Anthracene derivative, organic electroluminescent material, light-emitting device and consumer product

Abstract

The present invention belongs to the technical field of organic electroluminescence, and specifically relates to an anthracene derivative, an organic electroluminescent material, a light-emitting device and a consumer product. The anthracene derivative of the present invention is a novel organic electroluminescent compound having a seven-membered ring planar structure formed by anthracene, benzofuran, benzothiophene and the like. The seven-membered ring anthracene derivative increases molecular steric hindrance, hinders the formation of exciplexes between organic molecules, improves internal quantum efficiency, and has a shorter emission wavelength than existing compounds, thereby improving the efficiency and life of an organic electroluminescent device containing the compound; in addition, the compound improves solubility in a solution and solves the productivity and cost problems of a process previously possessed by blue light materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescence, and in particular relates to an anthracene derivative, 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 their uses, 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 those that meet the following characteristics:

[0003] First, the materials used in organic electroluminescent elements need to have 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, so when driven, 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 materials 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 anthracene derivative, an organic electroluminescent material, a light-emitting device and a consumer product. The anthracene derivative of the present invention emits blue to dark blue light and has high luminous efficiency.

[0007] The first object of the present invention is to provide an anthracene derivative.

[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 anthracene derivative, the general structural formula of the anthracene derivative is shown in formula (I):

[0013]

[0014] Wherein, X is selected from O, S, SiR 5 R 6 or CR 5 R 6 ;

[0015] R 1 ~R 6 are independently selected from hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C3~C 30 Cycloalkyl, substituted or unsubstituted C2~C 60 Heteroaryl, substituted or unsubstituted C1~C 30 Alkoxy, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C1~C 30 Alkylthio, substituted or unsubstituted C6~C 60 Arylthio, substituted or unsubstituted C1~C 30 Alkylamino, substituted or unsubstituted C6~C 60 Arylamine, substituted or unsubstituted C1~C 30 Alkylsilyl, substituted or unsubstituted C6~C 60 The group consisting of arylsilyl groups;

[0016] Ar 1Selected from hydrogen, deuterium, cyano, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C6~C 60 Arylamine, substituted or unsubstituted C2~C 60 The group consisting of heteroaryl;

[0017] R 1 , R 2 , R 3 , R 4 Each independently represents one or more substitutions to saturation.

[0018] The alkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a straight chain or branched saturated hydrocarbon having a carbon number of 1 to 30. Non-limiting examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, etc.;

[0019] The heteroalkyl group of the present invention refers to a hydrogen atom or -CH2- on the alkyl group substituted 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 refers to a hydrogen atom on the alkyl group partially or fully substituted by halogen, as non-limiting examples, there are fluorotoluene, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, trifluoroethyl, pentafluoroethyl, etc.

[0020] The alkenyl or alkynyl groups according to the invention contain at least two carbon atoms and are preferably taken, as non-limiting examples, to mean cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

[0021] The alkoxy or alkylthio groups of the present invention, preferably alkoxy or alkylthio groups having 1 to 30 carbon atoms, 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

[0022] Generally speaking, the cycloalkyl and cycloalkenyl groups of 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, and 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.

[0023] The alkylsilyl used in the present invention refers to a silyl group substituted by an alkyl group having 1 to 30 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.

[0024] The arylalkyl group of the present invention refers to an alkyl group in which at least one hydrogen atom of a straight-chain or branched saturated hydrocarbon having 1 to 30 carbon atoms is substituted by an aryl group having 6 to 60 carbon atoms, and non-limiting examples thereof include phenylmethyl, diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, and the like.

[0025] The alkylaryl group of 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 30 carbon atoms. Non-limiting examples thereof include methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl, isopropylphenyl, and the like.

[0026] The aryl group 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 may be attached to each other simply or in a condensed form, and further, may 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, phenanthrolinyl, 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.

[0027] The aryloxy group used in the present invention refers to R'O - The monovalent functional group represented by is an aryl group having a carbon number of 6 to 60. Non-limiting examples of such an aryloxy group include phenoxy, naphthoxy, biphenyloxy and the like.

[0028] The arylthio group used in the present invention refers to R"S -The monovalent functional group represented by is an aryl group having 6 to 60 carbon atoms. Non-limiting examples of such an arylthio group include phenylthio, naphthylthio, biphenylthio and the like.

