An organic electroluminescent compound and its application

Abstract

The present invention relates to an organic electroluminescent compound, a light-emitting device and a consumer product. By including the organic electroluminescent compound according to the present disclosure, an organic electroluminescent device having improved driving voltage and / or current efficiency characteristics can be provided.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescence, and in particular relates to an organic electroluminescent compound, an organic electroluminescent material, a light-emitting device and a consumer product. Background Art

[0002] Most of the substances used in organic electroluminescent elements are pure organic substances or organic metal complexes formed by organic substances and metals. According to the purpose, they can be divided into hole injectors, hole transporters, luminescent substances, electron transporters, electron injectors, etc. Here, organic substances with relatively small ionization energy are mainly used as hole injectors or hole transporters, and organic substances with large electronegativity are mainly used as electron injectors or electron transporters. In addition, the substances used as the light-emitting auxiliary layer are preferably able to meet the following characteristics.

[0003] First, the substances used in organic electroluminescent elements need good thermal stability. The reason is that Joule heat is generated inside the organic electroluminescent element due to the migration of charges. At present, the glass transition temperature of the materials commonly used as hole transport layers is low. Therefore, when driven at low temperatures, the luminous efficiency decreases due to crystallization. Second, in order to reduce the driving voltage, the organic substances adjacent to the cathode and anode need to be designed to have a small charge injection barrier and a high charge mobility. Third, there are always energy barriers at the interface between the electrode and the organic layer, and at the interface between the organic layer and the organic layer, and some charges are inevitably accumulated, so it is necessary to use substances with excellent electrochemical stability.

[0004] The light-emitting layer is composed of two substances, the main light-emitting body and the dopant. The dopant needs to have high quantum efficiency. Compared with the dopant, the main light-emitting body needs to have a large energy gap so that energy transfer to the dopant can easily occur. Displays used for televisions, mobile devices, etc. achieve full color based on the three primary colors of red, green, and blue. The light-emitting layer is composed of red main light-emitting body / dopant, green main light-emitting body / dopant, and blue main light-emitting body / dopant, respectively. At present, blue light materials still have the problems of low luminous quantum efficiency and poor color purity. The main reason for this situation is that blue light comes from the transition between energy levels with a wide energy gap, and wide bandgap organic compounds have certain difficulties in molecular design. Secondly, there is a strong π-π bond interaction in the system of blue light materials, and it has a strong charge transfer characteristic, so that there are more radiation-free relaxation channels in the wide band gap, which aggravates the fluorescence quenching between molecules and reduces the quantum yield of the blue light system.

[0005] In view of the above reasons, the present invention is proposed. Summary of the invention

[0006] In order to solve the above problems existing in the prior art, the present invention provides an organic electroluminescent compound, an organic electroluminescent material, a light-emitting device and a consumer product. The organic electroluminescent compound of the present invention is blue to dark blue and has high luminous efficiency.

[0007] The first object of the present invention is to provide an organic electroluminescent compound.

[0008] The second object of the present invention is to provide an organic electroluminescent material.

[0009] The third object of the present invention is to provide an organic electroluminescent device.

[0010] The fourth object of the present invention is to provide a consumer product.

[0011] In order to achieve the above object, the present invention adopts the following technical solution:

[0012] An organic electroluminescent compound, the general structural formula of the compound is shown in formula (I):

[0013]

[0014] Wherein, L is selected from a single bond, a substituted or unsubstituted C6-C 60 Arylene, substituted or unsubstituted C2-C 60 A heteroarylene group;

[0015] n is an integer selected from 0 to 5;

[0016] Ar 2 Selected from substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C5-C 60 heteroaryl;

[0017] Ar 1 Formula (II):

[0018]

[0019] In formula (II), X 1 , X 2 Each independently selected from O, S, SiR 5 R 6 or CR 5 R 6 ;

[0020] q and p are independently 0 or 1, preferably, p+q=1;

[0021] R 1 , R 2 , R 3 , R4 , R 5 , R 6 At each occurrence, each is identically or differently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C 40 Alkyl, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C5-C 60 Heteroaryl; any two or more adjacent groups may be cyclized or fused to form a substituted or unsubstituted ring;

[0022] R 1 , R 2 , R 3 , R 4 represent one or more substitutions to saturation, and at least one of R3 or R4 is connected to L.

