Heterocyclic compounds and uses thereof

Abstract

The application provides a heterocyclic compound and an organic electroluminescent element, organic electroluminescent material, and the structural formula of the heterocyclic compound is shown as formula I. Compared with the prior art, the compound with two quinoxaline conjugated dibenzothiophene, dibenzofuran, fluorene and other units as the mother nucleus is used as the light emitting unit, on the one hand, the HOMO and LUMO can be separated by using the charge transfer effect between the donor (D) and the acceptor (A), so that the TADF effect is realized, and the large plane heterocyclic unit can reduce the relaxation degree of the excited state structure, so that a relatively narrow half peak width is realized; on the other hand, by introducing different substituents on the rigid skeleton, the further adjustment of the delayed fluorescence lifetime and the half peak width can be realized.

Description

Technical Field

[0001] This invention belongs to the field of electroluminescence technology, specifically relating to a heterocyclic compound and an organic electroluminescent element and an organic electroluminescent material. Background Technology

[0002] Traditional fluorescent materials, limited by spin quantum statistics, can only utilize singlet excitons (comprising 25% of all excitons) during electroluminescence, while the remaining 75% of triplet excitons are deactivated through non-radiative transitions. The theoretical limit of the device's internal quantum efficiency is 25%. To improve exciton utilization, triplet excitons need to be converted into photons to achieve 100% internal quantum efficiency. Phosphorescent metal complexes can convert triplet excitons into photons using the spin-orbit coupling of heavy metal atoms, but this approach faces the problem of high cost. Another approach to utilizing triplet excitons is to develop luminescent materials with thermally activated delayed fluorescence (TADF) properties. These materials utilize a thermally activated reverse system crossing (RISC) process to transfer triplet excited states to singlet excited states, emitting fluorescence and thus fully utilizing both singlet and triplet excitons. Molecules with TADF properties generally need to satisfy two conditions: a small singlet-triple energy level difference (ΔE). ST It also exhibits high fluorescence quantum efficiency (PLQY). On the one hand, it has a smaller ΔE. ST The reverse intersystem crossing process, which is conducive to thermal activation, is beneficial to improving the utilization efficiency of triplet excitons. On the other hand, the material must have a high PLQY to promote the decay of singlet excitons in the form of light and improve device efficiency.

[0003] The main approach to developing TADF molecules currently involves introducing donor (D) and acceptor (A) groups to effectively separate the highest occupied orbital (HOMO) and lowest vacant orbital (LUMO) spatially, thereby achieving a small ΔE. ST However, this DA structure exhibits a large Stokes shift due to the vibrational relaxation of its excited state, and its emission spectrum is relatively broad, with a full width at half maximum (FWHM) typically between 70 nm and 100 nm. In practical applications, filters or optical microcavities are often required to improve color purity, but this can lead to a decrease in the external quantum efficiency of the device or a more complex device structure.

[0004] Therefore, how to develop fluorescent materials that have both TADF effect and narrow spectral characteristics through appropriate chemical structure design, and solve the defect of wide half-width of the above materials, has become one of the problems that many forward-looking researchers in the field urgently need to solve.

[0005] For the reasons stated above, this invention is proposed. Summary of the Invention

[0006] To address the aforementioned problems in the existing technology, this invention provides a heterocyclic compound and an organic electroluminescent element, as well as an organic electroluminescent material. When the heterocyclic compound described in this invention is used as a luminescent material, it can be tuned to emit deep blue to red light and has high luminous efficiency.

[0007] The first objective of this invention is to provide a heterocyclic compound.

[0008] A second objective of this invention is to improve an organic electroluminescent element.

[0009] A third objective of this invention is to provide an organic electroluminescent material.

[0010] To achieve the above objectives, the present invention adopts the following technical solution:

[0011] A heterocyclic compound, the general structural formula of which is shown in Formula I:

[0012]

[0013] Where: X represents O, S, SO, SO2, Se, CR 7 R 8 SiR 7 R 8 or NR 9 ;

[0014] Ar 1 Ar 2 Each is independently selected from substituted or unsubstituted C6-C. 60 aryl, substituted or unsubstituted C6-C 60 Aromatic amino group, substituted or unsubstituted C2-C 60 Groups composed of heteroaryl groups;

[0015] L 1 L 2 Each can independently represent a single bond, substituted or unsubstituted C6-C. 60 aryl, substituted or unsubstituted C6-C 60 Aromatic amines, substituted or unsubstituted C2-C 60 Groups composed of heteroaryl groups;

[0016] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9They may be the same as or different from each other, and each is independently selected from hydrogen, deuterium, substituted or unsubstituted C1 to C2. 30 Alkyl, substituted or unsubstituted C6-C 50 Aryl, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C2-C 50 heteroaryl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C6-C 50 aryloxy groups, substituted or unsubstituted C1-C 30 Alkyl thio, substituted or unsubstituted C5-C 50 aryl thio, substituted or unsubstituted C1-C 30 Alkylamine, substituted or unsubstituted C5-C 50 Arylamine, substituted or unsubstituted C1-C 30 Alkyl silyl, substituted or unsubstituted C5-C 50 A group consisting of arylsilyl, nitro, cyano, or halogen atoms, any two or more adjacent R groups. 1 ~R 9 They can be arbitrarily joined or fused to form substituted or unsubstituted rings, which may or may not contain heteroatoms N, O, S, P, B, Si or Se.

[0017] Furthermore, the heterocyclic compound is selected from any one of the following structures:

[0018]

[0019] Among them, R 1 ~R 9 L 1 L 2 Ar 1 Ar 2 The meaning is the same as the definition of Equation I above;

[0020] Ar 3 Ar 4 Ar 5 Ar 6 Each is independently selected from substituted or unsubstituted C6-C. 60 aryl, substituted or unsubstituted C6-C 60 Aromatic amino group, substituted or unsubstituted C2-C 60 Groups composed of heteroaryl groups; Ar 3 and Ar 4 Ar 5 and Ar 6They can be arbitrarily joined or fused to form substituted or unsubstituted rings, which may or may not contain heteroatoms N, O, S, P, B, Si or Se.

