electroluminescent device containing the organic electroluminescent compound to have a lower driving voltage, higher current efficiency and longer life.

[0129] 2. The present invention provides an organic electroluminescent material. By combining the compound of formula (1) and the compound of formula (2), the stability and carrier mobility balance of the organic electroluminescent material are further improved, thereby further reducing the driving voltage of the organic electroluminescent device containing the organic electroluminescent material and further increasing the lifespan.

[0130] Furthermore, an organic electroluminescent device comprising the organic electroluminescent material has higher current efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0131] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0132] Figure 1 This is a structural diagram of an organic electroluminescent device in an embodiment of the device of the present invention;

[0133] Among them, 1-substrate; 2-anode; 3-hole injection layer; 4-hole transport layer; 5-light-emitting layer; 6-electron transport layer; 7-electron injection layer; 8-cathode. DETAILED DESCRIPTION

[0134] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0135] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0136] The term "organic electroluminescent material" in the present disclosure means a material that can be used in an organic electroluminescent device and that can include at least one compound. If necessary, the organic electroluminescent material can be included in any layer constituting the organic electroluminescent device. For example, the organic electroluminescent material can be a hole injection material, a hole transport material, a hole assist material, a luminescence assist material, an electron blocking material, a luminescent material (containing a host material and a dopant material), an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0137] The term "multiple organic electroluminescent materials" in the present disclosure means one or more organic electroluminescent materials comprising a combination of at least two compounds, which may be included in any layer constituting an organic electroluminescent device. It may mean both a material before being included in an organic electroluminescent device (e.g., before vapor deposition) and a material after being included in an organic electroluminescent device (e.g., after vapor deposition). For example, a plurality of organic electroluminescent materials may be a combination of at least two compounds, which may be included in at least one of the following: a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescence auxiliary layer, an electron blocking layer, a light-emitting layer, an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer. At least two compounds may be included in the same layer or different layers and may be mixed-evaporated or co-evaporated, or may be evaporated individually.

[0138] Example 1

[0139] Synthesis of compound N-1

[0140]

[0141] Synthesis of N1-1: Take a 1-liter four-necked round-bottom flask and place a stirrer and a reflux line. After drying, fill with nitrogen. Take 10g of N1-A (48.4mmol, CAS: 781-43-1) and add it to the flask. Dissolve it with 168mL of anhydrous dichloromethane (DCM) and heat to reflux. Dissolve 20.9g of N1-B (96.9mmol, CAS: 20776-48-1) in 140mL of anhydrous tetrahydrofuran (THF) to prepare a N1-B / THF solution. Dissolve 14.2g of isoamyl nitrite in 126mL of anhydrous DCE to prepare an isoamyl nitrite / DCE solution. Simultaneously, add the N1-B / THF and isoamyl nitrite / DCE solutions dropwise, and keep the isoamyl nitrite content in the system always greater than the content of N1-B in the system. The addition time is controlled to about 4h. After the addition was complete, the mixture was stirred and reacted under reflux for 12 hours. Purification by column chromatography gave the target product, compound N1-1 (7 g, yield: 40%).

[0142] Synthesis of N1-2: To a 250 mL three-necked flask equipped with a thermometer and magnetic stirring, 14 g of compound N1-1 (38.8 mmol), 11.8 g of bispinacol borate (46.6 mmol, CAS: 73183-34-3), 7.6 g of potassium acetate (77.6 mmol) and 0.56 g of Pd(dppf)Cl2 (0.78 mmol) were added, and 100 mL of 1,4-dioxane was added. Under nitrogen protection, the temperature was raised to 110°C and the reaction was reacted for 4 h. 100 mL of toluene was added to the reaction solution, and the solution was extracted with 100 mL of water. The organic phase was mixed and passed through a column to obtain intermediate N1-2 (12 g, yield: 76%).

[0143] Synthesis of N-1: To a three-necked flask equipped with a magnetic stirrer and a condenser, 10.0 g (24.5 mmol) of N1-2, 6.87 g (25.7 mmol) of N1-D, 6.76 g (48.9 mmol) of potassium carbonate, and 0.566 g (0.5 mmol) of tetrakistriphenylphosphine palladium were added, followed by the addition of toluene: ethanol: water 54 mL: 18 mL: 18 mL (7V: 3V: 3V). The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. After post-treatment, extraction was performed, and the liquids were separated. The organic phase was mixed and passed through a column to obtain 7.5 g, with a yield of 60%.

[0144] Elemental analysis: C 37 H 27 N3 theoretical value: C, 86.52; H, 5.30; N, 8.18; found: C, 86.53; H, 5.31; N, 8.16; HRMS (ESI) m / z [M+H] +: theoretical value: 513.22; found: 514.39.

