WO2023138254A1 - Heterocyclic compound, and organic electroluminescent material and element - Google Patents

Abstract

The present invention relates to a heterocyclic compound, an organic electroluminescent material, and an organic electroluminescent element. The structure of the heterocyclic compound is as shown in formula (I). The heterocyclic compound of the present invention is of a bi-heterocyclic structure comprising at least one nitrogen atom, and has high stability performance and an electron transport capability. The organic electroluminescent element prepared by using the compound of the present invention can significantly reduce a starting voltage, and improve the light-emitting efficiency and brightness.

Description

Heterocyclic compounds, organic electroluminescent materials and components

cross reference

This application claims the priority of the Chinese patent application No. 202210073765.2 filed on January 21, 2022 with the title of "Heterocyclic Compounds, Organic Electroluminescent Materials and Components", the entire disclosure content of which is incorporated herein by reference in its entirety.

technical field

The invention belongs to the technical field of organic electroluminescence, and in particular relates to a heterocyclic compound, an organic electroluminescence material and an organic electroluminescence element.

Background technique

In general, the organic light-emitting phenomenon refers to a phenomenon in which light is emitted when electric energy is applied to an organic substance. That is, when the organic layer is arranged between the anode and the cathode, when a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition to the ground state, light and heat are emitted.

As a method of effectively manufacturing organic electroluminescent elements, research has been carried out on replacing the organic layer in a single-layer manufacturing element with a multilayer structure. In 1987, Tang proposed an organic electroluminescent element with a laminated structure of a hole layer and a functional layer of a light-emitting layer. Most of the organic electroluminescent elements currently used include: a substrate, an anode, a hole injection layer that receives holes from the anode, a hole transport layer that transports holes, a light-emitting layer that emits light by recombining holes and electrons, an electron transport layer that receives electrons from the cathode. Electron injection layer and cathode. The reason why the organic electroluminescent element is fabricated in multiple layers is that since holes and electrons move at different speeds, if an appropriate hole injection layer and transport layer, electron transport layer, and electron injection layer are fabricated, holes and electrons can be efficiently transported, and the balance of holes and electrons in the element can be achieved, which can improve the utilization rate of excitons.

An oxadiazole derivative is mentioned as the earliest report on an electron transport material. It was later disclosed that triazole derivatives and phenanthroline derivatives exhibit electron transport properties. Substances that can be applied to the electron transport layer are organic monomolecular substances. It has been reported that organometallic complexes with relatively excellent electron stability and electron movement speed are good candidates. Liq, which has excellent stability and high electron affinity, is the most excellent substance and is currently the most basically used substance.

Furthermore, many organic monomolecular substances having an imidazolyl group, an oxazolyl group, a thiazolyl group, a spirofluorenyl group, and a carboline have been reported as conventional substances applicable to electron injection layers and transport layers. For example, CN103833507B, CN107573328B, CN107556310B publicly authorized by the Chinese Patent Office, and CN109651364A and CN110294755A, which were first applied by the inventor, are derivatives with carboline as the parent nucleus. After testing, it was found that after incorporating two benzofuran, benzothiophene or indole rings on the basis of the pyridine ring, the LUMO energy level of the molecule increased and the HOMO The energy level is reduced, and the carrier mobility of the amorphous film is greatly improved.

In view of the above reasons, the present invention is proposed.

Contents of the invention

In order to solve the above problems in the prior art, the present invention provides a heterocyclic compound, an organic electroluminescent material, a light-emitting element and a consumer product. The compound of the present invention improves the thermal stability of the material and the ability to transport electrons. The organic electroluminescent element prepared by using the compound of the present invention can significantly reduce the starting voltage and improve luminous efficiency and brightness.

The first object of the present invention provides a kind of heterocyclic compound, described heterocyclic compound is shown in formula (I):

Wherein, adjacent W ¹ and W ² , W ³ and W ⁴ each independently represent a group represented by formula (II);

wherein G represents O, S, CR ³ R ⁴ , NR ⁵ , SiR ³ R ⁴ or GeR ³ R ⁴ , Z represents CR ¹ or N identically or differently at each occurrence, and ^ indicates the corresponding adjacent groups W ¹ and W ² , W ³ and W ⁴ in formula (I);

Ring B represents an aromatic ring containing at least two carbon atoms, preferably, selected from substituted or unsubstituted C ₆-C ₆₀Aryl, substituted or unsubstituted C ₆-C ₆₀Fused ring aryl, substituted or unsubstituted C ₆-C ₆₀Arylamino, substituted or unsubstituted C ₆~C ₆₀Arylboryl, substituted or unsubstituted C ₆~C ₆₀Arylphosphoryl, substituted or unsubstituted C ₆~C ₆₀Arylphosphinyl, substituted or unsubstituted C ₆~C ₆₀Arylsilyl, substituted or unsubstituted C ₂-C ₆₀Heteroaryl or substituted or unsubstituted C ₂-C ₆₀A group consisting of heteroarylamine groups;

R ¹, R ², R ³, R ⁴, R ⁵each independently selected from hydrogen, deuterium, halogen, nitrile, nitro, substituted or unsubstituted C ₆-C ₆₀Aryl, substituted or unsubstituted C ₆-C ₆₀Aryloxy, substituted or unsubstituted C ₆-C ₆₀Fused ring aryl, substituted or unsubstituted C ₆-C ₆₀Arylamino, C ₆~C ₆₀The aryl boron group, C ₆~C ₆₀The arylphosphoryl group, C ₆~C ₆₀Arylphosphinyl, substituted or unsubstituted C ₆-C ₆₀Aralkyl, C ₁~C ₄₀Alkylsilyl, C ₆~C ₆₀The arylsilyl group, or substituted or unsubstituted C ₂-C ₆₀Groups consisting of heteroaryl groups;

R ² is monosubstituted to saturated substituted.