[0021] Furthermore, the R 1 R 2 It is either hydrogen or deuterium.

[0022] Furthermore, the R 3 R 4 R 5 R 6 Each is independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, nitrile, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthraquinone, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted fluorenyl, and substituted or unsubstituted carbazolyl.

[0023] Furthermore, the R 3 R 4 R 5 R 6 Each is independently selected from groups consisting of hydrogen, deuterium, substituted or unsubstituted phenyl groups.

[0024] Furthermore, the R 7 R 8 Each time it appears, it is independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted fluorenyl.

[0025] Furthermore, the R 9 Each time it appears, it is selected from the group consisting of methyl, ethyl, substituted or unsubstituted phenyl, and substituted or unsubstituted biphenyl.

[0026] Furthermore, the L 1 L 2 Each is independently selected from a single bond or from the group consisting of the following groups from III-1 to III-24:

[0027]

[0028] Among them, G is selected from O, S, SO, SO2, and CR. ’ R”, ​​SiR ’ R” or NAr ’ ;

[0029] Z 11 Z 12Z 13 Z 14 Each is independently selected from hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidine group, hydrazine group, hydrazone group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C1-C 60 Alkyl, C2-C 60 alkenyl, C2-C 60 alkynyl group, C1-C 60 alkoxy groups, C3-C 60 Cycloalkane group, C3-C 60 Cycloolefinic, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C6-C 60 aryloxy, substituted or unsubstituted C6-C 60 aryl sulfide group, or substituted or unsubstituted C2-C 60 Groups composed of heteroaryl groups;

[0030] y1 represents an integer from 1 to 4; y2 represents an integer from 1 to 6; y3 represents an integer from 1 to 3; y4 represents an integer from 1 to 5; y5 represents an integer of 1 or 2.

[0031] R ’ Each of "R" is independently selected from C1-C. 60 Alkyl, C1-C 60 heteroalkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C6-C 60 Aromatic amino group, or substituted or unsubstituted C2-C 60 Groups composed of heteroaryl groups, R ’ R and R can optionally be joined or fused to form one or more additional substituted or unsubstituted rings, the formed rings containing or not containing one or more heteroatoms N, P, B, O or S; preferably, R ’ "R" represents methyl, phenyl, or fluorene;

[0032] Ar ’ Choose freely from C1 to C 60 Alkyl, C1-C 60 heteroalkyl, C3-C 60 cycloalkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C6-C 60 Fused aryl, substituted or unsubstituted C6-C 60 Aromatic amino group, or substituted or unsubstituted C2-C 60 Groups consisting of heterocyclic aryl groups; preferably, Ar ’ It can be methyl, ethyl, phenyl, biphenyl, or naphthyl;

[0033] In this context, the dashed lines represent the connection sites of functional groups.

[0034] Furthermore, the L 1 L 2 Each is independently selected from the group consisting of single bond, phenylene, biphenylene, naphthylene, and dibenzofuranyl.

[0035] In this invention, an aryl group contains 6 to 50 carbon atoms, and a heteroaryl group contains 2 to 50 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatom is at least 5; the heteroatom is preferably selected from N, O, or S. The aryl or heteroaryl group referred to herein specifically refers to a group derived from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, etc. Perylene, fluoranthene, tetraphenylene, pentaphenylene, benzo[a]pyrene, biphenyl, azobenzene, terphenyl, trimerene, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorene, cis or trans indocarbazole, cis or trans indol[a]carbazole, trimerin, isotrimerinin, spirotrimerinin, spiroisotrimerinin, furan, benzo[a]furan, isobenzo[a]furan, dibenzo[a]furan, thiophene, benzo[a]thiophene, isobenzo[a]thiophene, dibenzo[a]thiophene, 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, naphthiamidazole, phenanthrenemidazole, pyridinium pyridimazole, pyrazinium pyridimazole, quinoxaline pyridimazole, oxazole, benzoxazole, naphthiamidazole, anthraquinoxazole, phenanthreneium pyridimazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazabenziphenanthrene, benzopyridazine, pyrimidine, benzene Pyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescein ring, naphthidine, azacarbazole, benzo[a]carbline, carbline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzo[a]triazole, 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, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indazine, quinazoline, and benzothiadiazole, or groups derived from combinations of these systems.

[0036] The fused aryl group used in this invention refers to a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon with 6 to 50 carbon atoms that has two or more rings. In this case, the two or more rings can be simply attached to each other or attached in a condensed form. Non-limiting examples include phenanthrene, anthracene, fluoranthracene, pyrene, triphenylene, perylene, etc. Base, etc.

[0037] The aromatic amine group used in this invention refers to an amine substituted with an aryl group having 6 to 50 carbon atoms. Non-limiting examples of aromatic amine groups include diphenylamine, N-phenyl-1-naphthylamine, and N-(1-naphthyl)-2-naphthylamine. The heteroaryl amine group refers to an amine substituted with an aryl group having 6 to 50 carbon atoms or a heteroaryl group having 2 to 50 carbon atoms. Non-limiting examples of heteroaryl amine groups include N-phenylpyridin-3-amine, N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-2-amine, and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2-amine.

[0038] For aliphatic hydrocarbon groups or alkyl groups containing 1 to 30 carbon atoms, wherein individual hydrogen atoms or -CH2- groups can be replaced by the aforementioned groups, the preferred group is considered to be: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, or cyclooctenyl.

[0039] The alkoxy group preferably has 1 to 30 carbon atoms, and is considered to be alkoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexoxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy, and 2,2,2-trifluoroethoxy.