[0029] The substituents of the substituted alkyl, substituted aryl, substituted heteroaryl, and substituted arylamine described in the present invention are each 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-C 40 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 boron carbonyl, C6-C 60 Aryl (C1-C 40 ) alkyl, and C1-C 40 Alkyl (C6-C 60 )aryl.

[0030] The alkylamino group used in the present invention refers to an amino group substituted by an alkyl group having 1 to 40 carbon atoms, or an amino group substituted by two alkyl groups having 1 to 40 carbon atoms. Non-limiting examples of the alkylamino group include methylamino, dimethylamino, ethylamino, diethylamino, and the like.

[0031] The arylamino group used in the present invention refers to an amino group substituted by an aryl group having 6 to 60 carbon atoms, or an amino group substituted by two aryl groups having 6 to 60 carbon atoms. Non-limiting examples of the arylamino group include anilino, diphenylamino, 1-naphthylamino, 2-naphthylamino, N-phenylnaphthalene-1-amino, carbazole, phenoxazine, and the like.

[0032] The alkylsilyl group 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 a methylsilyl group substituted by at least one aryl group having 6 to 60 carbon atoms, and non-limiting examples include phenyldimethylsilyl, naphthyldimethylsilyl, diphenylmethylsilyl, and the like.

[0033] The "halogen" or "halogen atom" used in the present invention refers to a group selected from fluorine, chlorine, bromine or iodine.

[0034] Furthermore, the heteroaryl group is a group consisting of the groups shown in II-1 to II-17, and the specific structures of II-1 to II-17 are as follows:

[0035]

[0036] wherein Z1 and Z2 are each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidine, hydrazine, hydrazone, carboxyl or its carboxylate, sulfonic acid or its sulfonate, phosphate or its phosphate, C1-C 40 Alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C1-C 40 Alkoxy, C3-C 40 Cycloalkyl, C3-C 40 Cycloalkenyl, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Aryloxy, substituted or unsubstituted C6-C 60 aryl thioether group, or substituted or unsubstituted C2-C 60 The group consisting of heteroaryl;

[0037] x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5; T1 represents an oxygen atom or a sulfur atom; It represents the bond connecting the substituent to the main structure.

[0038] 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 can be combined to form partially or fully deuterated alkyl; halogen and alkyl can be combined to form haloalkyl substituents, such as trifluoromethyl, etc.; and halogen, alkyl and aryl can be combined to form haloaralkyl.

[0039] Furthermore, the R 1 ~R 4 each of which is identically or differently selected from hydrogen, deuterium, cyano, methyl, ethyl, isopropyl, isobutyl, tert-butyl, 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 peryl, a substituted or unsubstituted fluoranyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothiophene, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, and a substituted or unsubstituted triazinyl.

[0040] Furthermore, the R 5 , R 6 Each is identically or differently selected from the group consisting of hydrogen, deuterium, methyl, substituted or unsubstituted phenyl, and substituted or unsubstituted fluorenyl.

[0041] Furthermore, the Ar 1 selected from hydrogen, deuterium, cyano, 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 peryl, a substituted or unsubstituted fluoranyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothiophene, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, and a substituted or unsubstituted triazinyl.

[0042] Preferably, the R 1 ~R 4 Each is identically or differently selected from the group consisting of hydrogen, deuterium, tert-butyl, and substituted or unsubstituted phenyl.

[0043] Preferably, the R 5 , R 6 Each of the above groups is identically or differently selected from the group consisting of a methyl group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted fluorenyl group.

[0044] Preferably, the Ar 1 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 peryl, a substituted or unsubstituted fluoranyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothiophene, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, and a substituted or unsubstituted triazinyl.

[0045] Furthermore, the anthracene derivative is one of the following structures D751 to D879:

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054] wherein X is selected from O, S, C(CH3)2, C(Ph)2 or 9,9-fluorenyl;

[0055] Preferably, X is selected from O or S;

[0056] The hydrogen atoms in the structure may be partially or completely replaced by deuterium.

[0057] An organic electroluminescent material comprises the anthracene derivative.

[0058] The organic electroluminescent material may be composed of the compound of the present invention alone or may contain other compounds simultaneously.

[0059] 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 light refraction layer material.

[0060] An organic electroluminescent device comprises an organic electroluminescent element, wherein the organic electroluminescent element 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 an anthracene derivative provided by the invention.

[0061] Generally speaking, an organic electroluminescent device comprises at least one organic layer disposed between an anode and a cathode and electrically connected to the anode and the cathode. With respect to the organic electroluminescent element of the present invention, in addition to one or more of the organic layers comprising the anthracene derivatives described above, the organic layers and electrodes can be formed using materials and methods known in the art.