[0145] Example 2

[0146] Synthesis of compound N-18

[0147]

[0148] Synthesis of N-18: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 8.13 g (25.7 mmol, CAS: 1852465-61-2) of the intermediate N18-D, 10.0 g (24.5 mmol) of N1-2, 6.76 g (48.9 mmol) of potassium carbonate, and 0.566 g (0.5 mmol) of tetrakistriphenylphosphine palladium. Then, toluene: ethanol: water 54 mL: 18 mL: 18 mL (7V: 3V: 3V) were added. The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. After post-treatment, extraction was performed, and the liquids were separated. The organic phase was mixed and passed through a column to obtain 8.26 g, with a yield of 60%.

[0149] Elemental analysis: C 42 H 30 N2 theoretical value: C, 89.65; H, 5.37; N, 4.98; found value: C, 89.67; H, 5.38; N, 4.95; HRMS (ESI) m / z [M+H] +: theoretical value: 562.24; found value: 563.41.

[0150] Example 3

[0151] Synthesis of compound N-28

[0152]

[0153] Synthesis of N28-D: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 20 g (83.1 mmol, CAS: 29874-83-7) of the intermediate N28-a, 20.3 g (87.3 mmol, CAS: 1373767-70-4), 23 g (166.4 mmol) of potassium carbonate, and 1.92 g (1.6 mmol) of tetrakistriphenylphosphine palladium. Toluene: ethanol: water 108 mL: 46 mL: 46 mL (7V: 3V: 3V) were then added. The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. The mixture was extracted and separated, and the organic phase was mixed and passed through a column to obtain 19.6 g, with a yield of 60%.

[0154] Synthesis of N-28: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 10.1 g (25.7 mmol) of the intermediate N28-D, 10 g (24.5 mmol) of N1-2, 6.76 g (48.9 mmol) of potassium carbonate, and 0.566 g (0.5 mmol) of tetrakistriphenylphosphine palladium. Then, toluene: ethanol: water 54 mL: 18 mL: 18 mL (7V: 3V: 3V) were added. The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. After post-treatment, extraction was performed, the liquids were separated, and the organic phase was mixed and passed through a column to obtain 9.8 g, with a yield of 63%.

[0155] Elemental analysis: C 48 H 34 N2 theoretical value: C, 90.25; H, 5.36; N, 4.39; found: C, 90.21; H, 5.38; N, 4.41; HRMS (ESI) m / z [M+H] +: theoretical value: 638.27; found: 639.13.

[0156] Example 4

[0157] Synthesis of compound N-89

[0158]

[0159] Synthesis of N89-1: Place a 1-liter, four-necked round-bottom flask in a stirrer and connect it to a reflux line. After drying, fill the flask with nitrogen. Add 10 g of Ni-A (48.4 mmol, CAS: 781-43-1) to the flask, dissolve it in 168 mL of anhydrous DCM, and heat to reflux. Dissolve 20.9 g of N89-B (96.9 mmol, CAS: 5794-88-7) in 140 mL of anhydrous THF to prepare an N89-B / THF solution. Dissolve 14.2 g of isoamyl nitrite in 126 mL of anhydrous DCE to prepare an isoamyl nitrite / DCE solution. Simultaneously add the N89-B / THF and isoamyl nitrite / DCE solutions dropwise, maintaining the isoamyl nitrite content greater than the N89-B content. Control the addition time to approximately 4 hours. After the addition is complete, stir the reaction under reflux for 12 hours. Purification by column chromatography gave the target product, compound N89-1 (7 g, yield: 42%).

[0160] Synthesis of N89-2: To a 250 mL three-necked flask equipped with a thermometer and magnetic stirring, 7 g of compound N89-1 (19.4 mmol), 5.9 g of bispinacol borate (23.3 mmol, CAS: 73183-34-3), 3.8 g of potassium acetate (38.8 mmol) and 282 mg of Pd(dppf)Cl2 (0.39 mmol) were added, and 70 mL of 1,4-dioxane was added. Under nitrogen protection, the temperature was raised to 110°C and the reaction was reacted for 4 h. 100 mL of toluene was added to the reaction solution, and the solution was extracted with 100 mL of water. The organic phase was mixed and passed through a column to obtain intermediate N89-2 (6 g, yield: 76%).

[0161] Synthesis of N89-D: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 26.8 g (92.9 mmol, CAS: 1198396-48-3) of intermediate N89-b, 20 g (88.5 mmol, CAS: 1700-02-3), 23 g (166.4 mmol) of potassium carbonate, and 1.92 g (1.6 mmol) of tetrakistriphenylphosphine palladium. Toluene, ethanol, and water (108 mL:46 mL:46 mL, 7 V:3 V:3 V) were then added. The mixture was heated to 86°C under nitrogen and allowed to react for 6 h. After post-treatment, extraction and separation were performed, and the organic phase was mixed and passed through a column to yield 23.87 g, a 62% yield.