Further, the heterocyclic compound includes structures represented by formulas (III) to (VI):

Wherein, G ₁ and G ₂ each independently represent O, S, CR ³ R ⁴ , NR ⁵ or SiR ³ R ⁴ , and Z represents CR ¹ or N identically or differently at each occurrence;

Further, the R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently selected from hydrogen, deuterium, halogen atom, nitrile group, nitro group, substituted or unsubstituted C ₆ -C ₆₀ aryl group, substituted or unsubstituted C ₆ -C ₆₀ aryloxy group, substituted or unsubstituted C _{6 -C 60 fused ring aryl group, substituted or unsubstituted C 6 -C 60 arylamino group, C 6 -C 60 A group consisting of an arylphosphoryl group, a C 6 -C 60 arylphosphoryl group , or a} substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group.

Further, the ring B is one or more of the following structures:

Wherein, V represents CR ⁶ R ⁷ , NR ⁸ , O or S; the dotted bond represents the position of attachment to ring A, and in addition:

W is CR ⁹ or N identically or differently at each occurrence; or two adjacent groups W represent groups of the following formula (6) or (7),

Wherein, G, Z are identical with the definition of above-mentioned G, Z, and " " represents the corresponding adjacent group W in formula (2), (3), (4) or (5), and contains at least 2 carbon atoms in formula (2), (3), (4), (5);

R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently selected from hydrogen, deuterium, halogen atom, nitrile group, nitro group, substituted or unsubstituted C _{6 -C 60} aryl group, substituted or unsubstituted C ₆ -C ₆₀ aryloxy group, substituted or unsubstituted C ₆ -C ₆₀ condensed ring aryl group, substituted or unsubstituted C ₆ -C 60 arylamino group, C ₆ -C 60 arylphosphoryl group, C ₆ ~C ₆₀ arylphosphinyl, or a group consisting of substituted or unsubstituted C _{2 -C 60 heteroaryl} .

Further, the ring B is selected from the group consisting of the following groups:

Wherein, the meaning of G is the same as the above definition.

In some preferred embodiments, the ring B is selected from the group consisting of the following formulas B1-B15:

Among them, G is *—O—*, *—S—* or one of the following structures:

*—and—* represent the connecting bond with two benzene rings;

Each R in the B1～B15 structure ⁷can be independently selected from deuterium, halogen, nitrile, C ₁~C ₄₀Alkyl, C ₂~C ₄₀Alkenyl, C ₂~C ₄₀Alkynyl, C ₃~C ₄₀Cycloalkyl, C ₃~C ₄₀heterocycloalkyl, C ₆~C ₆₀Aryl, C ₂~C ₆₀The heteroaryl, C ₁~C ₄₀Alkoxyl, C ₆~C ₆₀Aryloxy group, C ₁~C ₄₀Alkylsilyl, C ₆~C ₆₀The arylsilyl group, C ₁~C ₄₀Alkylboryl, C ₆~C ₆₀The aryl boron group, C ₆~C ₆₀The arylphosphoryl group, C ₆~C ₆₀Arylphosphine, C ₆~C ₆₀A group consisting of arylamino groups. At this time, when there are more than one substituents, the plurality of substituents are the same or different from each other.

The alkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. As non-limiting examples thereof, there are methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, and the like.

The alkenyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon double bonds and having 2 to 40 carbon atoms. As non-limiting examples thereof, there are vinyl, allyl, isopropenyl, 2-butenyl and the like.

The alkynyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon triple bonds and having carbon atoms ranging from 2 to 40. As non-limiting examples thereof, there are ethynyl, 2-propynyl and the like.

The cycloalkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. As non-limiting examples thereof, there are cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl and the like.

The heterocycloalkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having 3 to 40 atomic nuclei. In this case, one or more carbons, preferably 1 to 3 carbons in the ring are substituted with heteroatoms such as N, O or S. As non-limiting examples thereof, there are tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine, and the like.

The aryl group used in the present invention refers to a monocyclic ring or a monovalent functional group obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms in two or more rings combined via a single bond. At this time, two or more rings may be attached to each other simply or in a condensed form. Non-limiting examples thereof include, for example, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, indenyl, 9,9-spirobifluorenyl, and the like.

The condensed ring aryl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms in which two or more rings are combined. At this time, two or more rings may be attached to each other simply or in a condensed form. As non-limiting examples thereof, there are, for example, phenanthrenyl, anthracenyl, fluoranthenyl, pyrenyl, triphenylene, perylenyl,

Base etc.

The arylamino group used in the present invention refers to an amine substituted by an aryl group with carbon atoms from 6 to 60. As non-limiting examples of the arylamino group, there are diphenylamino, N-phenyl-1-naphthylamino, N-(1-naphthyl)-2-naphthylamino and the like. Heteroarylamine refers to an amine substituted by an aryl group with 6 to 60 carbon atoms and a heteroaryl group with 2 to 60 carbon atoms. Non-limiting examples of the heteroarylamino group include N-phenylpyridin-3-amine, N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-2-amino, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2- Amino etc.

The heteroaryl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon with a carbon number of 2 to 60, and more than one carbon in the ring, preferably 1 to 3 carbons, are replaced by heteroatoms such as nitrogen, oxygen, sulfur or selenium. In this case, two or more rings of the heteroaryl group may be attached to each other simply or in a condensed form, and may further include a form condensed with an aryl group. Non-limiting examples of such heteroaryl groups include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathiyl, indolazinyl, indolyl, purinyl, quinolinyl, benzothiazolyl, carbazolyl, dibenzofuryl, and dibenzothienyl; and five-membered monocyclic rings such as 2-furyl, N-imidazolyl, and 2-isoxazolyl.

In the present invention, aryl, fused-ring aryl, and heteroaryl, as non-limiting examples, particularly refer to groups derived from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,

Perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, diphenyl, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, tripolyindene, isotriindene, spirotriindene, spiroisotriindene, furan, benzofuran, isobenzofuran, dibenzofuran, Thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthalene imidazole, phenanthromidazole, pyridoimidazole, pyrazinoimidazole, Quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthraxazole, phenanthraxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene Pyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorocycline, naphthyridine, azacarbazole, benzocarboline, carboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4 -oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, quinazoline and benzo Thiadiazole, etc., or groups derived from combinations of these systems.

The alkoxy group used in the present invention refers to a monovalent functional group represented by RO ^- , where R is an alkyl group with 1 to 40 carbon atoms, which may include straight chain, branched chain or ring structure. Non-limiting examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentyloxy, cyclopentyloxy, cyclohexyloxy and the like.