[0023] The alkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a straight or branched saturated hydrocarbon having a carbon number of 1 to 40. Non-limiting examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, and the like;

[0024] The aryl group in the sense of the present invention contains 6 to 60 carbon atoms, and the heteroaryl group contains 2 to 60 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. In this case, the two or more rings of the heteroaryl group can be attached to each other simply or in a condensed form, and further, can also include a condensed form with the aryl group. As non-limiting examples of aryl and heteroaryl groups, in particular, the following groups are selected: phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, pyrenyl, yl, peryl, fluoranthene, tetraphenyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenyl, quadriphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, triphenylene, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, cis- or trans-indenocarbazolyl, indolecarbazolyl, benzofuranocarbazolyl, benzothiophenocarbazolyl, benzocarbazolyl, dibenzocarbazolyl, azadibenzo[g,Id]naphtho[2,1,8-cde]azulene, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroisotrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridinyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo[5,6]quinolyl, benzo[6,7]quinolyl, benzo[7,8]quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, isoxazolyl, 1,2- Thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazatriphenylene radical, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorescein ring radical, naphthyridinyl, azacarbazolyl, benzocarbolinyl, carbolinyl, phenanthroline radical, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1 ,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, quinazolinyl, benzothiadiazolyl or a group derived from a combination of these systems.

[0025] The "halogen" or "halogen atom" used in the present invention refers to a group selected from fluorine, chlorine, bromine or iodine.

[0026] Furthermore, the organic electroluminescent compound is selected from any one of the following structures:

[0027]

[0028]

[0029] Among them, R 1 , R 2 , R 3 , R 4 , X 1 , X 2 , L, Ar 2 The definitions of , q, p and n are the same as those above.

[0030] Furthermore, the Ar 2 selected from substituted or unsubstituted phenyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted quaterphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted benzanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted The invention also comprises a group consisting of a substituted or unsubstituted perylene group, a substituted or unsubstituted fluoranthene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophene group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophene group.

[0031] The substituted alkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, etc. described in the present invention, each of the substituents is independently selected from at least one of the following groups: deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, C1-C 40 Alkyl, C1-C 40 Halogenated alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C1-C 40 Alkoxy, C1-C 40 Alkylthio, C3-C 40 Cycloalkyl, C3-C 40 Cycloalkenyl, 3- to 7-membered heterocycloalkyl, C6-C 60 Aryloxy, C6-C 60 Arylthio, unsubstituted or substituted with one or more C6-C 60 3- to 30-membered heteroaryl, unsubstituted or deuterated, one or more C1-C 40 C6-C substituted with at least one of an alkyl group and one or more 3- to 30-membered heteroaryl groups 60 Aryl, tri(C1-C 40 ) alkylsilyl, tri(C6-C 60 )Arylsilyl, di(C1-C 40 ) Alkyl C6-C 60 Arylsilyl, C1-C40 Alkyl di(C6-C 60 )Arylsilyl, C1-C 40 Alkylcarbonyl, C1-C 40 Alkoxycarbonyl, C6-C 60 Arylcarbonyl, di(C6-C 60 ) aryl borocarbonyl, di(C1-C 40 ) alkyl boron carbonyl, C1-C 40 Alkyl C6-C 60 Aryl boronyl, C6-C 60 Aryl C1-C 40 Alkyl, and C1-C 40 Alkyl C6-C 60 Aryl.

[0032] Heteroalkyl in the sense of the present invention means that the hydrogen atom or -CH2- on the alkyl group is replaced by at least one heteroatom, and the heteroatom is selected from halogen, nitrile, N, O, S or silicon, as non-limiting examples, there are difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl, nitrile, acetonitrile, methoxymethyl, methoxyethyl, trimethylsilyl, triisopropylsilyl, etc. Haloalkyl means that the hydrogen atom on the alkyl group is partially or fully replaced by halogen, as non-limiting examples, there are fluorotoluene, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, trifluoroethyl, pentafluoroethyl, etc.

[0033] The alkenyl or alkynyl group used in the present invention contains at least two carbon atoms. As non-limiting examples, alkenyl or alkynyl is preferably taken to mean the following groups: cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

[0034] The alkoxy and alkylthio groups used in the present invention are preferably alkoxy or alkylthio groups having 1 to 40 carbon atoms, and are considered to be methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio 4-(2-(4-(2-methyl-1-thio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1,4-dithio)-1

[0035] Generally speaking, the cycloalkyl and cycloalkenyl groups according to the present invention can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, and cycloheptenyl, wherein one or more -CH2- groups can be replaced by N, O or S to form heterocycloalkyl and heterocycloalkenyl groups, for example, one -CH2- group in the cyclopentyl group is replaced by O to form tetrahydrofuranyl, one -CH2- group in the cyclohexyl group is replaced by O to form tetrahydropyranyl, etc.; in addition, one or more hydrogen atoms can also be replaced by deuterium atoms, halogen atoms or nitrile groups.