[0162] Synthesis of N-89: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 11.1 g (25.6 mmol) of the intermediate N89-D, 10 g (24.5 mmol) of N89-2, 6.76 g (48.9 mmol) of potassium carbonate, and 0.566 g (0.5 mmol) of tetrakistriphenylphosphine palladium. Then, toluene: ethanol: water 54 mL: 18 mL: 18 mL (7V: 3V: 3V) were added. The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. After post-treatment, extraction and separation were carried out, and the organic phase was mixed and passed through a column to obtain 10.5 g, with a yield of 63%.

[0163] Elemental analysis: C 50 H 37 N3 theoretical value: C, 88.33; H, 5.49; N, 6.18; found: C, 88.36; H, 5.50; N, 6.14; HRMS (ESI) m / z [M+H] +: theoretical value: 679.30; found: 680.54.

[0164] Example 5

[0165] Synthesis of compound N-108

[0166]

[0167] Synthesis of N108-A-2: A 250 mL four-necked round-bottom flask was placed with a stirrer and a reflux tube. After drying, the flask was filled with nitrogen. At room temperature, 10 g of N108-A-1 (55.48 mmol, CAS: 613-31-0) was added to the flask and dissolved with 20 mL of deuterated dimethyl sulfoxide (99.9% atom D, CAS: 2206-27-1). 4.48 g of potassium hydride (0.1122 mol) was added, and the reaction mixture turned deep red. After stirring for 2 hours, 16 mL of heavy water (99.9% atom D, CAS: 7789-20-0) was added to the system, and a white precipitate immediately formed. The reaction was stirred for an additional 1 hour, and 8 g of the product was filtered, rinsed with water, and purified by recrystallization from ethanol to obtain the desired product N108-A-2 (7 g, yield: 73%).

[0168] Synthesis of N108-A: 7 g (38.04 mmol) of N108-A-2 obtained above was added to a 250 mL four-necked round-bottom flask, along with 37 g of 3,4,5,6-tetrachloro-1,2-benzoquinone (0.152 mol, CAS: 2435-53-2). 70 mL of 1,4-dioxane was added to the mixture, and the mixture was heated to 30°C and reacted for 48 hours. After completion of the reaction, the product was purified by column chromatography to obtain the desired product, compound NN108-A (6 g, 88% yield).

[0169] The synthesis of N108-1: get 1 liter of four-mouth round-bottomed flask and put into stirrer and upper connection reflux line, be filled with nitrogen after drying, get 6gN278-A (33.3mmol) and add in flask, molten clear with 100mL anhydrous DCM, be heated to reflux.14.4g N89-B (66.6mmol, CAS:20776-48-1) is dissolved in 84mL anhydrous THF and is mixed with N89-B / THF solution, 9.75g isoamyl nitrite (83.3mmol, CAS:110-46-3) is dissolved in 76mL anhydrous DCE, is mixed with isoamyl nitrite / DCE solution.N89-B / THF and isoamyl nitrite / DCE solution are dripped simultaneously, and the content of isoamyl nitrite in the maintenance system is always greater than the content of N89-B in the system.Time for adding is controlled at about 4h. After the addition was complete, the mixture was stirred and reacted under reflux for 12 hours. Purification by column chromatography gave the target product, compound N108-1 (7.5 g, yield: 68%).

[0170] Synthesis of N108-2: To a 250 mL three-necked flask equipped with a thermometer and magnetic stirring, 6.5 g of compound N108-1 (19.4 mmol), 5.9 g of bispinacol borate (23.3 mmol, CAS: 73183-34-3), 3.8 g of potassium acetate (38.8 mmol) and 282 mg of Pd(dppf)Cl2 (0.39 mmol) were added, and 70 mL of 1,4-dioxane was added. Under nitrogen protection, the temperature was raised to 110°C and the reaction was reacted for 4 h. 100 mL of toluene was added to the reaction solution, and the solution was extracted with 100 mL of water. The organic phase was mixed and passed through a column to obtain intermediate N108-2 (5.6 g, yield: 76%).

[0171] Synthesis of N108-D: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 23.2 g (135.0 mmol, CAS: 32316-92-0) of the intermediate N108-b-1, 30.0 g (128.5 mmol, CAS: 134517-55-8), 35.5 g (257.0 mmol) of potassium carbonate, and 2.97 g (2.57 mmol) of tetrakistriphenylphosphine palladium. Toluene:ethanol:water 162 mL:70 mL:70 mL (7V:3V:3V) were then added. The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. After post-treatment, extraction and separation were performed, and the organic phase was mixed and passed through a column to obtain 28.5 g of N108-a in a yield of 68%.