[0040] Heteroalkyl groups are preferably alkyl groups having 1 to 30 carbon atoms, referring to groups in which a single hydrogen atom or -CH2- group can be replaced by an oxygen, sulfur, or halogen atom. These are considered to be alkoxy, alkathio, fluorinated alkoxy, fluorinated alkathio, particularly methyl thio, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethyl thio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio. Trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroethylthio, ethyleneoxy, ethylenethio, propyleneoxy, propylenethio, butenthio, butenoxy, penenoxy, penenthio, cyclopentenoxy, cyclopententhio, hexenoxy, hexenthio, cyclohexenoxy, cyclohexenthio, acetylenoxy, acetylenthio, propylenoxy, propylenthio, butylenoxy, butylenthio, penylenoxy, penylenthio, hexylenoxy, hexylenthio.

[0041] Generally, the cycloalkyl group in this invention can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, or cycloheptenyl, wherein one or more -CH2- groups can be replaced by the above groups; in addition, one or more hydrogen atoms can be replaced by deuterium atoms, halogen atoms, or nitrile groups.

[0042] The alkylamine group used in this invention refers to an amine that is substituted with an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. Non-limiting examples of alkylamine groups include dimethylamine, diethylamine, dipropylamine, diisopropylamine, etc.

[0043] The alkenyl or alkynyl group in this invention has 2 to 30 carbon atoms, and the alkenyl or alkynyl group in which a single hydrogen atom can be replaced by the above-mentioned group R is preferably vinyl, propenyl, butenyl, isobutenyl, styryl, stilbene, acetyl, propynyl, butynyl, or phenylacetyl; in addition, one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms or nitrile groups.

[0044] The aryl group used in this invention refers to R'O - The monovalent functional group represented by R' is an aryl group with 6 to 50 carbon atoms. Non-limiting examples of such aryl groups include phenoxy, naphthoxy, and biphenoxy groups.

[0045] The aryl thio group used in this invention refers to R'S - The monovalent functional group represented by R' is an aryl group with 6 to 50 carbon atoms. Non-limiting examples of such arylthio groups include phenylthio, naphthio, and biphenylthio.

[0046] The alkylsilyl group used in this invention refers to a silyl group substituted with an alkyl group having 1 to 30 carbon atoms, and the alkylsilyl group has at least 3 carbon atoms. Non-limiting examples of alkylsilyl groups include trimethylsilyl and triethylsilyl. Arylsilyl refers to a silyl group substituted with an aryl group having 6 to 50 carbon atoms.

[0047] The arylphospho group used in this invention refers to a diarylphospho group substituted with an aryl group having 6 to 50 carbon atoms. Non-limiting examples of arylphospho groups include diphenylphospho and di(4-trimethylsilylphenyl)phospho. Aryloxophospho is formed when the phosphorus atom of a diarylphospho group is oxidized to its highest valence state.

[0048] The arylboryl group used in this invention refers to a diarylboryl group substituted with an aryl group having 6 to 50 carbon atoms. Non-limiting examples of arylboryl groups include diphenylboryl and di(2,4,6-trimethylphenyl)boryl. Alkylboryl groups refer to dialkylboryl groups substituted with an alkyl group having 1 to 30 carbon atoms. Non-limiting examples of alkylboryl groups include di-tert-butylboryl and diisobutylboryl.

[0049] In this invention, the terms "halogen", "halogen", "halogen atom", and "halogen group" are used interchangeably and refer to fluorine, chlorine, bromine, or iodine.

[0050] As used herein, “combination” or “group” means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that can be conceived by one of ordinary skill in the art from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl groups; halogen and alkyl groups can be combined to form haloalkyl substituents, such as trifluoromethyl; and halogen, alkyl and aryl groups can be combined to form haloaralkyl groups.

[0051] In this specification, the term "substituted or unsubstituted" refers to substances selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidine, hydrazine, hydrazone, carboxyl or their carboxylates, sulfonic acid or their sulfonates, phosphate or their phosphates, C1-C 30 Alkyl, C2-C 30 alkenyl, C2-C 30 Alkyne group, C1-C 30 Alkoxy, C3-C 30 cycloalkyl, C3-C 30 Cycloalkenyl, C6-C 50 Aryl, C6-C 50 Aryloxy group, C6-C 50 Aryl sulfide groups and C2-C 50 The heterocyclic aryl group is substituted or unsubstituted by one or more substituents, or is substituted or unsubstituted by a substituent formed by linking two or more substituents of the substituents exemplified above.

[0052] In one instance, the term substitution includes a combination of two to four listed groups.

[0053] In another example, the term substitution comprises a combination of two or three groups. In yet another example, the term substitution comprises a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations containing up to forty atoms that are not hydrogen or deuterium, or combinations containing up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will comprise up to twenty atoms that are not hydrogen or deuterium.

[0054] In this invention, the term "ring" refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle formed by the combination of adjacent groups. A condensed ring refers to a condensed aliphatic ring, a condensed aromatic ring, a condensed aliphatic heterocycle, a condensed aromatic heterocycle, or a combination thereof.

[0055] Furthermore, the compound of formula I is selected from one of the compounds shown in formulas B001 to B309:

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] In the above structure, hydrogen atoms can be partially or completely replaced by deuterium.

[0067] An organic electroluminescent material comprising the aforementioned heterocyclic compound.

[0068] An organic electroluminescent element includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the heterocyclic compound.

[0069] Furthermore, the organic layer comprises one or more electron injection layers, electron transport layers, hole injection layers, hole transport layers, hole blocking layers, electron blocking layers, and light-emitting layers.

[0070] Furthermore, the light-emitting layer comprises the heterocyclic compound.

[0071] Furthermore, the electron transport layer comprises the heterocyclic compound.

[0072] Furthermore, the light-emitting layer also includes a host material and a dopant material. The host material comprises compounds consisting of the following chemical groups: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azitrin, azicarbazole, azidibenzothiophene, azidibenzofuran, azidibenzoselenene, and triazine. The dopant material comprises the aforementioned heterocyclic compounds.