[0036] The aryloxy group used in the present invention refers to a monovalent functional group represented by R'O-, wherein R' is an aryl group having a carbon number of 6 to 60. Non-limiting examples of such aryloxy groups include phenoxy, naphthoxy, biphenyloxy and the like.

[0037] The arylthio group used in the present invention refers to a monovalent functional group represented by R"S-, wherein R" is an aryl group having 6 to 60 carbon atoms. Non-limiting examples of such arylthio groups include phenylthio, naphthylthio, biphenylthio and the like.

[0038] The alkylsilyl used in the present invention refers to a silyl group substituted by an alkyl group having 1 to 40 carbon atoms, and the number of carbon atoms constituting the alkylsilyl group is at least 3. Non-limiting examples of the alkylsilyl group include trimethylsilyl and triethylsilyl. The arylsilyl group refers to an alkylsilyl group substituted by at least one aryl group having 6 to 60 carbon atoms, and non-limiting examples include phenyldimethylsilyl, naphthyldimethylsilyl, phenyldiethylsilyl, diphenylmethylsilyl, diphenylethylsilyl, triphenylsilyl, and the like.

[0039] "Alkylcarbonyl", "alkoxycarbonyl", "arylcarbonyl", "arylborylcarbonyl" and "alkylborylcarbonyl" in the sense of the present invention refer to a substituted carbonyl group (-COR*), wherein R* is preferably selected from the group consisting of alkyl, alkoxy, cycloalkyl, aryl, heteroaryl, arylboryl and alkylboryl.

[0040] The arylphosphino group used in the present invention refers to a diarylphosphino group substituted with an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the arylphosphino group include diphenylphosphino group, di(4-trimethylsilylphenyl)phosphino group, etc. The aryloxyphosphino group is a diarylphosphino group in which the phosphorus atom is oxidized to the highest valence state.

[0041] The aryl boryl group used in the present invention refers to a diaryl boryl group substituted by an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the aryl boryl group include diphenyl boryl and di(2,4,6-trimethylphenyl)boryl. The alkyl boryl group refers to a dialkyl boryl group substituted by an alkyl group having 1 to 40 carbon atoms, and non-limiting examples of the alkyl boryl group include di-tert-butyl boryl and diisobutyl boryl.

[0042] The arylalkyl group according to the present invention refers to an alkyl group in which at least one hydrogen atom of a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms is substituted by an aryl group having 6 to 60 carbon atoms, and as non-limiting examples, may be phenylmethyl, diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, etc.

[0043] The alkylaryl group according to the present invention refers to an aryl group having 6 to 60 carbon atoms in which at least one hydrogen atom is substituted by a straight-chain or branched saturated hydrocarbon having 1 to 40 carbon atoms. As non-limiting examples, it may be methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl, isopropylphenyl, etc.

[0044] The arylene group in the present invention refers to a divalent functional group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having a carbon number of 6 to 60. Non-limiting examples thereof include phenylene, naphthylene, phenanthrylene, anthrylene, fluorenylene, and spirobifluorenylene.

[0045] The heteroarylene group or heteroarylene group in the present invention refers to a divalent functional group obtained by removing two hydrogen atoms from a heteroaromatic hydrocarbon having 5 to 60 carbon atoms. Non-limiting examples thereof include pyridylene, quinolylene, isoquinolylene, carbolylene, pyrimidylene, triazinylene and the like.

[0046] According to the above-mentioned arylene and heteroarylene as divalent functional groups and Ar 1 and anthracene, preferably, L is selected from a single bond or a group consisting of the following groups shown in III-1 to III-23:

[0047]

[0048] The dashed lines represent the attachment sites of the groups.

[0049] Furthermore, the anthracene derivative is one of the following structures CJHB950 to CJHB1090:

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057] The hydrogen atoms in the above formulae may be partially or completely replaced by deuterium.