[0062] In addition, the material that can be used as the anode contained in the organic electroluminescent element of the present invention is not particularly limited. As non-limiting examples, metals such as vanadium, chromium, copper, zinc, gold, aluminum, or their alloys can be used; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole and polyaniline; and carbon black, etc. The material that can be used as the cathode contained in the organic electroluminescent element of the present invention is not particularly limited. As non-limiting examples, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead, or their alloys can be used; and multilayer structure materials such as LiF / Al or Li2O / Al can be used. The material that can be used as the substrate included in the organic electroluminescent element of the present invention is not particularly limited, and non-limiting examples thereof include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets, and the like.

[0063] 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.

[0064] Likewise preferred is an organic electroluminescent arrangement 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.

[0065] 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.

[0066] These methods are generally known to those skilled in the art and they can apply them to organic electroluminescent elements comprising the compounds of the invention without inventive step. Therefore, the present invention also relates to a method for producing an organic electroluminescent device of 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 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.

[0067] In addition, the present invention relates to compounds of the present invention comprising at least one indicated above. The same preferences as indicated above for organic electroluminescent devices apply to the compounds of the present invention. In particular, the compounds may also preferably comprise other compounds. Processing the compounds of the present invention from the liquid phase, for example by spin coating or by a printing method, requires formulations of the compounds of the present 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 benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, 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, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or a mixture of these solvents.

[0068] 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.

[0069] Furthermore, the electron transport layer and / or the light-emitting layer comprises the anthracene derivative of the present invention.

[0070] Furthermore, the light-emitting layer comprises the anthracene derivative of the present invention.

[0071] Furthermore, the light-emitting layer includes a dopant and a light-emitting host, and the dopant includes anthracene, naphthalene, anthracene, pyrene, perylene, phenanthrene, fluoranthene, The group consisting of 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.

[0072] 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.

[0073] In order to avoid concentration quenching, the phosphorescent light emitter is preferably doped into the host material by co-evaporation in a range of 1 to 10% by weight relative to the light-emitting layer.

[0074] In addition, as the light-emitting doping material, 2-biphenyl-4,6-bis(12-phenylindole[2,3-a]carbazole-11-yl)-1,3,5-triazine (PIC-TRZ), 9,9″-(6-phenyl-1,3,5-triazine-2,4-diyl)bis((9H-3,9′-dicarbazole))(CC2TA), 10-(4-(4,6-diphenyl L-1,3,5-triazine-2-yl)phenyl)-10-hydrogen-phenoxazine (PXZ-TRZ), 2,4,5,6-tetrakis(9-carbazole) Materials that emit delayed fluorescence include triazine derivatives such as 2,12-di-tert-butyl-5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene-7-yl)-10H-spiro[acridine-9,9′-fluorene] (TDBA-SAF), and 2,12-di-tert-butyl-5,9-bis(4-(tert-butyl)phenyl)-5,9-dihydro-5,9-diaza-13b-boronaphtho[3,2,1-de]anthracene (PDBA), or compounds containing boron-oxygen, boron-nitrogen, etc.

[0075] Furthermore, the light-emitting host comprises the anthracene derivative of the present invention.

[0076] Furthermore, the mass ratio of the dopant to the light-emitting host is 1:99 to 50:50.

[0077] A consumer product made of the organic electroluminescent device, the consumer product comprising the organic electroluminescent device provided by the present invention. The consumer product described in the present invention can be one of the following products: a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a lamp for internal or external lighting and / or signaling, a head-up display, a fully transparent or partially transparent display, a flexible display, a laser printer, a telephone, a cellular phone, a tablet computer, a tablet phone, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, a viewfinder, a microdisplay with a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] The anthracene derivatives of the present invention are novel organic electroluminescent compounds having a seven-membered ring planar structure formed by anthracene, benzofuran, benzothiophene, etc. The seven-membered ring anthracene derivatives increase the conjugated area and steric hindrance of the anthracene molecule, hinder the formation of exciplexes between organic molecules, improve the internal quantum efficiency, and have a shorter emission wavelength than existing compounds, thereby improving the efficiency and life of the organic electroluminescent device containing the compound; in addition, the compound improves the solubility in the solution and solves the productivity and cost problems of the process of the previous blue light material.