[0073] Any substituent in the host material may be independently selected from non-fused substituents of the group consisting of: C n H 2n+1 OC n H 2n+1 OAr 7 、N(C n H 2n+1 2. N(Ar) 7 (Ar) 8 CH=CH-C n H 2n+1 C≡CC n H 2n+1 Ar 7 Ar 7 -Ar 8 C n H 2n -Ar 7 Or without substituents, where n is an integer from 1 to 10; and where Ar 7 with Ar 8 Independently selected from the following group: benzene, biphenyl, naphthalene, triphenylene, carbazole and their heteroaromatic analogs.

[0074] Furthermore, the main material is selected from one or more of the compounds shown in formulas A1 to A90:

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] Furthermore, the mass ratio of the doped material to the host material is 1:99 to 50:50.

[0081] The organic electroluminescent material described in this invention can be composed solely of the heterocyclic compounds of this invention, or it can contain other compounds simultaneously.

[0082] The present invention also includes an organic electroluminescent device comprising a cathode, an anode, and at least one emitting layer. In addition to these layers, it may also comprise other layers, such as, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers. An intermediate layer having, for example, exciton blocking functionality may also be introduced between two emitting layers. However, it should be noted that each of these layers is not necessarily required. The organic electroluminescent device described herein may comprise one emitting layer, or it may comprise multiple emitting layers. That is, a variety of luminescent compounds capable of emitting light are used in the emitting layers. A system having three emitting layers is particularly preferred, wherein the three layers can exhibit blue, green, and red light emission. If more than one emitting layer is present, according to the present invention, at least one of these layers comprises a compound of the present invention.

[0083] Furthermore, the organic electroluminescent element according to the present invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, that is, the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode.

[0084] In the other layers of the organic electroluminescent element according to the invention, particularly in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in accordance with the manner commonly used in the prior art. Those skilled in the art will therefore be able to combine all materials known about organic electroluminescent elements in the light-emitting layers according to the invention without inventive effort.

[0085] Furthermore, the following organic electroluminescent element is preferred, wherein one or more layers are applied to the element by means of a sublimation method, wherein in a vacuum sublimation apparatus at a temperature below 10 -5 Pa, preferably below 10 -6 The material is applied by vapor deposition at an initial pressure of Pa. However, the initial pressure may be even lower, for example, below 10 Pa. -7 Pa.

[0086] The organic electroluminescent element, preferably as described below, can be applied with one or more layers by means of organic vapor deposition or by means of carrier gas sublimation, wherein, in 10 -5 The material is applied at a pressure between 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 therefore structured.

[0087] Furthermore, the following organic electroluminescent elements are preferred, which produce one or more layers from solution, for example by spin coating, or by any desired printing method such as screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, inkjet printing, or nozzle printing. Soluble compounds, for example, obtained by appropriately substituting the heterocyclic compound. These methods are also particularly suitable for oligomers, dendritic macromolecules, and polymers. Additionally, mixing methods are feasible, in which one or more layers are applied from solution and one or more additional layers are applied by vapor deposition.

[0088] These methods are generally known to those skilled in the art, and they can be applied to organic electroluminescent devices containing heterocyclic compounds of the present invention without any inventive effort.

[0089] Therefore, the present invention also relates to a method for manufacturing an organic electroluminescent element according to the invention, wherein at least one layer may be applied by means of a sublimation method, and / or by means of an organic vapor deposition method or by means of carrier gas sublimation, and / or by means of spin coating or printing from a solution.

[0090] Furthermore, the present invention relates to a heterocyclic compound comprising at least one of the heterocyclic compounds of the present invention as described above. The same preferred embodiments as noted above regarding organic electroluminescent elements apply to the heterocyclic compounds of the present invention. In particular, the heterocyclic compounds may also preferably comprise other compounds. Processing the heterocyclic compounds of the present invention from the liquid phase, for example by spin coating or printing methods, requires formulations of the compounds according to the present invention. These formulations may be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents may be preferred. Suitable and preferred solvents include, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methyl anisole, 4-methyl anisole, 3,4-dimethyl anisole, 3,5-dimethyl anisole, acetophenone, α-terpenes. The solvents are benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-methylisopropylbenzene, phenethyl ether, 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, pentabenzene, hexene, heptene, octene, 1,1-bis(3,4-dimethylphenyl)ethane, or mixtures of these solvents.

[0091] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0092] This invention employs stable compounds with cores of diquinoxolinothiophene, diquinoxolinofuran, diquinoxolinopyrrole, diquinoxolinofluorene, and diquinoxolinoselenophene as luminescent units. On one hand, the charge transfer effect between the donor (D) and acceptor (A) enables the separation of HOMO and LUMO, thus achieving the TADF effect. Simultaneously, the large conjugated plane of the core reduces the relaxation degree of the excited-state structure, resulting in a narrower half-width at half-maximum (HWHM). On the other hand, by introducing different substituents onto the rigid framework, the delayed fluorescence lifetime and HWHM can be further adjusted, resulting in a narrower emission peak width and higher efficiency compared to previous compounds. Furthermore, these heterocyclic compounds exhibit high thermal stability, thereby improving the lifetime of organic electroluminescent devices containing them. In addition, these heterocyclic compounds improve solution solubility, solving the productivity and cost issues associated with previous blue, green, red, and near-infrared light materials. Moreover, they can be used to prepare the luminescent layer not in the vapor deposition process but in the solution preparation process. Attached Figure Description

[0093] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0094] Figure 1 A schematic diagram of an organic light-emitting device 100 is shown. The diagram is not necessarily drawn to scale. Device 100 may include a substrate 101, an anode layer 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, an electron transport layer 107, an electron injection layer 108, a cathode layer 109, and a capping layer (CPL) 110. Device 100 can be fabricated by sequentially depositing the described layers.