[0058] As used herein, "combinations thereof" or "groups" means that one or more members of the applicable list are combined to form known or chemically stable arrangements that can be envisioned by one of ordinary skill in the art from the applicable list. For example, alkyl and deuterium atoms can be combined to form partially or fully deuterated alkyls; halogens and alkyls can be combined to form haloalkyl substituents, such as trifluoromethyl, etc.; and halogens, alkyls, and aryls can be combined to form haloaralkyls.

[0059] An organic electroluminescent material comprises the organic electroluminescent compound.

[0060] The organic electroluminescent material may be composed of the compound of the present invention alone or may contain other compounds simultaneously.

[0061] The compound of the present invention contained in the organic electroluminescent material of the present invention can be used as, but not limited to, a light-emitting layer material, a carrier transport layer material or a capping layer material.

[0062] An organic electroluminescent device comprises 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 organic electroluminescent compound provided by the invention.

[0063] The organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer. In addition to these layers, it may also comprise other layers, for example, 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, an exciton blocking function may also be introduced between two light-emitting layers. However, it should be noted that each of these layers does not necessarily have to be present. The organic electroluminescent device described herein may comprise one light-emitting layer, or it may comprise multiple light-emitting layers. That is, a variety of light-emitting compounds capable of emitting light are used in the light-emitting layer. Preferably, a system with three light-emitting layers is provided, wherein the three layers can display blue, green and red light emission. If there is more than one light-emitting layer, then according to the present invention, at least one of these layers comprises a compound of the present invention.

[0064] Furthermore, the organic electroluminescent device according to the present invention does not include 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.

[0065] In the other layers of the organic electroluminescent device according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in the manner commonly used according to the prior art. A person skilled in the art will therefore be able to use all materials known about organic electroluminescent elements in combination with the emitting layer according to the invention without inventive effort.

[0066] Furthermore, preference is given to organic electroluminescent devices in which one or more layers are applied by means of a sublimation process, wherein the organic electroluminescent devices are deposited in a vacuum sublimation apparatus at temperatures below 10 -5 Pa, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 Pa. However, the initial pressure may also be even lower, for example below 10 -7 pa.

[0067] Likewise preferred is an organic electroluminescent device in which one or more layers are applied by means of an organic vapor phase deposition method or by means of carrier gas sublimation, wherein at 10 -5 The material is applied at a pressure of between 1000 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.

[0068] In addition, organic electroluminescent devices are preferred in which one or more layers are produced from solution, for example by spin coating, or by any desired printing method, for example screen printing, flexographic printing, lithography, photoinduced thermography, thermal transfer, inkjet printing or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution of the compounds of formula I. 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.

[0069] These methods are generally known to those skilled in the art, and they can apply them to organic electroluminescent elements comprising the compounds according to the invention without inventive step.

[0070] The present invention therefore also relates to a method for producing an organic electroluminescent device according to the invention, which applies at least one layer by means of a sublimation method and / or applies at least one layer by means of an organic vapor phase deposition method or by means of carrier gas sublimation and / or applies at least one layer from a solution by spin coating or by means of a printing method.

[0071] In addition, the present invention relates to compounds according to the invention comprising at least one indicated above. The same preferences as indicated above for organic electroluminescent devices apply to the compounds according to the invention. In particular, the compounds may also preferably comprise other compounds. Processing the compounds according to the invention from the liquid phase, for example by spin coating or by a printing method, requires formulations of the compounds according to the invention. These formulations may, for example, be solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fennel, 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, α-terpenes The solvents include 1,4-diisopropylbenzene, 2,4-diisopropylnaphthalene ...

[0072] Furthermore, the organic layer is selected from one or more of an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer and a light-emitting layer.

[0073] Furthermore, the electron transport layer and the light-emitting layer contain the organic electroluminescent compound of the present invention.

[0074] Furthermore, the light-emitting layer includes a dopant and a light-emitting host, and the dopant includes anthracene, naphthalene, anthracene, pyrene, perylene, phenanthrene, fluoranthene, , benzanthracene, fluorene, spirofluorene and pentacene and their derivatives or compounds containing boron atoms, in addition, various metal complexes, bisphenylenebenzene derivatives, oxazole derivatives, polyparaphenylenevinylene derivatives, heterocyclic compounds having an indole ring as a partial structure of the condensed ring, heterocyclic compounds having a carbazole ring as a partial structure of the condensed ring, carbazole derivatives, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, etc. In addition, as dopant materials, in addition to these, pyrene derivatives having a pyrene skeleton in the molecule, heterocyclic compounds having an indole ring as a partial structure of the condensed ring, heterocyclic compounds having a carbazole ring as a partial structure of the condensed ring, carbazole derivatives, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, quinacridone, coumarin, rubrene, perylene and their derivatives, benzopyran derivatives, indenophenanthrene derivatives, rhodamine derivatives, aminostyryl derivatives, etc. can also be used. They may be formed into a single film or a single layer formed by mixing with other materials, or may have a laminated structure between layers formed into a single film, between layers formed into a mixed film, or between layers formed into a single film and layers formed into a mixed film.