[0172] To a three-necked flask equipped with a magnetic stirrer and a condenser were added intermediate N108-b 7.9 g (64.8 mmol), N108-a 20 g (61.5 mmol), potassium carbonate 17 g (123.0 mmol), and tetrakistriphenylphosphine palladium 1.42 g (1.23 mmol), followed by toluene: ethanol: water 108 mL: 46 mL: 46 mL (7V: 3V: 3V). The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. After post-treatment, extraction and separation were carried out, and the organic phase was mixed and passed through a column to obtain 14.7 g, with a yield of 65%.

[0173] Synthesis of N-108: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 10.1 g (1.05 eq) of the intermediate N108-D, 10 g (26.2 mmol) of N108-2, 7.24 g (52.4 mmol) of potassium carbonate, and 0.605 g (0.524 mmol) of tetrakistriphenylphosphine palladium. Then, toluene: ethanol: water 54 mL: 18 mL: 18 mL (7V: 3V: 3V) were added. The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. After post-treatment, extraction was performed, the liquids were separated, and the organic phase was mixed and passed through a column to obtain 9.44 g, with a yield of 61%.

[0174] Elemental analysis: C 44 H26 D2N2 theoretical value: C, 90.07; H, 5.15; N, 4.77; found value: C, 90.04; H, 5.17; N, 4.79; HRMS (ESI) m / z [M+H] +: theoretical value: 586.24; found value: 587.51.

[0175] Example 6

[0176] Synthesis of compound N-137

[0177]

[0178] Synthesis of N137-1: Place a 1-liter, four-necked round-bottom flask in a stirrer and connect it to a reflux line. After drying, fill the flask with nitrogen. Add 10 g of Ni-A (48.4 mmol, CAS: 781-43-1) to the flask, dissolve it in 168 mL of anhydrous DCM, and heat to reflux. Dissolve 20.9 g of N89-B (96.9 mmol, CAS: 5794-88-7) in 140 mL of anhydrous THF to prepare an N89-B / THF solution. Dissolve 14.2 g of isoamyl nitrite in 126 mL of anhydrous DCE to prepare an isoamyl nitrite / DCE solution. Simultaneously add the N89-B / THF and isoamyl nitrite / DCE solutions dropwise, maintaining the isoamyl nitrite content greater than the N89-B content. Control the addition time to approximately 4 hours. After the addition is complete, stir the reaction under reflux for 12 hours. Purification by column chromatography gave the target product, compound N137-1 (7 g, yield: 42%).

[0179] Synthesis of N137-2: To a 250 mL three-necked flask equipped with a thermometer and magnetic stirring, 7 g of compound N137-1 (19.4 mmol), 5.9 g of bispinacol borate (23.3 mmol, CAS: 73183-34-3), 3.8 g of potassium acetate (38.8 mmol) and 282 mg of Pd(dppf)Cl2 (0.39 mmol) were added, and 70 mL of 1,4-dioxane was added. Under nitrogen protection, the temperature was raised to 110°C and the reaction was reacted for 4 h. 100 mL of toluene was added to the reaction solution, and the solution was extracted with 100 mL of water. The organic phase was mixed and passed through a column to obtain intermediate N137-2 (6 g, yield: 76%).

[0180] Synthesis of N-137: To a three-necked flask equipped with a magnetic stirrer and a condenser, 9.42 g (24.0 mmol, CAS: 2375162-72-2) of the intermediate N137-D, 10 g (22.9 mmol) of N137-2, 6.33 g (45.8 mmol) of potassium carbonate, and 0.529 g (0.02 eq) of tetrakistriphenylphosphine palladium were added. Toluene: ethanol: water 54 mL: 18 mL: 18 mL (7 V: 3 V: 3 V) were then added. The mixture was heated to 86°C under nitrogen protection and reacted for 6 h. After post-treatment, extraction and separation were performed. The organic phase was mixed and passed through a column to obtain 10.06 g of the mixture, with a yield of 66%.

[0181] Elemental analysis: C 49 H 35 N3 theoretical value: C, 88.39; H, 5.30; N, 6.31; found: C, 88.41; H, 5.32; N, 6.27; HRMS (ESI) m / z [M+H] +: theoretical value: 665.28; found: 666.05.