[0095] Figure 2A schematic diagram of an organic light-emitting device 200 with two light-emitting layers is shown. The device includes a substrate 201, an anode layer 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode layer 213. The device 200 can be fabricated by sequentially depositing the described layers. Because most common OLED devices have one light-emitting layer, and device 200 has a first light-emitting layer and a second light-emitting layer, the emission peaks of the first and second light-emitting layers can be overlapping, cross-overlapping, or non-overlapping. Materials similar to those described with respect to device 100 can be used in the corresponding layers of device 200. Figure 2 Provides an example of how to add layers from the structure of device 100. Detailed Implementation

[0096] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0097] In this invention, "EQE" refers to the external quantum efficiency of a device, which is the ratio of the number of photons emitted by the device to the number of electrons injected into the device.

[0098] Figure 1 and Figure 2 The simple layered structures described herein are provided as non-limiting examples, and it should be understood that embodiments of the invention can be used in combination with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. A functional OLED can be realized by combining the described layers in different ways based on design, performance, and cost factors, or several layers can be omitted entirely. Other layers not specifically described may also be included. Materials different from those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it will be understood that combinations of materials, such as mixtures of matrix and dopant, or more generally, mixtures, can be used. Furthermore, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 204 transports holes and injects holes into light-emitting layer 205, and can be described as a hole transport layer or an electron blocking layer. In one embodiment, the OLED can be described as having an organic layer disposed between a cathode and an anode. This organic layer may comprise a single layer or may further comprise, as exemplified... Figure 1 and Figure 2 Multiple layers of different organic materials are described.

[0099] Structures and materials not specifically described can also be used, such as PLEDs containing polymer materials. As another example, OLEDs with a single organic layer or multiple stacks can be used. OLED structures can be detached from... Figure 1 and Figure 2 The simple layered structure is illustrated in the diagram. For example, the substrate may include angled reflective surfaces to improve optical coupling.

[0100] Unless otherwise specified, any of the layers in the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, organic vapor deposition methods, or applying one or more layers by means of carrier gas sublimation, wherein, in 10 -5 The material is applied at a pressure between millibar and 1 bar. A particular example of this method is an organic vapor jet printing method, in which the material is applied directly through a nozzle and is therefore structured. Other suitable deposition methods include producing one or more layers, for example by spin coating, or by means of any desired printing method such as screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, inkjet printing, or nozzle printing. Soluble compounds, for example, are obtained through appropriate substitution. These methods are also particularly suitable for oligomers, dendritic macromolecules, and polymers. Furthermore, mixing methods are feasible, in which one or more layers are applied, for example, from a solution and one or more additional layers are applied by vapor phase deposition.

[0101] The device manufactured according to embodiments of the present invention may optionally further include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in the environment, including moisture, vapors, and / or gases. The barrier layer may be deposited on, under, or beside a substrate or electrode, or on any other part of the device, including edges. The barrier layer may comprise a single layer or multiple layers. The barrier layer may be formed using various known chemical vapor deposition techniques and may comprise compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds, or both. Preferably, the barrier layer comprises a mixture of polymeric and non-polymeric materials. For it to be considered a mixture, the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited under the same conditions and / or simultaneously. The weight ratio of the polymeric material to the non-polymeric material may be in the range of 95 / 5 to 5 / 95. In one example, the mixture of polymeric and non-polymeric materials is essentially composed of polymeric silicon and inorganic silicon.

[0102] In any of the compounds mentioned above used in each layer of the OLED element described above, hydrogen atoms may be partially or fully deuterated. Therefore, any specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., may be in their undeuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in their undeuterated, partially deuterated, and fully deuterated forms.

[0103] The materials and structures described herein can be applied to components other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures described herein.

[0104] Furthermore, organic devices, such as organic transistors, can utilize the aforementioned materials and structures.

[0105] In the following embodiments of the present invention, conventional preparation methods are used unless otherwise specified. All raw materials used are commercially available unless otherwise specified, and all percentages are by mass unless otherwise specified.

[0106] To more clearly illustrate the present invention, the technical solution of the present invention is described below in conjunction with some specific embodiments:

[0107] In the embodiments of the present invention, the performance testing conditions of the prepared electroluminescent device are as follows:

[0108] Chromaticity coordinates: tested using a PhotoResearch PR-715 spectral scanner;

[0109] Current-voltage: Tested using a Keithley 2420 digital source meter;

[0110] Power efficiency: Tested using NEWPORT 1931-C;

[0111] Brightness: Tested using a Minolta Cs-1000A luminance meter.

[0112] Example 1

[0113] The preparation method of compound B001 includes the following steps:

[0114] Step 1: Preparation of intermediate Int-1

[0115]

[0116] Under nitrogen protection, 40.0 mmol of 2-ethynylnaphthalene (reactant 2), 20.0 mmol of 2,5-dibromo-3,4-dicyanothiophene (reactant 1), 4.0 mmol of cuprous iodide, 4.0 mmol of PdCl2(PPh3)2, 8.0 mmol of triphenylphosphine and 80 mL of triethylamine were mixed, heated to reflux and stirred for 15 hours, cooled to room temperature, concentrated under reduced pressure and dried, and purified by silica gel column chromatography to give compound Int-1 as a yellow solid with a yield of 86%.

[0117] Step 2: Preparation of intermediate Int-2

[0118]

[0119] Under nitrogen protection, 20.0 mmol of the previously prepared Int-1, 80.0 mmol of nitromethane, 80.0 mmol of potassium hydroxide, and 60 mL of DMSO were mixed, heated to 110 °C, and stirred for 45 minutes. After cooling to room temperature, the reaction solution was poured into 150 mL of ice water, filtered, the filter cake was washed with water, and recrystallized from methanol to give compound Int-2, a red solid, with a yield of 82%.

[0120] Step 3: Preparation of intermediate Int-3

[0121]

[0122] 20.0 mmol of the previously prepared Int-2 was mixed with 100 mL of ethanol, 20 mL of concentrated hydrochloric acid and 0.2 g of 10% palladium / carbon were added, hydrogen gas was introduced under normal pressure, and the mixture was stirred at room temperature for 15 hours. The mixture was filtered, and the filtrate was concentrated under reduced pressure to dryness to obtain compound Int-3, a red solid with a yield of 100%.