[0075] In addition, phosphorescent light emitters can also be used as dopants. As phosphorescent light emitters, phosphorescent light emitters of metal complexes such as iridium and platinum can be used. Green phosphorescent light emitters such as Ir(ppy)3, blue phosphorescent light emitters such as Firpic and Fir6, red phosphorescent light emitters such as Btp2Ir(acac), etc. can be used. As the main material at this time, it is preferred to use the organic electroluminescent compound of the present invention. In addition, as a main material for hole injection and transport, carbazole derivatives such as 4,4'-di(N-carbazolyl)biphenyl (CBP), TCTA, and mCP can be used. As a main material for electron transport, para-bis(triphenylsilyl)benzene (UGH2), 2,2',2"-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (TPBI), etc. can be used, and high-performance light-emitting elements can be produced.

[0076] In order to avoid concentration quenching, the phosphorescent light-emitting material is preferably doped into the host material by co-evaporation in a range of 1 to 10 wt % based on the entire light-emitting layer.

[0077] In addition, as the light-emitting doping material, a material that emits delayed fluorescence, such as PIC-TRZ, CC2TA, PXZ-TRZ, or CDCB derivatives such as 4CzIPN, may be used.

[0078] Furthermore, the mass ratio of the dopant to the light-emitting host is 1:99 to 50:50.

[0079] A consumer product made from the organic electroluminescent device, wherein the consumer product comprises the organic electroluminescent device provided by the present invention.

[0080] The consumer product described in the present invention can be one of the following products: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cellular phones, tablet computers, tablet phones, 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 reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, light therapy devices and signage.

[0081] Unless otherwise specified, the raw materials used in the present invention can be obtained commercially. Any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0082] Compared with the prior art, the present invention has the following beneficial effects:

[0083] The organic electroluminescent compound of the present invention has a large planar conjugated Ar 1 The organic electroluminescent compound represented by the general formula (I) of the present invention has the following characteristics: (1) large carrier mobility; (2) high internal quantum efficiency; (3) stable thin film state; and (4) excellent heat resistance. Therefore, it is suitable for use as a constituent material of the light-emitting layer of the organic electroluminescent element of the present invention.

[0084] As for the organic electroluminescent element of the present invention which uses the organic electroluminescent compound represented by the above-mentioned general formula (I) of the present invention as the main material of the light-emitting layer, since a compound having a larger carrier mobility than previous materials, a high internal quantum efficiency, excellent amorphous properties and a stable thin film state is used, it is possible to realize an organic electroluminescent element with high efficiency, low driving voltage and long life.

[0085] Furthermore, in the present invention, the light-emitting layer is formed by using the organic electroluminescent compound of the general formula (I), so that the high quantum efficiency and heat resistance of the compound can be effectively utilized to the maximum extent, and an organic electroluminescent element with higher efficiency and longer life can be realized.

[0086] In addition, in the present invention, for the organic electroluminescent element of the present invention which uses the organic electroluminescent compound represented by the above-mentioned general formula (I) as its constituent material in at least any layer of the above-mentioned light-emitting layer or a stacked film configured with two or more light-emitting layers, since a compound having high carrier mobility, high internal quantum efficiency and excellent amorphous property and stable thin film state is used, it is possible to realize an organic electroluminescent element with high efficiency, low driving voltage and long life. BRIEF DESCRIPTION OF THE DRAWINGS

[0087] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0088] Figure 1 A schematic diagram of an organic light-emitting device 100 is shown. The illustration is not necessarily drawn to scale. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 may be manufactured by depositing the described layers in order.