The aryloxy group used in the present invention refers to a monovalent functional group represented by ^R'O- , where R' is an aryl group having 6 to 60 carbon atoms. As non-limiting examples of such aryloxy groups, there are phenoxy, naphthyloxy, biphenoxy and the like.

The alkylsilyl group used in the present invention refers to a silyl group substituted by an alkyl group with 1 to 40 carbon atoms, and the number of carbon atoms constituting the alkylsilyl group is at least 3. As non-limiting examples of the alkylsilyl group, there are trimethylsilyl, triethylsilyl and the like. The arylsilyl group refers to a silyl group substituted with an aryl group having from 6 to 60 carbon atoms.

The arylphosphoryl group used in the present invention refers to a diarylphosphoryl group substituted by an aryl group having 6 to 60 carbon atoms. Non-limiting examples of the arylphosphoryl group include diphenylphosphoryl, bis(4-trimethylsilylphenyl)phosphoryl, and the like. An arylphosphoryl group is a diarylphosphoryl group in which the phosphorus atom is oxidized to the highest valence state.

The arylboryl group used in the present invention refers to a diarylboryl group substituted by an aryl group having 6 to 60 carbon atoms. Non-limiting examples of the arylboryl group include diphenylboryl group, bis(2,4,6-trimethylphenyl)boryl group, and the like. The alkylboryl group refers to a dialkylboryl group substituted with an alkyl group having 1 to 40 carbon atoms. Non-limiting examples of the alkylboryl group include di-tert-butylboryl group, diisobutylboryl group and the like.

The substituents described in the present invention are selected from the group consisting of hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or its carboxylate, sulfonic acid or its sulfonate, phosphoric acid or its phosphate, C ₁-C ₆₀Alkyl, C ₂-C ₆₀Alkenyl, C ₂-C ₆₀Alkynyl, C ₁-C ₆₀Alkoxy, C ₃-C ₆₀Cycloalkane, C ₃-C ₆₀Cycloalkenyl, C ₆-C ₆₀Aryl, C ₆-C ₆₀Aryloxy, C ₆-C ₆₀Arylthio, C ₆-C ₆₀Arylphosphonyl, C ₆-C ₆₀Arylphosphoxy, or C ₂-C ₆₀A group consisting of heterocyclic aryl groups.

Further, the heterocyclic compound, as a non-limiting example, includes the following structures of C740-C1093:

Among them, *—T ₂ —* is *—O—*, *—S—* or one of the following structures:

*— and —* represent linkages to two benzene rings.

The second object of the present invention is to provide an organic electroluminescent material, wherein the raw material of the organic electroluminescent material includes the above-mentioned heterocyclic compound.

Preferably, the organic electroluminescent material comprising the compound of the present invention has the ability to transport carriers.

The third object of the present invention provides an organic electroluminescent element, comprising a first electrode, a second electrode, a capping layer and at least one organic layer placed between the first electrode and the second electrode, at least one layer of the organic layer or the capping layer comprising the compound shown in the formula (I). In this case, the above compounds may be used alone or in combination of two or more.

The above one or more organic layers may be any one or more of a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and an electron blocking layer. Preferably, the organic layer comprising the compound of the above chemical formula (I) may be an emissive layer, an electron transport layer, and an electron transport auxiliary layer further laminated on the electron transport layer, more preferably, an electron transport layer and an emissive layer.

The light-emitting layer of the organic electroluminescent element according to the present invention may contain a host material (preferably a phosphorescent host material), and in this case, the compound of the above chemical formula I may be included as the host material. In this way, when the light-emitting layer contains the compound represented by the above-mentioned chemical formula I, the electron transport ability increases, and the bonding force between holes and electrons in the light-emitting layer is enhanced, so it is possible to provide an organic electroluminescent element excellent in efficiency (luminous efficiency and power efficiency), lifespan, brightness and driving voltage. In addition, the light-emitting layer dopant of the organic electroluminescent device of the present invention may contain the compound of the above chemical formula (I), or may contain other compounds as hosts or dopants.

The electron transport layer of the organic electroluminescent device of the present invention may contain an electron transport material. In this case, the electron transport layer material may contain the heterocyclic compound described in the above formula (I). In this way, when the electron transport layer contains the compound represented by the above formula (I), the electron transport ability is increased due to the strong carrier mobility, and the injected electrons can be smoothly supplied to the light emitting layer, so it is possible to provide an organic electroluminescence device excellent in efficiency (luminous efficiency and power efficiency), lifespan, brightness and driving voltage. However, an electron transport auxiliary layer may be further laminated on the above-mentioned electron transport layer. In the case where the electron transport auxiliary layer contains a compound represented by the above-mentioned heterocyclic compound, the effect (triplet-triplet fusion, TTF) of preventing exciton transition from the light-emitting layer and the electron transport layer due to the high _T1 value is large, so the efficiency (luminous efficiency and power efficiency), life, and driving voltage of the blue organic electroluminescence device can be improved especially.

The structure of the organic electroluminescent element of the present invention is not particularly limited. As a non-limiting example, a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode can be stacked in sequence. Wherein, a capping layer (CPL layer) may be further stacked on the cathode layer, as shown in FIG. 2 . In addition, the structure of the organic electroluminescent element of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted between the electrode and the organic layer.

On the other hand, in the organic electroluminescent device of the present invention, except that one or more layers of the above-mentioned organic layer contain the compound represented by the above-mentioned heterocyclic compound, the organic layer and the electrode can be formed using materials and methods known in the art.

In addition, the material that can be used as the anode contained in the organic electroluminescent element according to the present invention is not particularly limited. As a non-limiting example, metals such as vanadium, chromium, copper, zinc, gold, aluminum or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); metal oxides such as ZnO:Al or SnO2:Sb The combination of oxides; polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1 ,2-Dioxy)thiophene] (PEDT), polypyrrole and polyaniline and other conductive polymers; and carbon black, etc.