[0123] Step 4: Preparation of compound B001

[0124]

[0125] Under nitrogen protection, 20.0 mmol of Int-3 prepared in the previous step, 40.0 mmol of glyoxal hydrate (reactant 3) and 60 mL of glacial acetic acid were mixed, heated to reflux and stirred for 10 hours, cooled to room temperature, concentrated under reduced pressure to dryness, and purified by silica gel column chromatography to give compound B001, a yellow solid, with a yield of 64% and MS (TOF) m / z: 541.1425. 1 HNMR (δ, CDCl3): 9.17~9.15(2H,d); 8.86(2H,s); 8.67(2H,s); 8.01~7.98(4H,m); 7.86~7.82(4H,m); 7.57~7.47(6H,m).

[0126] Following a similar synthetic method as described above, the following compounds were prepared.

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] Example 2

[0134] Preparation of compound B103:

[0135]

[0136] Under nitrogen protection, 20.0 mmol of Int-4 (prepared according to the synthesis method in Example 1), 44.0 mmol of 9,10-dihydro-9,9-dimethylacridine, 4.0 mmol of cuprous iodide, 4.0 mmol of Pd2(dba)3, 8.0 mmol of 10% tri-tert-butylphosphide toluene solution and 80 mL of toluene were mixed, heated to 100 °C, stirred for 15 hours, cooled to room temperature, 50 mL of water was added, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was dried, filtered, the filtrate was concentrated under reduced pressure and dried, and purified by silica gel column chromatography to give compound B103, a yellow solid, in 82% yield, MS (TOF) m / z: 855.3204; 1 HNMR (δ, CDCl3): 9.17~9.15(4H,d); 8.79(2H,s); 7.49~7.45(4H,m); 7.30~7 .24(8H,m); 7.09~7.03(4H,m); 7.01~6.98(8H,m); 1.76(6H,s); 1.64(6H,s).

[0137] Example 3

[0138] Preparation of compound B104:

[0139]

[0140] 10.0 mmol of B103 and 40 mL of glacial acetic acid were mixed, and 1.0 mmol of ferric nitrate nonahydrate was added. Oxygen was bubbled into the reaction solution, the temperature was raised to 50 °C, and the reaction was stirred for 1 hour. The mixture was concentrated and dried under reduced pressure, and 50 mL of saturated sodium bicarbonate aqueous solution was added. The mixture was filtered, the filter cake was washed with water, and purified by silica gel column chromatography to give compound B104 with a yield of 95%. MS (TOF) m / z: 871.3233. 1 HNMR (δ, CDCl3): 9.12~9.10(4H,d); 8.89(2H,s); 7.55~7.50(4H,m); 7.30~7 .25(8H,m); 7.14~7.09(4H,m); 7.03~6.98(8H,m); 1.76(6H,s); 1.64(6H,s).

[0141] Example 4

[0142] Preparation of compound B105:

[0143]

[0144] 10.0 mmol of B103 and 40 mL of glacial acetic acid were mixed, and 1.0 mmol of ammonium molybdate and 5 mL of 30% hydrogen peroxide were added. The mixture was stirred at room temperature for 15 hours, concentrated and dried under reduced pressure, and 50 mL of saturated sodium bicarbonate aqueous solution was added. The mixture was filtered, the filter cake was washed with water, and purified by silica gel column chromatography to give compound B105 with a yield of 98% and MS (TOF) m / z: 887.3106. 1 HNMR(δ, CDCl3): 9.41(2H,s); 9.03(2H,s); 8.93(2H,s); 7.69~7.65(4H,m); 7.3 0~7.25(8H,m); 7.19~7.14(4H,m); 7.04~6.98(8H,m); 1.76(6H,s); 1.64(6H,s).

[0145] Following a similar synthesis method to Examples 2 to 4 above, the following compounds were prepared.

[0146]

[0147]

[0148]

[0149] Example 5

[0150] The preparation method of compound B176 includes the following steps:

[0151] Step 1: Preparation of intermediate Int-6

[0152]

[0153] Under nitrogen protection, 20.0 mmol of Int-5 (prepared by replacing 2-ethynylnaphthalene with propyne cyanide in step 1 of Example 1), 0.1 mol of sodium hydroxide, and 60 mL of water were mixed, heated to reflux, stirred for 15 hours, cooled to room temperature, and adjusted to acidity with dilute hydrochloric acid. The mixture was filtered, and the filter cake was washed with water to obtain compound Int-6, a white solid with a yield of 96%.

[0154] Step 2: Preparation of intermediate Int-7

[0155]

[0156] Under nitrogen protection, 20.0 mmol of Int-6 prepared in the previous step, 42.0 mmol of N-hydroxyphthalimide, 80.0 mmol of triethylamine, and 80 mL of dichloromethane were mixed and cooled to 0 °C. 42.0 mmol of N,N'-dicyclohexylcarboimide was added dropwise, and the mixture was stirred for 1 hour. The mixture was then heated to room temperature and stirred for 15 hours. The mixture was cooled to -5 °C, filtered, and the filtrate was concentrated and dried under reduced pressure. The filtrate was purified by silica gel column chromatography to obtain compound Int-7 as a yellow solid with a yield of 92%.

[0157] Step 3: Preparation of intermediate Int-8

[0158]

[0159] Under nitrogen protection, 20.0 mmol of Int-7, 80.0 mmol of pinacol diboronate and 6.0 mmol of tert-butyl isonicotinate were mixed and 100 mL of dry trifluoromethylbenzene was added. The mixture was heated to 110 °C and stirred for 15 hours. After cooling to room temperature, the mixture was concentrated to dryness under reduced pressure and purified by silica gel column chromatography to give compound Int-8 as a yellow solid with a yield of 84%.