[0182] Example 7

[0183] Synthesis of compound N-220

[0184]

[0185] Synthesis of N220-1: A 1000 ml three-necked flask was dried and filled with nitrogen. 2 g of N220-A (66.6 mmol, CAS: 1499-10-1) and 180 ml of 1,2-dichloroethane were added and dissolved by stirring at 80°C. 20 ml of isoamyl nitrite (150.2 mmol) was added and stirred at 80°C for 5 minutes. 25 g of anthranilic acid N89-B (115.7 mmol) dissolved in 100 ml of diethylene glycol dimethyl ether was added dropwise and stirred at 150°C for 3 hours. After cooling to room temperature, the resulting reaction mixture was purified by silica gel column chromatography. The mixture was then reslurried by heating with chloroform to obtain 16.5 g of intermediate N220-.

[0186] Synthesis of N220-2: To a 250 mL three-necked flask equipped with a thermometer and magnetic stirring, 6.4 g of compound N220-A (19.4 mmol), 5.9 g of bispinacol borate (23.3 mmol, CAS: 73183-34-3), 3.8 g of potassium acetate (38.8 mmol) and 282 mg of Pd(dppf)Cl2 (0.39 mmol) were added, and 70 mL of 1,4-dioxane was added. Under nitrogen protection, the temperature was raised to 110°C and the reaction was reacted for 4 h. 100 mL of toluene was added to the reaction solution, and the solution was extracted with 100 mL of water. The organic phase was mixed and passed through a column to obtain the intermediate N220-2 (7.9 g, yield: 76%).

[0187] Synthesis of N220-D: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 127.8 g (134.9 mmol) of the intermediate N220-b, 130 g (128.5 mmol) of N108-a, 35.5 g (2.0 eq) of potassium carbonate, and 2.97 g (0.02 eq) of tetrakistriphenylphosphine palladium. Toluene:ethanol:water 162 mL:70 mL:70 mL (7V:3V:3V) were then added. The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. The mixture was extracted and separated, and the organic phase was mixed and passed through a column to obtain 28.5 g of N220-a in a yield of 68%.

[0188] To a three-necked flask equipped with a magnetic stirrer and a condenser were added 7.9 g (64.6 mmol) of the intermediate N108-a, 20 g (61.5 mmol) of N220-a, 17 g (2.0 eq) of potassium carbonate, and 1.42 g (0.02 eq) of tetrakistriphenylphosphine palladium. Toluene:ethanol:water 108 mL:46 mL:46 mL (7V:3V:3V) were then added. The temperature was raised to 86°C under nitrogen protection and the reaction was carried out for 6 h. After post-treatment, extraction and separation were performed, and the organic phase was mixed and passed through a column to obtain 14.68 g of N220-D in a yield of 65%.

[0189] Synthesis of N-220: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 7.24 g (1.05 eq) of the intermediate N220-D, 18.8 mmol (18.8 mmol) of N220-210 g (5.2 g (37.6 mmol) of potassium carbonate, and 0.434 g (0.376 mmol) of tetrakistriphenylphosphine palladium. Toluene: ethanol: water 54 mL: 18 mL: 18 mL (7V: 3V: 3V) were then added. The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. After post-treatment, extraction was performed, the liquids were separated, and the organic phase was mixed and passed through a column to obtain 8.7 g, with a yield of 63%.

[0190] Elemental analysis: C 56 H 36Theoretical value of N2: C, 91.27; H, 4.92; N, 3.80; Measured value: C, 91.23; H, 4.93; N, 3.84;

[0191] HRMS (ESI) m / z [M+H] + : Required: 736.29; Found: 737.32.

[0192] Example 8

[0193] Synthesis of compound N-231

[0194]

[0195] Synthesis of N-231: To a three-necked flask equipped with a magnetic stirrer and a condenser were added 8.35 g (19.7 mmol, CAS: 2760136-31-8) of the intermediate N231-D, 18.8 mmol (18.8 mmol) of N220-210 g (37.6 mmol) of potassium carbonate, and 0.434 g (0.376 mmol) of tetrakistriphenylphosphine palladium. Then, toluene: ethanol: water 54 mL: 18 mL: 18 mL (7V: 3V: 3V) were added. The temperature was raised to 86°C under nitrogen protection, and the reaction was carried out for 6 h. After post-treatment, extraction and separation were carried out, and the organic phase was mixed and passed through a column to obtain 9.69 g of N-231 with a yield of 65%.

[0196] Elemental analysis: C 57 H 35 N3S theoretical value: C, 86.23; H, 4.44; N, 5.29; S, 4.04; found: C, 86.25; H, 4.45; N, 5.25; S, 4.05; HRMS (ESI) m / z [M+H]+: theoretical value: 793.26; found: 794.58.

[0197] Examples 9-17 refer to the above preparation method. Specifically, the raw materials used in Examples 9-17 and the products obtained are shown in Table 1 below.