[0080] The anthracene derivatives described in the present invention have a novel rigid structure of a large planar conjugated benzofuran, benzothiophene or indenothracene. As for the compounds represented by the general formula (I) of the present invention, they have the following characteristics: (1) large carrier mobility; (2) high internal quantum efficiency; (3) stable thin film state; and (4) excellent heat resistance. Therefore, they are suitable for use as constituent materials of the light-emitting layer of organic electroluminescent elements.

[0081] As for the organic electroluminescent element using the anthracene derivative represented by the above-mentioned general formula (I) of the present invention as the main material of the light-emitting layer, compared with previous materials, the carrier mobility of the compound of the present invention is large, the internal quantum efficiency is high, the amorphous property is excellent, and the thin film state is stable. Therefore, the organic electroluminescent element can achieve high efficiency, low driving voltage and long life.

[0082] Furthermore, in the present invention, by forming a light-emitting layer with the anthracene derivative of the general formula (I), the high quantum efficiency and heat resistance of the compound can be utilized to the maximum extent, and an organic electroluminescent element with higher efficiency and longer life can be realized.

[0083] In addition, in the present invention, with respect to the organic electroluminescent element, since the anthracene derivative represented by the above-mentioned general formula (I) is used as its constituent material in its light-emitting layer, or in at least any one layer of a stacked film having two or more light-emitting layers, based on the high carrier mobility, high internal quantum efficiency, excellent amorphous property, and thin film state stability of the compound, an organic electroluminescent element with high efficiency, low driving voltage, and long life can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0085] Figure 1One of the structural schematic diagrams of the organic electroluminescent element provided by the present invention;

[0086] Figure 2 The second structural schematic diagram of the organic electroluminescent element provided by the present invention;

[0087] Among them, 101-substrate, 102-anode, 103-hole injection layer, 104-hole transport layer, 105-electron blocking layer, 106-light-emitting layer, 107-hole blocking layer, 108-electron transport layer, 109-electron injection layer, 110-cathode, 111-capping layer, 112-charge generation layer. DETAILED DESCRIPTION

[0088] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the drawings of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0089] 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 N,N-diphenylamine derivatives, which can be synthesized by skilled operation skills and are not described in detail in the present invention.

[0090] The test instruments and methods for testing the performance of OLED materials and components in the following embodiments are as follows:

[0091] OLED component performance testing conditions:

[0092] Brightness and chromaticity coordinates: tested using a spectral scanner PhotoResearch PR-715;

[0093] Current density and lighting voltage: tested using Keithley 2420 digital source meter;

[0094] Power efficiency: tested using NEWPORT 1931-C;

[0095] Life test: Use LTS-1004AC life test device.

[0096] Example 1

[0097] The preparation method of compound D778 comprises the following steps:

[0098] Step 1: Preparation of Compound Int.-1

[0099]

[0100] Under nitrogen protection, 20.0 mmol of 1-bromodibenzo[b,d]furan or 1-bromodibenzo[b,d]thiophene or 4-bromo-9,9-dimethylfluorene was dissolved in 80 mL of dry THF, cooled to -78°C with liquid nitrogen, and 22.0 mmol of 2.5 M n-butyllithium n-hexane solution was added dropwise. The mixture was stirred for 30 minutes, and then 22.0 mmol of 2,6-dibromo-N,N-dimethylbenzamide was added dropwise in THF. The mixture was heated to room temperature and stirred for 1 hour. 50 mL of saturated aqueous ammonium chloride solution was added dropwise, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure to dryness. The intermediate Int.-1 was obtained with a yield of 80% to 85%.

[0101] Step 2: Preparation of Compound Int.-2

[0102]

[0103] Under nitrogen protection, 30.0 mmol of the intermediate Int.-1 prepared in the previous step was dissolved in 60 mL of pyridine, and 0.15 mol of 85% potassium hydroxide was added. The temperature was raised to 150°C and stirred for reaction for 5 hours. The temperature was cooled to room temperature, and the reaction solution was poured into 150 mL of ice water and filtered. The filter cake was washed with water and then separated and purified by silica gel column to obtain compound Int.-2 with a yield of 65% to 70%.

[0104] Step 3: Preparation of Compound Int.-3

[0105]

[0106] Under nitrogen protection, 40.0 mmol of Int.-2 was dissolved in 100 mL of dry THF, cooled to 0°C, and 44.0 mmol of phenylmagnesium bromide THF solution was added dropwise. The reaction was stirred for 30 minutes, and the mixture was heated to room temperature and stirred for 1 hour. 50 mL of 2N dilute hydrochloric acid aqueous solution was added, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure. The intermediate Int.-3 was obtained with a yield of 85% to 90%.