[0089] Figure 2 Schematic diagram of an organic light-emitting device 200 showing two light-emitting layers. The device includes a substrate 201, an anode 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 213. The device 200 can be prepared by depositing the described layers in sequence. Because the most common OLED device has one light-emitting layer, and the device 200 has a first light-emitting layer and a second light-emitting layer, the light emission peaks of the first light-emitting layer and the second light-emitting layer can be overlapping, cross-overlapping, or non-overlapping. In the corresponding layers of the device 200, materials similar to those described with respect to the device 100 can be used. Figure 2 One example is provided of how some layers may be added from the structure of device 100 . DETAILED DESCRIPTION

[0090] 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. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0091] In the present invention, the preparation methods are conventional methods unless otherwise specified. The raw materials used can be obtained from public commercial channels unless otherwise specified, and the percentages are mass percentages unless otherwise specified. In the series of novel organic compounds provided by the present invention, all reactions are carried out under well-known suitable conditions, and some involve simple organic preparations, such as the preparation of phenylboronic acid derivatives, which can be synthesized by skilled operation skills and are not described in detail in the present invention.

[0092] The test instruments and methods for testing the performance of OLED materials and components in the following embodiments are as follows:

[0093] OLED component performance testing conditions:

[0094] Brightness and chromaticity coordinates: tested using a spectral scanner PhotoResearch PR-715;

[0095] Current density and lighting voltage: tested using Keithley 2420 digital source meter;

[0096] Power efficiency: tested using NEWPORT 1931-C;

[0097] Life test: Use LTS-1004AC life test device.

[0098] Example 1

[0099] The preparation method of compound CJHB950 comprises the following steps:

[0100] Step 1: Preparation of compound Int-1

[0101]

[0102] Under nitrogen protection, 90.0 mmol of 1,8-dibromonaphthalene, 100.0 mmol of 2-hydroxy-1-naphthaleneboric acid and 300 mL of toluene were mixed, 117.0 mmol of anhydrous sodium carbonate and 1.0 g of Pd(PPh3)4 catalyst were added, and then 100 mL of ethanol and 50 mL of water were added. The temperature was raised to reflux and stirred for reaction for 10 hours. The mixture was cooled to room temperature, 100 mL of water was added, the organic phase was separated, the aqueous phase was extracted with toluene, the organic phase was concentrated under reduced pressure, 100 mL of methanol was added, stirred and filtered to obtain Int-1 as a yellow solid. The yield was 76%.

[0103] Step 2: Preparation of compound Int-2

[0104]

[0105] Take 55.0 mmol of the intermediate Int-1 prepared in the first step and dissolve it in 300 mL of DMF. Under nitrogen protection, add 82.5 mmol of anhydrous potassium carbonate, raise the temperature to 120°C, stir and react for 15 hours, cool to room temperature, pour the reaction solution into 1500 mL of water, extract with ethyl acetate, collect the organic phase, dry and filter, concentrate the filtrate under reduced pressure, and separate and purify it with a silica gel column to obtain Int-2 as a yellow solid. Yield: 82%.

[0106] Step 3: Preparation of compound Int-3

[0107]

[0108] Under nitrogen protection, 40.0 mmol of intermediate Int-2 was dissolved in 120 mL of THF, cooled to 0°C in an ice bath, 40.0 mmol of N-bromosuccinimide was added in batches, stirred for 5 hours, 50 mL of saturated sodium thiosulfate aqueous solution was added, extracted with ethyl acetate, the organic phase was collected, dried and filtered, the filtrate was concentrated under reduced pressure, and recrystallized with toluene and ethanol to obtain Int-3 as a yellow solid. The yield was 92%.

[0109] Step 4: Preparation of Compound A1

[0110]

[0111] Under nitrogen protection, 20.0 mmol of intermediate Int-3 was dissolved in 60 mL of DMF, and 24.0 mmol of bipyralidin, 30.0 mmol of anhydrous potassium acetate and 0.2 mmol of PdCl2 (dppf) were added. The temperature was raised to 90°C and stirred for reaction for 10 hours. The mixture was cooled to room temperature and poured into 150 mL of ice water. The mixture was extracted with ethyl acetate, and the organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure. The mixture was separated and purified by silica gel column to obtain intermediate A1 with a yield of 87%.

[0112] According to the above-mentioned synthesis method, the following compounds were prepared:

[0113]

[0114]

[0115] Step 5: Preparation of compound CJHB950

[0116]

[0117] Under nitrogen protection, 24.0 mmol of A1, 20.0 mmol of 9-bromo-10-phenylanthracene-d8 and 80 mL of toluene were mixed, 40.0 mmol of anhydrous sodium carbonate and 5.0 mg of Pd132 catalyst were added, and then 40 mL of ethanol and 40 mL of water were added. The temperature was raised to reflux and stirred for reaction for 10 hours, cooled to room temperature, 50 mL of water was added, the organic phase was separated, the aqueous phase was extracted with toluene, the organic phase was concentrated under reduced pressure, and recrystallized from toluene / THF to obtain compound CJHB950 as a light yellow solid. The yield was 74%, MS (TOF): m / z 529.23 [M+H] + .