[0198] Table 1

[0199]

[0200]

[0201] The characterization data of the products prepared in Examples 9-17 are shown in Table 2:

[0202] Table 2

[0203]

[0204] Example 18

[0205] This embodiment provides a method for preparing compound H1 of formula (2). The structure and synthesis route of H1 are shown below. The preparation steps are:

[0206]

[0207] Synthesis of Compound H1: A 25 ml three-necked flask was charged with H1-A (1 mmol), H1-B (1 mmol), Pd2(dba)3 (0.05 mmol), 50% tri-tert-butylphosphine solution (0.1 mmol), NaOtBu (2.2 mmol), and toluene (10 ml). The mixture was stirred at reflux for 6 hours. After the reaction was complete, the reaction mixture was cooled to room temperature and the organic solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (ethyl acetate:n-hexane (volume ratio 1:10)) to obtain Compound H1 (0.28 g, 48% yield).

[0208] Elemental analysis: C 48 H 31 NO2 Required: C, 88.18; H, 4.78; N, 2.14; Found: C, 88.24; H, 4.76; N, 2.13; HRMS (ESI) m / z [M+H] + : Theoretical value: 653.24; measured value: 654.30.

[0209] Examples 19-21 were prepared with reference to the method of Example 18. Specifically, the raw materials used in Examples 19-21 and the products obtained are shown in Table 3 below.

[0210] Table 3

[0211]

[0212] The characterization data of the products prepared in Examples 19-21 are shown in Table 4:

[0213] Table 4

[0214]

[0215]

[0216] Device Examples and Comparative Examples

[0217] The embodiment and comparative example provide an organic electroluminescent device, such as Figure 1As shown, it includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 8 stacked in sequence on a substrate 1, and its device structure is: substrate + anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0218] The materials used to manufacture the organic electroluminescent device are as follows:

[0219]

[0220] The preparation of the organic electroluminescent device comprises the following steps:

[0221] 1) Substrate cleaning:

[0222] A glass substrate coated with transparent ITO was ultrasonically treated in an aqueous detergent (the composition and concentration of the aqueous detergent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (acetone and ethanol volume ratio of 1:1), baked in a clean environment to completely remove moisture, and then cleaned with ultraviolet light and ozone.

[0223] 2) Preparation of organic layer:

[0224] The ITO transparent substrate was transferred to the evaporation equipment and vacuumed to 1×10 -6 to 2×10 -4 Pa, 10nm hole injection layer 3 (HIL) / 80nm hole transport layer 4 (HTL) / 30nm light emitting layer 5 (EML) / 30nm electron transport layer 6 (ETL) / 1nm electron injection layer 7 (EIL) / 80nm thick cathode 8 (Al) are sequentially deposited on the anode 2.

[0225] in:

[0226] The material of the hole injection layer 3 (HIL) is a mixture of HAT(CN)6 and HT, wherein the mass ratio of HAT(CN)6 to HT is 3:97;

[0227] The material of the hole transport layer 4 (HTL) is HT;

[0228] The materials of the light-emitting layer 5 (EML) include a host material and a guest material, wherein the guest material is (piq)2Ir(acac). The specific materials and ratios of the host material and the guest material are shown in Table 5. The evaporation method is vacuum evaporation by co-evaporation.

[0229] The material of the electron transport layer 6 (ETL) is a mixture of BPhen and LiQ, wherein the mass ratio of BPhen to LiQ is 1:1; the evaporation method is vacuum evaporation in a co-evaporation manner;

[0230] The material of the electron injection layer 7 (EIL) is LiQ; some layers of the organic electroluminescent device and their materials and thicknesses are shown in Table 5.

[0231] Table 5

[0232]

[0233]

[0234]

[0235] Test Case

[0236] The organic electroluminescent devices obtained from device examples 1 to 22 and comparative examples 1 to 3 in the device examples were tested.

[0237] Instruments: The device's current, voltage, brightness, luminous spectrum and other characteristics are tested synchronously using a PR 650 spectrum scanning luminance meter and a Keithley K2400 digital source meter system;

[0238] Test conditions: Photoelectric characteristics test conditions: current density is 10mA / cm2.

[0239] Life test: The current density is 50 mA / cm2, and the time (in hours) when the device brightness drops to 95% of the original brightness is recorded.