[0107] Step 4: Preparation of Compound Int.-4

[0108]

[0109] Under nitrogen protection, 40.0 mmol of Int.-3 was dissolved in 100 mL of dichloromethane, 80.0 mmol of triethylsilane was added, the temperature was lowered to 0°C, 30 mL of trifluoroacetic acid was slowly added dropwise, the temperature was raised to room temperature and stirred for 12 hours, 50 mL of water was added, the mixture was extracted with dichloromethane, the organic phase was collected and dried, filtered, the filtrate was concentrated under reduced pressure, and purified by silica gel column to obtain Int.-4 with a yield of 85% to 90%.

[0110] Step 5: Preparation of Compound Int.-5

[0111]

[0112] Under nitrogen protection, 40.0 mmol of intermediate Int.-4 was dissolved in 120 mL of dry THF, cooled to -78°C, 44.0 mL of 2.5 M n-butyl lithium hexane solution was added dropwise, stirred for reaction for 1 hour, 80.0 mmol of DMF was added, the temperature was raised to room temperature, stirred for reaction for 1 hour, 50 mL of 2N dilute hydrochloric acid aqueous solution was added, the organic phase was separated, the aqueous phase was extracted with dichloromethane, the organic phase was collected, dried and filtered, and the filtrate was concentrated under reduced pressure to obtain Int.-5 with a yield of 85% to 90%.

[0113] Step 6: Preparation of Compound Int.-6

[0114]

[0115] Under nitrogen protection, 40.0 mmol of intermediate Int.-5 was dissolved in 80 mL of dichloromethane, and 8.0 mmol of trifluoromethanesulfonic acid was added. The mixture was stirred at room temperature for 1 hour, concentrated to dryness under reduced pressure, and separated and purified by silica gel column to obtain intermediate Int.-6 with a yield of 90% to 95%.

[0116] Step 7: Preparation of Compound Int.-7

[0117]

[0118] 40.0mmol of the intermediate Int.-6 was dissolved in 120mL of dichloromethane, and then 4.0mmol of p-toluenesulfonic acid was added. The temperature was lowered to -20°C, and 44.0mL of NBS was added in batches. The reaction was stirred for 1 hour, and 100mL of water was added. The organic phase was separated and washed with water 3 times. The organic phase was collected, dried and filtered, and the filtrate was concentrated under reduced pressure. Purification was performed by silica gel column to obtain Int.-7 with a yield of 90% to 95%.

[0119] Step 8: Preparation of compound D778

[0120]

[0121] Under nitrogen protection, 15.0 mmol of intermediate Int.-7 (reactant 1) was mixed with 60 mL of toluene, 18.0 mmol of (3-(10-phenylanthracenyl-9-yl)phenyl)boric acid (reactant 2), 54.0 mmol of anhydrous sodium carbonate and 0.3 mg of Pd132 catalyst were added, and 30 mL of ethanol and 30 mL of water were added. The mixture was heated to reflux and stirred for reaction 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 ethanol, and separated and purified by silica gel column to obtain compound D778;

[0122] X is O, yield 76%, EI-MS / FAB, m / e: 671.23 [M+H].

[0123] X is S, yield 74%, EI-MS / FAB, m / e: 687.21 [M+H].

[0124] X is CPh2, yield 75%, EI-MS / FAB, m / e: 821.31 [M+H].

[0125] Example 2 to Example 74

[0126] According to the above-mentioned synthesis method, the following compounds were prepared:

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134] In the above embodiments, X is selected from O, S, C(CH3)2 or CPh2; wherein Ph is phenyl.

[0135] Embodiment 75

[0136] The preparation method of compound D787 comprises the following steps:

[0137] Step 1: Preparation of Compound Int.-8

[0138]

[0139] Under nitrogen protection, 20.0 mmol of Int.-7 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 temperature was cooled to room temperature, 150 mL of water was added, and the mixture was extracted with ethyl acetate. The organic phase was collected, washed with saturated brine, dried, filtered, and the filtrate was concentrated under reduced pressure. The compound Int.-8 was obtained with a yield of 80% to 85%.