[0118] According to the above-mentioned synthesis method, the following compounds were prepared:

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] Example 2

[0129] The preparation of compound CJHB1073 comprises the following steps:

[0130] Step 1: Preparation of compound Int-4

[0131]

[0132] Take 15.0 mmol of m-bromochlorobenzene and mix it with 60 mL of toluene. Under nitrogen protection, add 18.0 mmol of 3-methoxy-2-naphthaleneboric acid, 54.0 mmol of anhydrous sodium carbonate and 173.0 mg of Pd(PPh3)4 catalyst, then add 30 mL of ethanol and 30 mL of water, heat to reflux and stir to react for 12 hours, cool to room temperature, filter, wash the filter cake with water and ethanol, and separate and purify it with silica gel column to obtain compound Int-4 as a white solid. Yield: 78%.

[0133] Step 2: Preparation of compound Int-5

[0134]

[0135] Under nitrogen protection, 20.0 mmol of Int-4 was dissolved in 80 mL of dichloromethane, cooled to 0°C, 30.0 mmol of boron tribromide was added dropwise, and the reaction was stirred for 2 hours. 100 mL of water and 20 mL of ethanol were added, the organic phase was separated, dried, filtered, and the filtrate was concentrated under reduced pressure. It was separated and purified by silica gel column to obtain compound Int-5 as a white solid. The yield was 98%.

[0136] Step 3: Preparation of compound Int-6

[0137]

[0138] Under nitrogen protection, 20.0 mmol of Int-5 was dissolved in 150 mL of carbon tetrachloride, cooled to 0°C, 21.0 mmol of N-bromosuccinimide was added in batches, the temperature was raised to room temperature and stirred for 3 hours, 50 mL of saturated sodium thiosulfate aqueous solution was added, the organic phase was separated, dried, filtered, and the filtrate was concentrated under reduced pressure and purified by silica gel column to obtain compound Int-6 as a white solid. The yield was 92%.

[0139] Step 4: Preparation of compound Int-7

[0140]

[0141] Under nitrogen protection, 20.0 mmol of Int-6 was dissolved in 60 mL of dry THF, cooled to -78°C with liquid nitrogen, and 42.0 mmol of 2.5 M n-butyl lithium n-hexane solution was added dropwise. The reaction was stirred for half an hour, and 30.0 mmol of trimethyl borate was added dropwise. The temperature was raised to room temperature and stirred for 1 hour. 50 mL of 3 M dilute hydrochloric acid aqueous solution was added dropwise, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was dried, filtered, and the filtrate was concentrated under reduced pressure, dispersed with n-hexane, and filtered to obtain compound Int-7 as a white solid. The yield was 85%.

[0142] Step 5: Preparation of compound Int-8

[0143]

[0144] Referring to the synthesis method of the first step of Example 1, only the 2-hydroxy-1-naphthaleneboric acid in the first step of Example 1 was replaced by Int-7 to prepare compound Int-8 as a yellow solid with a yield of 71%.

[0145] Step 6: Preparation of compound Int-9

[0146]

[0147] Referring to the synthesis method of the second step of Example 1, only Int-1 in the second step of Example 1 was replaced by Int-8 to prepare compound Int-9 as a yellow solid with a yield of 80%.

[0148] Step 7: Preparation of Compound A11

[0149]

[0150] Referring to the synthesis method of the fourth step of Example 1, only Int-3 in the fourth step of Example 1 was replaced by Int-9 to prepare compound A11 as a yellow solid with a yield of 83%.

[0151] According to the above-mentioned synthesis method, the following compounds were prepared:

[0152]

[0153]

[0154]

[0155] Step 8: Preparation of compound CJHB1073

[0156]

[0157] Referring to the synthesis method of the fifth step of Example 1, A1 in the fifth step of Example 1 was replaced by A11, and 9-bromo-10-phenylanthracene-d8 was replaced by 9-bromo-10-(2-naphthyl)anthracene-d8 to prepare compound CJHB1073, light yellow solid, yield: 72%, MS (TOF): m / z 655.29 [M+H] + .