The material that can be used as the negative electrode contained in the organic electroluminescent element according to the present invention is not particularly limited. As a non-limiting example, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof;

Substrates that can be used as substrates included in the organic electroluminescent element according to the present invention are not particularly limited, and as non-limiting examples, silicon wafers, quartz, glass plates, metal plates, or plastic films and sheets can be used.

Furthermore, preference is given to organic electroluminescent components in which one or more layers are applied by means of a sublimation method, in which the material is applied by vapor deposition in a vacuum sublimation apparatus at an initial pressure below 10 ⁻⁵ Pa, preferably below 10 ⁻⁶ Pa. However, the initial pressure may also be even lower, for example below 10 ⁻⁷ Pa.

Preference is likewise given to organic electroluminescent components in which one or more layers are applied by means of organic vapor deposition methods or by means of carrier gas sublimation, the materials being applied at a pressure of between 10 ⁻⁵ Pa and 1 Pa. A particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is thus structured.

Furthermore, preference is given to organic electroluminescent components in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing methods, such as screen printing, flexographic printing, lithographic printing, photoinduced thermography, thermal transfer printing, inkjet printing or nozzle printing. Soluble compounds, for example obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Also possible are hybrid methods in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

These methods are generally known to those skilled in the art and they can apply them without inventive effort to organic electroluminescent components comprising the compounds according to the invention.

Accordingly, the present invention also relates to a method for producing an organic electroluminescent element according to the invention, applying at least one layer by means of a sublimation method, and/or applying at least one layer by means of an organic vapor deposition method or by means of carrier gas sublimation, and/or applying at least one layer from solution by spin coating or by means of a printing method.

In addition, the present invention relates to comprising at least one compound represented by the formula (I). The same preferences as indicated above for organic electroluminescent elements apply to the compounds according to the invention. In particular, the compounds can preferably also comprise further compounds. Processing of the compounds of formula (I) according to the invention from the liquid phase, for example by spin coating or by printing methods, requires processing of formulations of the compounds of the invention. These formulations may, for example, be solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenzone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1- Methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methyl benzoate Pyrrolidone, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl) ethane, or a mixture of these solvents.

The fourth object of the present invention provides a consumer product, including the organic electroluminescence element, the light-emitting element comprising a first electrode, a second electrode, a CPL layer and at least one organic layer placed between the first electrode and the second electrode, the organic layer or the CPL layer comprising the compound provided by the present invention.

A consumer product as described in the present invention may be one of the following: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and/or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays with a diagonal of less than 2 inches, 3-D displays, virtual or augmented reality displays, transportation tools, video walls with multiple displays tiled together, theater or stadium screens, light therapy units, and signage.

In addition, unless otherwise specified, the raw materials used in the present invention can be obtained commercially, and any range described in the present invention includes any value between the end value and any value between the end value and any sub-range formed by the end value or any value between the end value.

Compared with prior art, the beneficial effect of the present invention is:

The heterocyclic compound of the invention has high thermal stability and carrier transport ability, and the organic electroluminescent element prepared by using the compound of the invention can significantly reduce the driving voltage and improve luminous efficiency and brightness.

Description of drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings required in the description of the embodiments or prior art. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other accompanying drawings can also be obtained according to these drawings without creative work.

1 is a schematic diagram of an organic electroluminescent element device 100 of the present invention;

FIG. 2 is a schematic diagram of an organic electroluminescent element device 200 of the present invention.

reference sign

In the device 100 of Fig. 1, 101 is a substrate, 102 is an anode layer, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light-emitting layer, 107 is a hole blocking layer, 108 is an electron transport layer, 109 is an electron injection layer, 110 is a cathode layer, and 111 is a CPL layer.

In the device 200 of Fig. 2, 101 is a substrate, 102 is an anode layer, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light emitting layer, 107 is an electron transport layer, 108 is an electron injection layer, 109 is a cathode layer, and 110 is a CPL layer.

Detailed ways

In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other implementations obtained by persons of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.

The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental raw materials and related equipment used in the following examples can be obtained from commercial sources unless otherwise specified, and the stated percentages are all mass percentages unless otherwise specified.

The testing apparatus and method that following embodiment carries out performance test to OLED material and element are as follows:

OLED component performance testing conditions:

Luminance and chromaticity coordinates: tested using spectral scanner PhotoResearch PR-715;

Current density and lighting voltage: Tested with Keithley 2420 digital source meter;

Power efficiency: tested with NEWPORT 1931-C;

Life test: use LTS-1004AC life test device.

Example

As a non-limiting example, the heterocyclic compound represented by the formula (I) is prepared by the method of the following synthetic route 1, synthetic route 2, synthetic route 3 or synthetic route 4.

Synthetic route 1:

Synthetic route 2:

Synthetic route 3:

Synthetic route 4:

The symbols Z, G ₁ , G ₂ and B used above are as defined above, and X and Y represent OH, OTf, Cl, Br, I, MgBr, MgI or Li. Hereinafter, the present invention will be described in detail through more specific examples. However, the following examples merely illustrate the present invention and are not limited to the following examples.

Example 1

The preparation method of compound C875, comprises the steps:

The first step: preparation of compound Int-1

20.0mmol of 3-iodo-2-cyanindole (CAS: 51796-65-7, reactant 1) and 20.0mmol of o-methoxyphenylacetylene (reactant 2), 2.0mmol of cuprous iodide, then added 0.2mmol of PdCl ₂ (PPh ₃ ) ₂ catalyst and 60mL of triethylamine, under the protection of nitrogen, stirred at room temperature for 12 hours, filtered, and the filtrate was concentrated to dryness under reduced pressure. Separation and purification with a silica gel column gave compound Int-1 as a yellow solid with a yield of 95%.

The second step: the preparation of compound Int-2

20.0mmol's INT-1 and 22.0 mmol iodine, 2.0 mmol iodide copper, and then add 4.0 mmol N, N’-dihydramine diharamine, 40.0 mmol potassium-free potassium carbonate, and 80ml ditene. The pressure concentration is separated, and the silicone column is separated and purified.