[0160] Step 4: Preparation of compound B176

[0161]

[0162] Under nitrogen protection, 24.0 mmol of Int-8 (reactant 1) prepared in the previous step, 10.0 mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine (reactant 2) and 40 mL of toluene were mixed, and then 60.0 mmol of anhydrous potassium carbonate, 0.01 mmol of Pd132, 20 mL of ethanol and 20 mL of water were added. The mixture was heated to reflux and stirred for 12 hours, cooled to room temperature, 50 mL of water was added, and the mixture was filtered. The filter cake was washed with water and purified by silica gel column chromatography to give compound B176, a white solid with a yield of 72% and MS (TOF) m / z: 751.2159. 1 HNMR (δ, CDCl3): 9.47(2H,s); 9.29~9.27(4H,d); 8.78~8.73(8H,m); 7.56~7.50(8H,m); 7.45~7.39(4H,m).

[0163] Following a similar synthetic method as described above, the following compounds were prepared.

[0164]

[0165]

[0166]

[0167] Example 6

[0168] The preparation method of compound B136 includes the following steps:

[0169] Step 1: Preparation of intermediate Int-9

[0170]

[0171] Under nitrogen protection, 20.0 mmol of Int-8, 20.0 mmol of copper bromide, 30 mL of isopropanol, and 30 mL of DMF were mixed, heated to reflux, and stirred for 5 hours. Then, 10.0 mmol of copper bromide was added, and the mixture was refluxed for another 5 hours. After cooling to room temperature, 100 mL of water was added, and the mixture was filtered. The filter cake was washed with water and purified by silica gel column chromatography to obtain compound Int-9 as a yellow solid with a yield of 84%.

[0172] Step 2: Preparation of compound B136

[0173]

[0174] Under nitrogen protection, 20.0 mmol of Int-9, 42.0 mmol of 5-phenyl-5,10-dihydrophenazine, 60.0 mmol of sodium tert-butoxide, 0.2 mmol of Pd2(dba)3, 0.4 mmol of Xantphos, and 80 mL of toluene were mixed, heated to 100 °C, and stirred for 15 hours. After cooling to room temperature, 100 mL of water was added, and the mixture was filtered. The filter cake was washed with toluene and water, purified by silica gel column chromatography, and recrystallized from dichloromethane to give compound B136 as a yellow solid with a yield of 83%. MS (TOF) m / z: 801.2565. 1 HNMR (δ, CDCl3): 9.09~9.07(4H,d); 8.14(2H,s); 7.16~7.04(12H,m); 7.02~6.98(8H,m); 6.94~6.89(2H,m); 6.86~6.81(4H,m).

[0175] Example 7

[0176] Preparation of compound B137:

[0177]

[0178] Following the synthesis method of Example 3, except that B103 in Example 3 was replaced with B136, compound B137 was prepared as a yellow solid with a yield of 94% and MS (TOF) m / z: 817.2512. 1 HNMR (δ, CDCl3): 9.09(2H,s); 9.02(2H,s); 8.14(2H,s); 7.16~7.04(12H,m); 7.02~6.98(8H,m); 6.94~6.89(2H,m); 6.86~6.81(4H,m).

[0179] Example 8

[0180] Preparation of compound B138:

[0181]

[0182] Following the synthesis method of Example 4, except that B103 in Example 4 was replaced with B136, compound B138 was prepared as a white solid with a yield of 96% and MS (TOF) m / z: 833.2385. 1 HNMR (δ, CDCl3): 9.36(2H,s); 8.96(2H,s); 8.36(2H,s); 7.15~7.03(12H,m); 7.01~6.94(8H,m); 6.92~6.87(2H,m); 6.85~6.80(4H,m).

[0183] Following a similar synthesis method to Examples 6 to 8 above, the following compounds were prepared:

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193] Example 9

[0194] An organic electroluminescent device 100, such as Figure 1 As shown, the organic electroluminescent device has a substrate 101, an anode layer 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, an electron transport layer 107, an electron injection layer 108, a cathode layer 109, and a CPL layer 110 may be included above the cathode layer 109.

[0195] An organic light-emitting device 200 containing two light-emitting layers, such as Figure 2 As shown, the device includes a substrate 201, an anode layer 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode layer 213.

[0196] This embodiment Figure 1 The method for fabricating the organic electroluminescent device shown includes the following steps:

[0197] (1) The glass substrate coated with the ITO conductive layer was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonically treated in an acetone / ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, irradiated with a UV cleaner for 10 minutes, and bombarded with a low-energy cation beam. The treated ITO glass substrate was then placed in a vacuum chamber and evacuated to a vacuum level of less than 1 × 10⁻⁶. -5Pa, metallic silver is deposited on the above ITO film, with a film thickness of [missing value]. The anode layer is obtained.

[0198] (2) The compound DNTPD is then deposited as a hole injection layer on the aforementioned anolyte film, with a film thickness of [missing information]. HTM is then deposited onto the aforementioned hole injection layer to form a hole transport layer, with a deposition thickness of [missing information].

[0199] (3) A layer of compound HT2O2 is deposited on the hole transport layer as an electron blocking layer, with a deposition thickness of [missing information].

[0200] (4) A heterocyclic compound of Formula I and A85 are deposited on the electron blocking layer as an organic light-emitting layer, wherein A85 is the host material and the heterocyclic compound of Formula I is the dopant material, the doping concentration of the heterocyclic compound of Formula I in A85 is 8%, and the deposited film thickness is [missing information].

[0201] (5) A further layer of compounds LiQ and ET2O5 is deposited on the above-mentioned light-emitting layer as an electron transport layer of the device, wherein the mass ratio of LiQ and ET2O5 is 1:1, and the thickness of the deposited film is [missing information].

[0202] (6) A further layer of compound LiF is deposited on the above electron transport layer as the electron injection layer of the device, with a deposition thickness of [missing information].

[0203] (7) Magnesium and silver are deposited as the cathode layer of the element on the electron injection layer, wherein the mass ratio of magnesium to silver is 2:1, and the thickness of the deposited film is [missing information].

[0204] (8) Compound HTO38 is deposited as a CPL layer on the cathode layer described above, with a deposition film thickness of [missing information].