[0158] According to the above-mentioned synthesis method, the following compounds were prepared:

[0159]

[0160]

[0161]

[0162] Example 3

[0163] An OLED element, such as Figure 1 As shown, the preparation method of the OLED element comprises the following steps:

[0164] 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 an ultraviolet cleaning machine for 10 minutes, and bombarded with a low-energy cation beam.

[0165] 2) Place the treated ITO glass substrate in a vacuum chamber and evacuate the chamber to a vacuum of less than 1×10 -5 Pa, and silver is evaporated on the above ITO film as an anode, and the thickness of the evaporated film is Continue to evaporate the compounds DNTPD and F4TCNQ as the hole injection layer, F4TCNQ is 3% of the mass of DNTPD, and the evaporated film thickness is NPD is continuously evaporated on the hole injection layer to form a hole transport layer with a thickness of

[0166] 3) Continue to evaporate a layer of compound HT202 on the hole transport layer as an electron blocking layer, and the evaporated film thickness is

[0167] 4) A layer of the compound represented by formula (I) of the present invention and BD025 is continuously evaporated on the electron blocking layer as an organic light-emitting layer, wherein BD025 is a doping material and the compound represented by formula (I) of the present invention is a main material, the doping concentration of the compound represented by formula (I) in BD025 is 8%, and the evaporated film thickness is

[0168] 5) A layer of compound LiQ and ET210 is further evaporated on the above-mentioned light-emitting layer as the electron transport layer of the device, wherein the mass ratio of LiQ to ET210 is 1:1, and the evaporated film thickness is

[0169] 6) A layer of compound LiF is further evaporated on the above electron transport layer as the electron injection layer of the device, and the evaporated film thickness is Finally, magnesium and silver were evaporated on the electron injection layer as the cathode layer of the element. The mass ratio of magnesium to silver was 1:10 and the thickness of the evaporated film was

[0170] The structure of the compound used in the above Example 3 is as follows:

[0171]

[0172] Comparative Example 1

[0173] The same steps as in Example 3 were followed, except that compound B01 was used instead of the compound represented by formula (I). The structure of compound B01 is:

[0174]

[0175] At the same brightness, a digital source meter and a brightness meter were used to measure the driving voltage and current efficiency of the organic electroluminescent elements prepared in Example 3 and Comparative Example 1, as well as the life of the elements. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent element was measured when it reached 1000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the LT90% life test is as follows: use a brightness meter at 1000cd / m 2 At the same brightness, the current is kept constant and the brightness decay of the organic electroluminescent element is measured to be 900cd / m 2 All results are summarized in Table 1, and all results are reported as relative values ​​standardized with respect to the results of Comparative Example 1.

[0176] Table 1 Performance test results of each component

[0177]

[0178]

[0179]

[0180]

[0181] As can be seen from Table 1, the compound of the present invention is used as a blue light material to obtain a blue light organic electroluminescent element, the driving voltage of the element is reduced, the current efficiency is improved, and the LT90% life is also well improved.

[0182] The difference between the compound B01 in Comparative Example 1 and the compound of the present invention is that the planar conjugation ability of oxa-dibenzoanthracene is weak, the transmission of holes and electrons is unbalanced, and its ability to accept holes is stronger than its ability to accept electrons. This unbalanced transmission affects the formation of excitons in the light-emitting layer, resulting in high voltage, low efficiency, and reduced lifespan. The compound of the present invention has a large conjugated and non-planar structure of oxa-dibenzoanthracene, which reduces the formation of anthracene derivative fluorescent molecular excimers, so it has excellent performance in molecular film formation and charge transmission, the charge transmission in the element is more balanced, and the element performance is improved.

[0183] The organic electroluminescent device of the present invention can be used in planar light emitters of wall-mounted televisions, flat-panel displays, lighting, etc., backlight sources of copiers, printers, liquid crystal displays, light sources of measuring instruments, etc., display panels, sign lights, etc.

[0184] 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 by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. An organic electroluminescent compound, characterized in that: The compound is selected from one of the following structures: The hydrogen atoms in the above formulae may be partially or completely replaced by deuterium.

2. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises the organic electroluminescent compound according to claim 1.

3. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises 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 organic electroluminescent compound according to claim 1.

4. The organic electroluminescent device according to claim 3, characterized in that: The organic electroluminescent compound is contained in the light-emitting layer.

5. A consumer product, characterized in that: The organic electroluminescent device according to claim 3 is included.

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