The third step: preparation of compound Int-3

10.0 mmol of the intermediate Int-2 prepared in the second step was dissolved in 50 mL of dichloromethane, 10.0 mmol of iodine was added, and under nitrogen protection, the reaction was stirred at room temperature for 16 hours, 50 mL of saturated aqueous sodium thiosulfate solution was added, the organic phase was separated, dried, filtered, the filtrate was concentrated to dryness, and separated and purified by silica gel column to obtain intermediate Int-3 as a white solid, yield: 87%.

Step 4: Preparation of compound Int-4

Dissolve 15.0 mmol of p-dibromobenzene (reactant 3) in 80 ml of dry THF, under the protection of nitrogen, cool down to -80°C, add dropwise 16.0 mmol of n-butyllithium, stir and react for 30 minutes for later use, dissolve 15.0 mmol of intermediate Int-3 in 80 ml of dry THF, cool down to 0°C, add dropwise the p-bromophenyllithium solution prepared above, rise to room temperature and stir for 1 hour, heat to reflux and stir for 2 hours, cool After reaching room temperature, 50 mL of saturated ammonium chloride aqueous solution was added, extracted with ethyl acetate, the organic phase was dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and then separated and purified by silica gel column to obtain compound Int-4 as a white solid, yield: 82%.

Step 5: Preparation of Compound Int-5

10.0mmol of Int-4 was dissolved in 60ml of dry DMF. Under nitrogen protection, 12.0mmol of diboronic acid pinacol ester, 15.0mmol of potassium acetate and 0.1mmol of PdCl ₂ (dppf) catalyst were added, the temperature was raised to 90°C, the reaction was stirred for 12 hours, and cooled to room temperature. Separation and purification on a silica gel column gave compound Int-5 as a white solid with a yield of 88%.

Step 6: Preparation of Compound C875

12.0mmol of Int-5 was dissolved in 40ml of toluene, under the protection of nitrogen, 10.0mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine (reactant 4), 36.0mmol of anhydrous potassium carbonate, 0.01mmol of Pd132 catalyst, 20ml of ethanol and 20ml of water were added, the temperature was raised to reflux and stirred for 12 hours, cooled to room temperature, added 50mL of water, and washed with ethanol Extracted with ethyl acetate, dried the organic phase, filtered, concentrated the filtrate to dryness under reduced pressure, and then separated and purified with silica gel column to obtain compound C875, a white solid, yield: 86%, HRMS: 642.2304 [M+H]; ¹H-NMR (CDCl ₃,TMS)δ8.68～8.66(d,2H),8.53～8.51(m,1H),8.35～8.30(m,4H),7.96～7.92(m,3H),7.69～7.62(m,4H),7.58～7.47(m,9H),7.37～7.32(m,2H),7.21 ~7.15(m,2H).

Referring to the synthetic method of the above-mentioned Example 1, the following compounds were prepared, that is, the steps of the method were the same as those in Example 1. The only difference was that depending on the desired product, different cyano-containing halides were used to replace the 3-iodo-2-cyanindole in the first step of Example 1, different aryl acetylenes were used to replace the o-methoxyphenylacetylene in the first step of Example 1, and different halides were used to replace 2-chloro-4,6-diphenyl-1,3,5-triazine in the sixth step of Example 1, and changed according to the molar weight The mass consumption of this halide, prepares following compound:

Example 2

The preparation method of compound C761, comprises the steps:

The first step: preparation of compound Int-6

12.0mmol of 1-phenylindole-3-boronic acid (reactant 1) and 10.0mmol of N-(3-bromobenzofuran-2-yl)-4-chlorobenzamide (reactant 2) were dissolved in 40ml of toluene, under nitrogen protection, 36.0mmol of anhydrous sodium carbonate and 0.01mmol of Pd132 catalyst, 20ml of ethanol and 20ml of water were added, and the temperature was raised to reflux and stirred for reaction 12 hours, cooled to room temperature, added 50mL of water, extracted with ethyl acetate, dried the organic phase, filtered, concentrated the filtrate to dryness under reduced pressure, and then separated and purified with a silica gel column to obtain compound Int-6 as a white solid, yield: 78%.

The second step: the preparation of compound Int-7

15.0 mmol of Int-6 was dissolved in 80 ml of dry nitrobenzene. Under nitrogen protection, 22.5 mmol of phosphorus oxychloride was added dropwise. After stirring for 30 minutes, the temperature was raised to 140°C. After stirring for 16 hours, it was cooled to room temperature. 80 mL of saturated sodium carbonate aqueous solution was added, stirred and reacted for 2 hours, filtered, the filter cake was washed with water, and then separated and purified by silica gel column to obtain compound Int-7, a yellow solid, yield: 52%.

The third step: preparation of compound Int-8

10.0mmol of Int-7 was dissolved in 60ml of dry DMF. Under nitrogen protection, 12.0mmol of diboronic acid pinacol ester, 15.0mmol of potassium acetate and 0.1mmol of PdCl ₂ (dppf) catalyst were added, the temperature was raised to 100°C, the reaction was stirred for 12 hours, and cooled to room temperature. Separation and purification with a silica gel column gave compound Int-8 as a yellow solid with a yield of 86%.

The fourth step: preparation of compound C761

12.0mmol of Int-8 was dissolved in 40ml of toluene, under nitrogen protection, 10.0mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine (reactant 3), 36.0mmol of anhydrous potassium carbonate, 0.01mmol of Pd132 catalyst, 20ml of ethanol and 20ml of water were added, heated to reflux and stirred for 12 hours, cooled to room temperature, added 50mL of water, and washed with ethyl Extracted with ethyl acetate, dried the organic phase, filtered, concentrated the filtrate to dryness under reduced pressure, and separated and purified with silica gel column to obtain compound C761, a white solid, yield: 77%, HRMS: 642.2304 [M+H]; ¹H-NMR (CDCl ₃,TMS)δ8.68～8.66(d,2H),8.53(s,1H),8.34～8.30(m,4H),7.96～7.92(m,4H),7.61～7.56(m,4H),7.53～7.42(m,8H),7.38～7.32(m,3H),7.21～7.15 (m,1H).