[0240] The device performance test results are shown in Table 6:

[0241] Table 6

[0242]

[0243]

[0244] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. An organic electroluminescent compound, characterized in that Has the following structure: R 13 、R 14 Each independently selected from deuterium, unsubstituted C1-C20 alkyl, and unsubstituted C3-C30 aryl; Among them, R 1 -R 12 One of them has the structure shown below, and the others are hydrogen and deuterium: X 1 -X 5 middle, X 1 N, X 2 N, X 3 CR X3 , X 4 CR X4 , and X 5 CR X5 ;or X 1 N, X 3 N, X 2 CR X2 , X 4 CR X4 , and X 5 CR X5 ;or X 1 N, X 2 N, X 3 N, X 4 CR X4 , and X 5 CR X5 ;or X 1 N, X 5 N, X 2 CR X2 , X 3 CR X3 , and X 4 CR X4 ;or X 1 CR X1 , X 2 CR X2 , X 3 CR X3 , X 4 CR X4 , and X 5 CR X5 ; R X1 -R X5 are each independently selected from hydrogen, deuterium, tritium, substituted or unsubstituted C6-C30 aryl, unsubstituted C3-C30 heteroaryl, R X1 -R X5 Each exists independently, or two adjacent rings are connected to form ring A, wherein ring A is a substituted or unsubstituted benzene ring or pyrimidine ring; L is selected from a connecting bond, an unsubstituted C6-C30 aromatic ring; n is an integer from 0 to 5; The substituent in the substituted C6-C30 aryl group is selected from one or a combination of deuterium and C1-C6 alkyl groups; the substituent in the substituted or unsubstituted benzene ring or pyrimidine ring is selected from deuterium and C5-C12 aryl groups.

2. The organic electroluminescent compound according to claim 1, characterized in that L is selected from a single bond, an unsubstituted phenylene group, an unsubstituted biphenylene group, an unsubstituted terphenylene group, and an unsubstituted naphthylene group.

3. The organic electroluminescent compound according to claim 1, characterized in that L is selected from phenylene, biphenylene, and naphthylene; n is 0 or 1.

4. The organic electroluminescent compound according to claim 1, characterized in that R X1 -R X5 Each exists independently; or R X1 -R X5 Among them, two adjacent ones are connected to form ring A, and the others exist independently; R X1 -R X5 Each is independently selected from hydrogen, unsubstituted C6-C30 aryl, and unsubstituted C3-C30 heteroaryl.

5. The organic electroluminescent compound according to claim 1, characterized in that R X2 -R X5 Each is independently selected from hydrogen, a substituted or unsubstituted A group, wherein the A group is selected from one of the following groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, pyrenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dinaphthothiophenyl, dinaphthofuranyl, benzophenanthrofuryl, dinaphthothiophenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, benzonaphthothiophenyl, phenyldibenzocarbazolyl, phenylbenzocarbazolyl, phenylcarbazolyl, dibenzocarbazolyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, and dimethylfluorenylphenyl; The substituent of the substituted A group is selected from hydrogen, C1-C6 alkyl, or a combination of both.

6. The organic electroluminescent compound according to claim 1, characterized in that The formula (a) is selected from one of the following groups: Among them, R X2 -R X5 Each is independently selected from hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, and unsubstituted C3-C30 heteroaryl; R X15 、R X16 Each independently selected from hydrogen, deuterium, and C5-C12 aryl; The substituent in the substituted C6-C30 aryl group is selected from hydrogen, C1-C6 alkyl, or a combination of both.

7. The organic electroluminescent compound according to claim 1, characterized in that R X2 -R X5 Each is independently selected from hydrogen, a substituted or unsubstituted A group, wherein the A group is selected from one of the following groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, pyrenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dinaphthothiophenyl, dinaphthofuranyl, benzophenanthrofuryl, dinaphthothiophenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, benzonaphthothiophenyl, phenyldibenzocarbazolyl, phenylbenzocarbazolyl, phenylcarbazolyl, dibenzocarbazolyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, and dimethylfluorenylphenyl; R X15 、R X16 Each is independently selected from hydrogen, phenyl, biphenyl, naphthyl; The substituent of the substituted A group is selected from hydrogen, C1-C6 alkyl, or a combination of both.

8. The organic electroluminescent compound according to claim 1, characterized in that R X2 -R X5 each independently selected from hydrogen, phenyl, biphenyl, naphthyl, phenanthrenyl, triphenylene, pyrenyl, benzonaphthothienyl, benzodimethylfluorenyl, dibenzofuranyl, triphenylfuranyl, spirobifluorenyl; R X15 、R X16 Each is independently selected from hydrogen, phenyl, biphenyl, and naphthyl.

9. The organic electroluminescent compound according to claim 1, characterized in that R 13 、R 14 Each is independently selected from deuterium and C1-C6 alkyl.

10. The organic electroluminescent compound according to claim 1, characterized in that R 13 、R 14 Each is independently selected from deuterium, methyl, and ethyl.