[0140] Step 2: Preparation of compound D787

[0141]

[0142] 12.0 mmol of intermediate Int.-8 (reactant 1) was mixed with 60 mL of toluene, and under nitrogen protection, 10.0 mmol of 2-biphenyl-4-chloro-6-phenyl-1,3,5-triazine (reactant 2), 48.0 mmol of potassium phosphate hydrate and 1.0 mg of Pd132 catalyst were added, and then 30 mL of ethanol and 30 mL of water were added, and the temperature was raised to reflux and stirred for reaction for 12 hours, cooled to room temperature, filtered, and the filter cake was washed with water and ethanol, and separated and purified by silica gel column to obtain compound D787;

[0143] X is O; yield 73%, EI-MS / FAB, m / e: 650.22 [M+H].

[0144] X is S; yield 70%, EI-MS / FAB, m / e: 666.19 [M+H].

[0145] X is C(CH3)2; yield 74%, EI-MS / FAB, m / e: 676.27 [M+H].

[0146] Embodiment 76 to Embodiment 84

[0147] According to the above-mentioned synthesis method, the following compounds were prepared:

[0148]

[0149]

[0150] In the above embodiments, X is selected from O, S, C(CH3)2 or CPh2; wherein Ph is phenyl.

[0151] Embodiment 85

[0152] Preparation of compound D839:

[0153]

[0154] 10.0 mmol of the intermediate Int.-7 (reactant 1) was dispersed in 80 mL of toluene, and 10.0 mmol of N-([1,1′-biphenyl]-4-yl)dibenzo[b,d]furan-2-amine (reactant 2) was added, and then 20.0 mmol of sodium tert-butoxide, 0.05 mmol of Pd2(dba)3CHCl3 catalyst and 0.01 mL of 10% tri-tert-butylphosphine toluene solution were added, and the temperature was raised to 90° C. and stirred for reaction for 12 hours. After the reaction was completed, 50 mL of water was added, and the organic phase was separated. The aqueous phase was extracted with toluene-THF, and the organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure to dryness, and separated and purified by silica gel column to obtain yellow solid D839;

[0155] X is O, yield 70%, EI-MS / FAB, m / e: 676.22 [M+H].

[0156] X is S, yield 65%, EI-MS / FAB, m / e: 692.20 [M+H].

[0157] X is C(CH3)2, yield 72%, EI-MS / FAB, m / e: 702.27 [M+H].

[0158] Embodiment 86 to Embodiment 90

[0159] According to the above-mentioned synthesis method, the following compounds were prepared:

[0160]

[0161]

[0162] In the above embodiments, X is selected from O, S, C(CH3)2 or CPh2; wherein Ph is phenyl.

[0163] Embodiment 91

[0164] The preparation method of compound D842 comprises the following steps:

[0165] Step 1: Preparation of Compound Int.-10

[0166]

[0167] Under nitrogen protection, 10.0 mmol of intermediate Int.-9 (prepared according to the synthetic method of Example 1, reactant 1) was mixed with 40 mL of toluene, 12.0 mmol of phenylboric acid (reactant 2), 30.0 mmol of anhydrous potassium carbonate and 0.2 mg of Pd132 catalyst were added, and then 20 mL of water and 20 mL of ethanol were added. The temperature was raised to reflux and stirred for reaction for 12 hours, cooled to room temperature, 50 mL of water was added to dilute, extracted with toluene-THF, the organic phase was collected, dried, filtered, the filtrate was concentrated under reduced pressure, and separated and purified by silica gel column to obtain compound Int.-10 with a yield of 70% to 75%.

[0168] Step 2: Preparation of Compound Int.-11

[0169]

[0170] Referring to the synthesis method of the seventh step of Example 1, only Int.-6 in the seventh step of Example 1 was replaced by Int.-10 to prepare compound Int.-11 with a yield of 90% to 95%.

[0171] Step 3: Preparation of compound D842

[0172]

[0173] Referring to the synthesis method of step 8 of Example 1, Int.-7 in step 8 of Example 1 was replaced by Int.-11, and (3-(10-phenylanthracenyl-9-yl)phenyl)boric acid was replaced by 2-naphthaleneboric acid (reactant 3) to prepare compound D842;

[0174] X is O, yield 76%, EI-MS / FAB, m / e: 545.18 [M+H].

[0175] X is S, yield 73%, EI-MS / FAB, m / e: 561.16 [M+H].

[0176] X is CPh2, yield 74%, EI-MS / FAB, m / e: 695.27 [M+H].

[0177] Example 92 to Example 96

[0178] According to the above-mentioned synthesis method, the following compounds were prepared:

[0179]

[0180] In the above embodiments, X is selected from O, S, C(CH3)2 or CPh2; wherein Ph is phenyl.