With reference to the synthetic method of above-mentioned embodiment 2, prepare following compound:

Example 3

The preparation method of compound C797, comprises the steps:

The first step: preparation of compound Int-9

Dissolve 20.0mmol of 3-iodo-2-cyanobenzofuran (reactant 1) in 80ml of dry THF, under the protection of nitrogen, cool down to -10°C, add dropwise 22.0mmol of 1M isopropylmagnesium chloride THF solution, stir for 10 minutes, then add dropwise 24.0mmol of isopropoxy pinacol borate, stir for 1 hour, warm to room temperature, add 50mL of saturated ammonium chloride aqueous solution, and extract with ethyl acetate , the organic phase was dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and then separated and purified by silica gel column to obtain compound Int-9 as a white solid, yield: 87%.

The second step: the preparation of compound Int-10

12.0 mmol of p-chlorobromobenzene (reactant 2) and 12.0 mmol of anhydrous lithium chloride were dissolved in 120 ml of dry THF. Under the protection of nitrogen, the temperature was lowered to -78°C, and 13.0 mmol of 2.5M n-butyllithium n-hexane solution was added dropwise. After stirring for 30 minutes, 10.0 mmol of Int-9 dissolved in THF was added dropwise. The reaction was stirred for 1 hour, raised to room temperature, and 50 mL of saturated ammonium chloride aqueous solution was added. The reaction was stirred for 2 hours, extracted with ethyl acetate, the organic phase was dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and then separated and purified by silica gel column to obtain compound Int-10 as a white solid, yield: 92%.

The third step: preparation of compound Int-11

12.0 mmol of Int-10 was dissolved in 60 ml of THF, under nitrogen protection, 10.0 mmol of 3-bromo-2-nitroindole (reactant 3), 24.0 mmol of anhydrous sodium carbonate, 0.01 mmol of Pd132 catalyst and 20 ml of water were added, the temperature was raised to reflux and the reaction was stirred for 5 hours, cooled to room temperature, 50 mL of water was added, extracted with ethyl acetate, the organic phase was dried, filtered, and the filtrate was concentrated under reduced pressure Dry it, and then separate and purify it with a silica gel column to obtain compound Int-11 as a yellow solid, with a yield of 82%.

Step 4: Preparation of Compound Int-12

15.0 mmol of Int-11 was dissolved in 80 ml of glacial acetic acid, 60.0 mmol of iron powder was added, heated to reflux and stirred for 2 hours, cooled to room temperature, filtered, the filtrate was concentrated to dryness under reduced pressure, dissolved in 100 mL of dichloromethane, washed with 5% aqueous sodium hydroxide solution, washed with water, the organic phase was dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and then separated and purified by silica gel column to obtain compound Int-12, a yellow solid, yield: 76%.

Step 5: Preparation of Compound Int-13

Dissolve 10.0mmol of Int-12 in 50ml of xylene, add 12.0mmol of bromobenzene, 15.0mmol of sodium tert-butoxide, 0.1mmol of palladium acetate and 0.2mmol of SPhos, raise the temperature to reflux and stir for 12 hours, cool to room temperature, add 50mL of water, extract with ethyl acetate, dry the organic phase, filter, and concentrate the filtrate to dryness under reduced pressure. Solid, yield: 84%.

Step 6: Preparation of Compound Int-14

Referring to the synthesis method in the third step of Example 2, only Int-7 in the third step of Example 2 was replaced with Int-13 to prepare compound Int-14 with a yield of 85%.

Step 7: Preparation of compound C797

Referring to the synthesis method in the fourth step of Example 2, only Int-8 in the fourth step of Example 2 was replaced by Int-14 to prepare compound C797 with a yield of 72%, HRMS: 642.2312 [M+H]; ¹H-NMR (CDCl ₃,TMS)δ8.67～8.64(m,2H),8.52(s,1H),8.36～8.31(m,4H),7.97～7.92(m,4H),7.62～7.53(m,4H),7.51～7.41(m,8H),7.38～7.30(m,3H),7.19～7.16 (m,1H).

With reference to the synthetic method of above-mentioned embodiment 3, prepare following compound:

Example 4

The preparation method of compound C779, comprises the steps:

The first step: preparation of compound Int-15

20.0 mmol of 2-cyano-inden-1-one (reactant 1) was dissolved in 20 mL of phosphorus tribromide. Under nitrogen protection, the temperature was raised to reflux and stirred for 1 hour, and then cooled to room temperature. The reaction solution was poured into 200 g of crushed ice, and sodium carbonate solid was added to make it neutral. It was extracted with ethyl acetate, the organic phase was dried, filtered, the filtrate was concentrated under reduced pressure to dryness, and then separated and purified by a silica gel column to obtain compound Int-15, a yellow solid, yield: 66%.

The second step: the preparation of compound Int-16

12.0 mmol of benzofuran-3-boronic acid (reactant 2) was dissolved in 60 mL of THF, under nitrogen protection, 10.0 mmol of Int-15, 24.0 mmol of anhydrous sodium carbonate, 0.01 mmol of Pd132 catalyst and 20 mL of water were added, the temperature was raised to reflux and the reaction was stirred for 5 hours, cooled to room temperature, 50 mL of water was added, extracted with ethyl acetate, the organic phase was dried, filtered, and the filtrate was decompressed Concentrate to dryness, and then separate and purify with silica gel column to obtain compound Int-16 as a yellow solid, yield: 75%.

The third step: preparation of compound Int-17

15.0mmol of Int-16 was dissolved in 80mL of dichloromethane, under the protection of nitrogen, the temperature was lowered to -5°C, a solution of 16.5mmol of NBS dissolved in acetonitrile was added dropwise, and the reaction was stirred for 2 hours, 50mL of saturated aqueous sodium bisulfite solution was added dropwise, the organic phase was separated, the aqueous phase was extracted with dichloromethane, the organic phase was dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and then separated and purified by silica gel column to obtain compound Int-17, a yellow solid, yield: 77% .

Step 4: Preparation of Compound Int-18

Referring to the synthesis method in the fourth step of Example 1, only Int-3 in the fourth step of Example 1 was replaced with Int-17, and p-dibromobenzene was replaced with p-chlorobromobenzene to prepare compound Int-18 with a yield of 85%.