11. The organic electroluminescent compound according to any one of claims 1 to 10, characterized in that The organic electroluminescent compound is selected from one of the following structures:

12. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises a first host material and a second host material, wherein the first host material comprises the organic electroluminescent compound according to any one of claims 1 to 11, and the second host material comprises a compound having the structure of the following formula (2): Among them, Ar W1 、Ar W2 、Ar W3 are independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, Ar W1 、Ar W2 、Ar W3 They are not connected to each other or two adjacent ones are connected to form a ring; L W1 、L W2 、L W3 Each independently selected from a connecting bond, an unsubstituted C6-C30 arylene group; The substituents in the substituted C6-C60 aryl group and the substituted C3-C60 heteroaryl group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C5-C12 aryl, and C3-C12 heteroaryl groups.

13. The organic electroluminescent material according to claim 12, characterized in that L W1 、L W2 、L W3 Each is independently selected from a linker, a phenylene group, a biphenylene group, or a naphthylene group.

14. The organic electroluminescent material according to claim 12 or 13, characterized in that: In formula (2), Ar W1 、Ar W2 、Ar W3 Each is independently selected from phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, anthracenyl, phenanthrenyl, triphenylene, pyridyl, and a group represented by formula (b-1): Wherein W is selected from O, S, CR W1 R W2 , and NR w , R w -L W R W3 ; When Ar W1 、Ar W2 、Ar W3 When any one, two or three of the following are selected from formula (b-1), R in formula (b-1) 10’ -R 17’ 、R W1 、R W2 、R W3 Any one of them is chemically bonded to L W1 、L W2 or L W3 connect; When formula (2) contains multiple groups of formula (b-1), the multiple groups of formula (b-1) are the same or different; R 10’ -R 17’ 、R W1 、R W2 、R W3 Each is independently selected from a linker, hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group; R 10’ -R 17’ Each exists independently or two adjacent rings are connected to form ring B, and the ring B is an unsubstituted C6-C30 aromatic ring; L W Selected from a connecting bond, an unsubstituted C6-C30 arylene group; The substituent in the substituted C1-C30 alkyl group is selected from one or a combination of two of deuterium, a C1-C6 alkyl group, a C3-C30 cycloalkyl group, and a C3-C12 heteroaryl group.

15. The organic electroluminescent material according to claim 12, characterized in that Formula (b-1) is selected from the structures shown in any one of the following: Among them, R 10’ -R 17’ each independently selected from hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, anthracenyl, phenanthrenyl, triphenylenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzonaphthofuranyl, and benzonaphthothiophenyl; W is selected from O, S, CR W1 R W2 , and NR w , R w -L W R W3 ; Among them, R W1 -R W2 are independently selected from hydrogen, deuterium, methyl, ethyl, and phenyl, or R W1 -R W2 Connected into spiro ring by chemical bonds; R W3 a substituted or unsubstituted group selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, benzonaphthothiophene, dinaphthofuranyl, dinaphthothiophenyl, dibenzofuranphenyl, dibenzothiophenephenyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, and dimethylfluorenylphenyl; L W is selected from a linker, a phenylene group, a biphenylene group, and a naphthylene group.

16. The organic electroluminescent material according to claim 12, characterized in that The formula (b-1) is selected from the unsubstituted D group: Wherein the D group is selected from one of the following groups:

17. The organic electroluminescent material according to claim 12, characterized in that Ar W1 、Ar W2 、Ar W3 Each is independently selected from phenyl, naphthyl, dibenzofuranyl, spirobifluorenyl, phenylcarbazolyl, benzodimethylfluorenyl, and dibenzocarbazolyl.

18. The organic electroluminescent material according to claim 12, characterized in that The compound of formula (3) is selected from one of the following compounds:

19. The organic electroluminescent material according to claim 12, characterized in that The mass ratio of the compound represented by formula (1) to the compound represented by formula (2) is 3:7-7:

3.

20. The organic electroluminescent material according to claim 12, characterized in that The mass ratio of the compound represented by formula (1) to the compound represented by formula (2) is 4:6-6:

4.

21. Use of the organic electroluminescent material according to any one of claims 12 to 20 in the preparation of optical devices.

22. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode and a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the organic electroluminescent compound according to any one of claims 1 to 11 or the organic electroluminescent material according to any one of claims 12 to 20.

23. The organic electroluminescent device according to claim 22, characterized in that: The light-emitting layer in the organic layer comprises the organic electroluminescent compound according to any one of claims 1 to 11 or the organic electroluminescent material according to any one of claims 12 to 20.

24. An organic electroluminescent device, characterized in that The organic electroluminescent device comprises the organic electroluminescent device according to claim 22 .

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