[0181] Embodiment 97

[0182] Preparation of compound D851:

[0183]

[0184] Under nitrogen protection, 10.0 mmol of compound A2 (prepared according to the synthesis method of Example 1, except that the raw materials such as 1-bromodibenzo[b,d]furan or 1-bromodibenzo[b,d]thiophene or 4-bromo-9,9-dimethylfluorene in the first step of Example 1 are replaced with raw materials such as 1-bromonaphtho[2,3-b]benzofuran or 1-bromonaphtho[2,3-b]benzothiophene or 4-bromo-11,11-dimethylbenzo[b]fluorene) is mixed with 40 mL of toluene. Add 12.0 mmol of 2,4-diphenylbenzeneboronic acid pinacol ester, 30.0 mmol of anhydrous sodium carbonate and 0.1 mmol of Pd(PPh3)4 catalyst, then add 20 mL of water and 20 mL of ethanol, heat to reflux and stir to react for 12 hours, cool to room temperature, add 50 mL of water to dilute, extract with toluene-THF, collect the organic phase, dry, filter, concentrate the filtrate under reduced pressure, separate and purify with silica gel column to obtain compound D851;

[0185] X is O; yield 70%, EI-MS / FAB, m / e: 621.21 [M+H].

[0186] X is S; yield 66%, EI-MS / FAB, m / e: 637.19 [M+H].

[0187] X is C(CH3)2; yield 68%, EI-MS / FAB, m / e: 647.27 [M+H].

[0188] Embodiment 98 to Embodiment 129

[0189] According to the above-mentioned synthesis method, the following compounds were prepared:

[0190]

[0191]

[0192]

[0193]

[0194] In the above embodiments, X is selected from O, S, C(CH3)2 or CPh2; wherein Ph is phenyl.

[0195] Application Examples 1 to 129

[0196] An OLED element, such as Figure 1As shown, the OLED element of this embodiment is a top emitting light element, including 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 111. The OLED element omits the hole blocking layer 107, and the preparation method 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 an ultraviolet cleaning machine for 10 minutes, and bombarded with a low-energy cation beam.

[0198] 2) Place the treated ITO glass substrate (as substrate 101) in a vacuum chamber and evacuate the chamber to a pressure less than 1×10 -5 Pa, silver is evaporated on the above ITO film as the anode 102, and the evaporated film thickness is Continue to evaporate the compound HI101 and F4TCNQ as the hole injection layer 103, wherein F4TCNQ is 3% of the mass of HI101 and the evaporated film thickness is NPD is continuously evaporated on the hole injection layer to form a hole transport layer 104, and the evaporated film thickness is

[0199] 3) A layer of compound HT202 is continuously evaporated on the hole transport layer as an electron blocking layer 105, and the evaporated film thickness is

[0200] 4) On the electron blocking layer, a layer of one of the anthracene derivatives represented by D751-D879 obtained in the above-mentioned Examples 1 to 129 (e.g., Application Example 1 uses the anthracene derivative obtained in Example 1, Application Example 2 uses the anthracene derivative obtained in Example 2, and so on) and BD015 are continuously evaporated as the organic light-emitting layer 106, wherein BD015 is the doping material and the anthracene derivative is the main material, the doping concentration of BD015 in the anthracene derivative is 10%, and the evaporated film thickness is

[0201] 5) A layer of compound LiQ and ET225 is further evaporated on the above-mentioned light-emitting layer as the electron transport layer 108 of the device, wherein the mass ratio of LiQ and ET225 is 1:1, and the evaporated film thickness is

[0202] 6) A layer of compound LiF is further evaporated on the electron transport layer as the electron injection layer 109 of the device, and the evaporated film thickness is

[0203] 7) On the electron injection layer, magnesium and silver are evaporated as the transparent cathode 110 of the element, wherein the mass ratio of magnesium to silver is 2:1 and the thickness of the evaporated film is

[0204] Finally, a layer of compound NPD is evaporated on the transparent cathode as a capping layer 111, and the evaporated film thickness is

[0205] The structure of the compound used in Example 6 is as follows:

[0206]

[0207] Application Example 130

[0208] An organic electroluminescent element is a top-emitting multi-light-emitting layer element, and its structure is as follows Figure 2 As shown, the device includes a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, a light emitting layer 106 (as a first light emitting layer), an electron transport layer 108, a charge generation layer 112, a hole injection layer 103, a hole transport layer 104, a light emitting layer 106 (as a second light emitting layer), an electron transport layer 108, an electron injection layer 109, and a cathode 110. The element can be prepared by depositing the described layers in order.