[0205] Prepared by similar methods as described above Figure 2 The organic electroluminescent device shown.

[0206] The compound structure used in this embodiment is shown below:

[0207]

[0208] Comparative Example 1

[0209] The organic electroluminescent device was prepared according to the same steps as in Example 9, except that compound B020 was used instead of the heterocyclic compound of the present invention in step (4).

[0210] The structure of compound B020 is as follows:

[0211]

[0212] Example 10

[0213] The organic electroluminescent device was prepared according to the same steps as in Example 9, except that in step (4), compound B020 was used instead of the heterocyclic compound of the present invention, and in step (5), the heterocyclic compound of the present invention was used instead of compound ET205.

[0214] The organic electroluminescent devices prepared in Examples 9 and 10, as well as Comparative Example 1, were subjected to performance testing. Specifically, the voltage was increased at a rate of 0.1V per second, and the luminance of the organic electroluminescent element was measured when it reached 1000 cd / m². 2 The voltage at that time is the driving voltage, and the current density at that time is measured simultaneously; the ratio of brightness to current density is the current efficiency; the LT95% lifespan test is as follows: using a luminance meter at 1000 cd / m² 2 At a constant current under the given brightness, the brightness decay of the organic electroluminescent element was measured to be 950 cd / m². 2 The time is in hours. The data listed in Table 1 are relative to Comparative Example 1. The results are shown in Table 1.

[0215] Table 1 Performance Test Results

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223] The experimental data above show that the compounds of this invention achieve the separation of HOMO and LUMO through charge transfer between the donor (D) and acceptor (A), thereby realizing the TADF effect. Simultaneously, the hybrid units of diquinoxaline and the large planar conjugated groups such as dibenzothiophene possess rigid framework structures, which can reduce the relaxation degree of the excited-state structure, thus achieving a narrower half-width, lower driving voltage, and higher luminous efficiency. As a luminescent material, compared to using BO20, the difference lies in the smaller acceptor conjugated area of ​​BD020, allowing the donor to rotate freely in the excited state, resulting in energy loss of the excited-state molecule and a decrease in quantum efficiency. As an electron transport material, compared to using ET205, the driving voltage is lower, and the efficiency is significantly improved. Therefore, the heterocyclic compounds of this invention exhibit superior device performance.

[0224] The industrial applications of the compounds of this invention are possible:

[0225] Organic electroluminescent devices containing the compounds of this invention can be used in wall-mounted televisions, flat panel displays, lighting and other planar light sources, copiers, printers, backlights of liquid crystal displays or light sources of measuring instruments, display panels, indicator lights, etc.

[0226] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A heterocyclic compound, characterized in that, The heterocyclic compound is selected from any of the following structures: in, Ar 1 Ar 2 Each is independently selected from unsubstituted C6-C 60 Aryl, unsubstituted C6-C 60 Aromatic amino group, unsubstituted C2-C 60 Groups composed of heteroaryl groups; The R 1 R 2 It is hydrogen; R 3 R 4 R 5 R 6 Each is independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, or unsubstituted phenyl; R 7 R 8 Each time it appears, it is independently selected from hydrogen, methyl, ethyl or unsubstituted phenyl; R 9 Each time it appears, it is selected from methyl, ethyl, or unsubstituted phenyl; Ar 3 Ar 4 Ar 5 Ar 6 Each is independently selected from unsubstituted C6-C 60 Aryl, unsubstituted C6-C 60 Aromatic amino group, unsubstituted C2-C 60 Groups composed of heteroaryl groups; The L 1 L 2 Each is independently selected from a single bond or from the group consisting of the following groups from III-1 to III-24: Wherein, G is selected from O, S, SO, SO2, CR'R”, SiR'R” or NAr’; Z 11 Z 12 Z 13 Z 14 Each is independently selected from hydrogen, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidine group, hydrazine group, hydrazone group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C1-C 60 Alkyl, C2-C 60 alkenyl, C2-C 60 alkynyl group, C1-C 60 alkoxy groups, C3-C 60 Cycloalkane group, C3-C 60 Cycloolefin group, unsubstituted C6-C 60 Aryl, unsubstituted C6-C 60 aryloxy group, unsubstituted C6-C 60 aryl sulfide group, or unsubstituted C2-C 60 Groups composed of heteroaryl groups; y1 represents an integer from 1 to 4; y2 represents an integer from 1 to 6; y3 represents an integer from 1 to 3; y4 represents an integer from 1 to 5; y5 represents an integer of 1 or 2. R ’ "R" represents methyl, phenyl, or fluorene; Ar ’ It can be methyl, ethyl, phenyl, biphenyl, or naphthyl; In this context, the dashed lines represent the connection sites of functional groups.

2. The heterocyclic compound according to claim 1, characterized in that, The heterocyclic compound is selected from one of the compounds shown in formulas B001 to B309:

3. An organic electroluminescent element, comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, characterized in that, The organic layer comprises the heterocyclic compound as described in any one of claims 1-2.

4. The organic electroluminescent element according to claim 3, characterized in that, The organic layer comprises one or more electron injection layers, electron transport layers, hole injection layers, hole transport layers, hole blocking layers, electron blocking layers, and light-emitting layers, wherein the light-emitting layer or electron transport layer comprises the heterocyclic compound as described in any one of claims 1-2.

5. The organic electroluminescent element according to claim 4, characterized in that, The light-emitting layer further includes a host material and a dopant material. The host material comprises a compound consisting of the following chemical groups: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azirtriphenylene, azircarbazole, azirdibenzothiophene, azirdibenzofuran, azirdibenzoselenene, or triazine. The dopant material comprises a heterocyclic compound as described in any one of claims 1-2.

6. The organic electroluminescent element according to claim 5, characterized in that, The mass ratio of the doped material to the host material is 1:99 to 50:

50.

7. The use of the heterocyclic compound according to any one of claims 1-2 in organic electroluminescent devices.

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