Step 5: Preparation of Compound Int-19

Dissolve 15.0 mmol of Int-18 in 80 mL of THF, cool down to 0°C, add 37.5 mmol of 65% sodium hydride solid (oil dispersion) in batches, stir for 1 hour, then add 60.0 mmol of methyl iodide, heat up to reflux and stir for 12 hours, cool down to room temperature, add 50 mL of ice water dropwise, separate the organic phase, extract the aqueous phase with ethyl acetate, dry the organic phase, filter, concentrate the filtrate to dryness under reduced pressure, and separate through a silica gel column After purification, compound Int-19 was obtained as a white solid, yield: 62%.

Step 7: Preparation of Compound C779

Referring to the synthesis method in the fourth step of Example 2, only Int-8 in the fourth step of Example 2 was replaced by (4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid, and 2-chloro-4,6-diphenyl-1,3,5-triazine was replaced by Int-19 to prepare compound C779, yield: 84%, HRMS: 669.2668 [M+H]; ¹H-NMR (CDCl ₃,TMS)δ8.78～8.75(m,4H),8.61～8.57(d,1H),8.38～8.29(m,4H),7.97～7.84(m,4H),7.79～7.74(m,2H),7.66～7.41(m,10H),7.23～7.19(m,1H),1.8 6(s,6H).

With reference to the synthetic method of above-mentioned embodiment 1 and embodiment 4, prepare following compound:

Example 5

An organic electroluminescent element, as shown in Figure 1 and Figure 2, the organic electroluminescent element has 101 is a substrate, 102 is an anode layer, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light emitting layer, 107 is an electron transport layer, 108 is an electron injection layer, 109 is a cathode layer, 110 is a CPL layer. The preparation method that the OLED element shown in Figure 2 does not comprise the CPL layer comprises the following steps:

1) The glass substrate coated with the ITO conductive layer was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonicated in acetone/ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, irradiated with a UV cleaning machine for 10 minutes, and bombarded the surface with a low-energy cationic beam to obtain an anode.

2) Place the above-mentioned treated ITO glass substrate in a vacuum chamber, vacuumize to 1×10 ^-5 ~ 9×10 ^-3 Pa, evaporate metal aluminum on the above-mentioned anode layer film as an anode, and the thickness of the evaporated film is

Continue to vapor-deposit the compound DNTPD respectively as the hole injection layer, and the vapor-deposited film thickness is

Continue to vapor-deposit NPB on the above-mentioned hole injection layer film to be a hole-transport layer, and the vapor-deposited film thickness is

3) Continue to evaporate a layer of compound HT102 on the hole transport layer as an electron blocking layer, and the thickness of the evaporated film is

4) Continuously vapor-deposit a layer of RH022 and RD025 on the electron blocking layer as the organic light-emitting layer, wherein, RH022 is the host material and RD025 is the dopant material, the doping concentration of RD025 is 5%, and the vapor-deposited film thickness is

5) Continue to vapor-deposit one layer of compound LiQ and the compound formula (I) of the present invention on the above-mentioned light-emitting layer as the electron transport layer of the device, wherein the mass ratio of LiQ and the compound formula (I) of the present invention is 3:2, and the vapor-deposited film thickness is

6) Continue to vapor-deposit a layer of compound LiF on the above-mentioned electron transport layer as the electron injection layer of the device, and the thickness of the vapor-deposited film is

Finally, metal silver and magnesium are vapor-deposited on the above-mentioned electron injection layer as the cathode layer of the element, the mass ratio of magnesium and silver is 1:1, and the vapor-deposited film thickness is

The compound structure used in the above-mentioned embodiment 5 is as follows:

Example 6

According to the same steps as in Example 5, without using the compound formula (I) in step 5), a comparative element 1 was obtained.

Example 7

According to the same steps as in Example 5, the compound formula (I) in step 5) was replaced by ET15 to obtain comparative element 2;

The structure of the ET15 is:

Test example 1

The performance of the organic electroluminescent element prepared in Example 5 was tested, wherein the driving voltage, current efficiency, color coordinates (1931CIE), and half peak width were obtained under the condition that the current density of the element was 10mA/cm ² , and the data of the driving voltage, current efficiency, and half peak width were normalized compared with those of comparative element 1, and the LT95% life of the element was measured under the condition of 50mA/cm ² , and compared with comparative element 1, the data was normalized.

Table 1

It can be seen from Table 1 that under the same current density conditions, the light-emitting element prepared by the compound of the present invention has lower driving voltage, higher current efficiency, and consistent luminous peak than LiQ and ET15 elements as electron transport materials, and the LT95% lifetime of the element has been greatly improved.

Above-mentioned embodiment has only listed the performance of a kind of organic electroluminescent element structure, and the present inventor has also done above-mentioned similar test to other element structures, such as shown in Figure 1, and other metal complexes or fluorescent materials as light-emitting layer, or the compound described in the present invention as light-emitting layer material, and the results are basically the same, and due to limited space, they are not listed one by one.

The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed in the present invention, and all should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.

Claims (10)

1. A heterocyclic compound, characterized in that, the heterocyclic compound is as shown in formula (I):

   

   Wherein, adjacent W ¹ and W ² , W ³ and W ⁴ each independently represent a group represented by formula (II);

   

   wherein G represents O, S, CR ³ R ⁴ , NR ⁵ , SiR ³ R ⁴ or GeR ³ R ⁴ , Z represents CR ¹ or N identically or differently at each occurrence, and ^ indicates the corresponding adjacent groups W ¹ and W ² , W ³ and W ⁴ in formula (I);

   Ring B represents an aromatic ring containing at least two carbon atoms, preferably, selected from substituted or unsubstituted C ₆-C ₆₀Aryl, substituted or unsubstituted C ₆-C ₆₀Fused ring aryl, substituted or unsubstituted C ₆-C ₆₀Arylamino, substituted or unsubstituted C ₆~C ₆₀Arylboryl, substituted or unsubstituted C ₆~C ₆₀Arylphosphoryl, substituted or unsubstituted C ₆~C ₆₀Arylphosphinyl, substituted or unsubstituted C ₆~C ₆₀Arylsilyl, substituted or unsubstituted C ₂-C ₆₀Heteroaryl or substituted or unsubstituted C ₂-C ₆₀A group consisting of heteroarylamine groups;