[0209] Because the most common organic electroluminescent devices have a single-color light-emitting layer or three light-emitting layers of three primary colors, Figure 2 The element shown has two light-emitting layers of the same light color, and the light-emitting peaks of the first light-emitting layer and the second light-emitting layer of the element may be overlapping, cross-overlapping, or non-overlapping. Figure 2 In the corresponding layers of the elements shown, the same Figure 1 The elements shown are made of materials similar to those described. Figure 2 Provides information on how to Figure 1 The structure of the element shown is an example of adding some layers. The specific preparation method is the same as Figure 1 The OLED element shown.

[0210] Figure 1 and Figure 2The simple layered structures illustrated in are provided as non-limiting examples, and it will be appreciated that embodiments of the invention may be used in conjunction with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or several layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials different from those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it will be appreciated that combinations of materials may be used, such as a mixture of a matrix and a dopant, or more generally, a mixture. Furthermore, the layers may have various sub-layers. The names given to the various layers herein are not intended to be strictly limiting. For example, in Figure 2 In the illustrated element, hole transport layer 104 transports holes and injects holes into light emitting layer 106 and may be described as a hole transport layer or an electron blocking layer. In one embodiment, an OLED may be described as having an organic layer disposed between a cathode and an anode. This organic layer may include a single layer or may further include, for example, Figure 1 and Figure 2 Multiple layers of different organic materials are described.

[0211] Comparative Example 1

[0212] The same steps as in Application Example 1 are used, except that compound BH01 is used instead of the anthracene derivative (D751 (X: CMe2)) prepared in Example 1. The structure of compound BH01 is:

[0213]

[0214] At a current density of 10 mA / cm 2 Under the same conditions, the driving voltage, half-maximum width FWHM, current efficiency and the brightness of OLED components were measured at 1000cd / m 2 The device life under the initial conditions is LT90%, and the above data is normalized compared with Comparative Example 1. The performance test results of the obtained organic light-emitting element are shown in the following table:

[0215]

[0216]

[0217]

[0218] As can be seen from the above table, the compound of the present invention is used as the main material to obtain a blue light organic electroluminescent device. Compared with the organic electroluminescent element using BH01 as the blue light main material, the current efficiency of the element is higher (1.03-1.44), the driving voltage is lower (0.8-0.98), and the initial brightness of the device is 1000cd / m 2 Under the conditions, the LT90% life of the device has also been greatly improved (1.15~1.96), making it a main material with excellent performance.

[0219] The main difference between the anthracene derivatives of the present invention and the comparative compound BH01 is that the comparative compound BH01 has a small planar conjugation, while the anthracene derivatives of the present invention have greatly improved planar conjugation area after introducing large planar conjugated units such as dibenzofuran, dibenzothiophene or fluorene, so their molecular film-forming performance and electron transport performance are more excellent. In terms of component performance, the driving voltage is low and the efficiency is significantly improved.

[0220] 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.

[0221] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An anthracene derivative, characterized in that: The anthracene derivative is one of the following structures D751 to D879: wherein X is selected from O, S, C(CH3)2, C(Ph)2 or 9,9-fluorenyl; The hydrogen atoms in the structure may be partially or completely replaced by deuterium.

2. The anthracene derivative according to claim 1, characterized in that The X is selected from O or S.

3. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises the anthracene derivative according to claim 1 or 2.

4. 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 anthracene derivative according to claim 1 or 2.

5. The organic electroluminescent device according to claim 4, characterized in that: 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.

6. The organic electroluminescent device according to claim 5, characterized in that: The electron transport layer and the light-emitting layer contain the anthracene derivative according to claim 1 or 2.

7. The organic electroluminescent device according to claim 5, characterized in that: The light-emitting layer includes a dopant and a light-emitting host, wherein the dopant includes anthracene, naphthalene, pyrene, perylene, phenanthrene, fluoranthene, A group consisting of benzanthracene, fluorene, spirofluorene and pentacene and their derivatives; the light-emitting host comprises the anthracene derivative described in claim 1 or 2.

8. The organic electroluminescent device according to claim 7, characterized in that: The mass ratio of the dopant to the light-emitting main body is 1:99 to 50:

50.

9. A consumer product, characterized in that: An organic electroluminescent device comprising any one of claims 4 to 8.

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