   R ¹, R ², R ³, R ⁴, R ⁵each independently selected from hydrogen, deuterium, halogen, nitrile, nitro, substituted or unsubstituted C ₆-C ₆₀Aryl, substituted or unsubstituted C ₆-C ₆₀Aryloxy, substituted or unsubstituted C ₆-C ₆₀Fused ring aryl, substituted or unsubstituted C ₆-C ₆₀Arylamino, C ₆~C ₆₀The aryl boron group, C ₆~C ₆₀The arylphosphoryl group, C ₆~C ₆₀Arylphosphinyl, substituted or unsubstituted C ₆-C ₆₀Aralkyl, C ₁~C ₄₀Alkylsilyl, C ₆~C ₆₀The arylsilyl group, or substituted or unsubstituted C ₂-C ₆₀Groups consisting of heteroaryl groups;

   R ² is monosubstituted to saturated substituted.
2. The heterocyclic compound according to claim 1, characterized in that the heterocyclic compound comprises structures represented by formulas (III) to (VI):

   

   Wherein, G ₁ and G ₂ each independently represent O, S, CR ³ R ⁴ , NR ⁵ or SiR ³ R ⁴ , and Z represents CR ¹ or N identically or differently at each occurrence;

   R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently selected from hydrogen, deuterium, halogen atom, nitrile group, nitro group, substituted or unsubstituted C ₆ -C ₆₀ aryl group, substituted or unsubstituted C _{6 -C 60} aryloxy group, substituted or unsubstituted C ₆ -C 60 fused ring aryl group, substituted or unsubstituted C ₆ -C 60 arylamino group, C ₆ -C ₆₀ arylphosphoryl group , a C ₆ -C ₆₀ arylphosphoryl group, or a group consisting of a substituted or unsubstituted C _{2 -C 60 heteroaryl} group.
3. The heterocyclic compound according to claim 1 or 2, wherein the ring B is one or more of the following structures:

   

   Wherein, V represents CR ⁶ R ⁷ , NR ⁸ , O or S; the dotted bond represents the position of attachment to ring A, and in addition:

   W is CR ⁹ or N identically or differently at each occurrence; or two adjacent groups W represent groups of the following formula (6) or (7),

   

   Wherein, G, Z are identical with the definition of G, Z in claim 1, and " " represents the corresponding adjacent group W in formula (2), (3), (4) or (5), and contains at least 2 carbon atoms in formula (2), (3), (4), (5);

   R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently selected from hydrogen, deuterium, halogen atom, nitrile group, nitro group, substituted or unsubstituted C _{6 -C 60} aryl group, substituted or unsubstituted C ₆ -C ₆₀ aryloxy group, substituted or unsubstituted C ₆ -C ₆₀ condensed ring aryl group, substituted or unsubstituted C ₆ -C 60 arylamino group, C ₆ -C 60 arylphosphoryl group, C ₆ ~C ₆₀ arylphosphinyl, or a group consisting of substituted or unsubstituted C _{2 -C 60 heteroaryl} .
4. The heterocyclic compound according to any one of claims 1 to 3, characterized in that, the aryl group, condensed ring aryl group, heteroaryl group, especially refers to groups derived from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,

   

   Perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, diphenyl, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, tripolyindene, isotriindene, spirotriindene, spiroisotriindene, furan, benzofuran, isobenzofuran, dibenzofuran, Thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthalene imidazole, phenanthromidazole, pyridoimidazole, pyrazinoimidazole, Quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthraxazole, phenanthraxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene Pyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorocycline, naphthyridine, azacarbazole, benzocarboline, carboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4 -oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, quinazoline and benzo Thiadiazoles or groups derived from combinations of these systems.
5. The heterocyclic compound according to any one of claims 1 to 4, wherein the ring B is selected from the group consisting of the following groups:

   

   

   

   Wherein, G is the same as the definition of G in claim 1.
6. The heterocyclic compound according to any one of claims 1-5, wherein the ring B is selected from the group consisting of the following formulas B1-B15:

   

   

   Among them, *—G—* is *—O—*, *—S—* or one of the following structures:

   

   *—and—* represent the connecting bond with two benzene rings;

   Each R in the B1～B15 structure ⁷each independently selected from deuterium, fluorine, nitrile, C ₁~C ₄₀Alkyl, C ₂~C ₄₀Alkenyl, C ₂~C ₄₀Alkynyl, C ₃~C ₄₀Cycloalkyl, C ₃~C ₄₀heterocycloalkyl, C ₆~C ₆₀Aryl, C ₂~C ₆₀The heteroaryl, C ₁~C ₄₀Alkoxyl, C ₆~C ₆₀Aryloxy group, C ₁~C ₄₀Alkylsilyl, C ₆~C ₆₀The aryl silyl group, C ₁~C ₄₀Alkylboryl, C ₆~C ₆₀The aryl boron group, C ₆~C ₆₀The arylphosphoryl group, C ₆~C ₆₀Arylphosphine, C ₆~C ₆₀A group consisting of arylamino groups. At this time, when there are more than one substituents, the multiple substituents are the same or different from each other.
7. The heterocyclic compound according to any one of claims 1-6, characterized in that the heterocyclic compound is selected from the group consisting of the following formulas C740-C1093:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   Among them, *—T ₂ —* is *—O—*, *—S—* or one of the following structures:

   

   *— and —* represent linkages to two benzene rings.
8. An organic electroluminescent material, characterized in that the raw material of the organic electroluminescent material comprises the heterocyclic compound described in any one of claims 1-7.
9. An organic electroluminescent element, characterized in that it comprises a first electrode, a second electrode, a capping layer, and at least one organic layer placed between the first electrode and the second electrode, at least one of the organic layer or the capping layer comprising the heterocyclic compound according to any one of claims 1 to 7.
10. The organic electroluminescent element according to claim 9, wherein the organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer or an electron blocking layer;

    Preferably, the light emitting layer, electron transport layer, hole blocking layer and capping layer comprise the heterocyclic compound described in any one of claims 1-7.

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