A heteroaryl-based amine compound and organic electroluminescent device thereof

Abstract

The present invention provides a heteroaromatic amine compound for a covering layer, which relates to the technical field of organic optoelectronic materials. The N heterobenzo five-membered ring structure contained in the compound of the present invention has the characteristics of high refractive index, neat molecular orientation, high glass transition temperature, high thermal stability, and not easy to crystallize after being heated and cooled. After the covering layer of an OLED device is applied with the compound of the present invention, the service life and luminous efficiency of the OLED device can be effectively improved. It can be widely used in panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, signboard, signal lamp and other fields.

Description

Technical Field

[0001] The invention relates to the technical field of organic photoelectric materials, and in particular to an amine compound based on a heteroaryl group and an organic electroluminescent device thereof. Background Art

[0002] Organic electroluminescence refers to the phenomenon of using organic materials to convert electrical energy into light energy. The light emission comes from the carriers injected by the electrode. Different carriers recombine in pairs, that is, the recombination of electrons and holes, which causes light emission. In order to make organic electroluminescent elements practical, a lot of improvements have been made to the structure of light-emitting elements. The element structure is further subdivided according to different functions. Generally, it is composed of a substrate, an anode, an organic functional layer and a metal cathode. The organic functional layer includes an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, etc.

[0003] The efficiency of organic light-emitting elements can usually be divided into internal luminous efficiency and external luminous efficiency. The internal luminous efficiency is related to the efficiency of generating excitons and realizing light conversion in organic layers such as hole transport layer, luminescent layer and electron transport layer between cathode and anode. Theoretically, the internal luminous efficiency of fluorescence is 25%, while that of phosphorescence is 100%. The external luminous efficiency refers to the efficiency of light generated in the organic layer being extracted to the outside of the organic light-emitting element. It is known that usually about 20% of the internal luminous efficiency can be extracted to the outside. The reason is that when the light emitted from the luminescent layer is incident on other films, total reflection will occur at the interface between the ITO film and the glass substrate and the interface between the glass substrate and the air. The light emitted to the external space of the OLED device is mainly limited in the organic film, ITO film and glass substrate in the form of waveguide. In the end, only about 20% of the photons reach the outside, and nearly 80% of the light cannot be emitted, and is limited to the inside of the device as heat dissipation. Excessive heat accumulation will have an adverse effect on the life of other organic materials inside the device, which greatly restricts the development and application of OLED.

[0004] In order to improve the efficiency of light extraction, a light-emitting element is proposed in which a "covering layer" with a high refractive index is provided on the outside of a semi-transparent electrode with a low refractive index. As a method of improving the above light extraction efficiency, in order to prevent the light irradiated to the outside from being lost due to total reflection, various organic compounds with a refractive index of 1.7 or more are usually used as a covering layer. In order to improve the performance of organic light-emitting elements, efforts have been made to develop an organic compound with a high refractive index and thin film stability that can improve the external light emission efficiency. Summary of the invention

[0005] In view of the above problems existing in the prior art, the object of the present invention is to provide an amine compound based on a heteroaryl group and an organic electroluminescent device thereof, which can effectively improve the light extraction efficiency of the OLED device, thereby improving the luminous efficiency of the OLED device.

[0006] The present invention provides an amine compound based on a heteroaryl group, characterized in that the structure of the compound is as shown in Chemical Formula 1,

[0007]

[0008] In formula 1,

[0009] Ar1 is selected from the structure shown in Chemical Formula 2; Ar2 is selected from the structure shown in Chemical Formula 2 or Chemical Formula 3; Ar3 is selected from any one of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C2-C30 heteroaryl groups, provided that when Ar3 is an N-containing heteroaryl group, the number of N atoms does not exceed 2;

[0010]

[0011] Said X, X1, X2, X3, X4 are independently selected from any one of N and CR1, provided that at least one of X1, X2, X3, X4 is selected from N;

[0012] Said Y is selected from O or S;

[0013] Said Z is selected from CR2;

[0014] The R1 and R2 are independently selected from any one of a connecting bond, hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C2-C30 heteroaryl group, or two adjacent R1 groups may be bonded to form a ring;

[0015] The ring A and the ring B are independently selected from any one of a substituted or unsubstituted benzene ring and a substituted or unsubstituted naphthalene ring;

[0016] The L1, L2, and L3 are independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted pyrimidylene group, a substituted or unsubstituted pyridazinylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted quinazolinylene group, and a substituted or unsubstituted quinoxalylene group;

[0017] Said n1, n2, n3 are independently selected from 0, 1, 2 or 3;

[0018] The substituent group in the "substituted or unsubstituted" is selected from one or more of the following groups: deuterium, halogen atoms, cyano, amino, nitro, C1-C12 alkyl, C3-C12 cycloalkyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidyl; the phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidyl can be further substituted by deuterium, halogen atoms, cyano, C1-C12 alkyl, C3-C12 cycloalkyl; in the case of being substituted by multiple substituents, the multiple substituents may be the same or different, or adjacent substituents may be bonded to form a ring.

[0019] The present invention also provides an organic electroluminescent device, comprising a substrate, an anode, an organic layer, and a cathode, wherein the organic layer comprises the heteroaryl-based amine compound of the present invention.

[0020] Beneficial effects of the present invention:

[0021] The present invention provides a heteroaryl-based amine compound for a covering layer, wherein the N-heterobenzo five-membered ring structure has a high refractive index, a neat molecular orientation, a high glass transition temperature, a high thermal stability, and is not easy to crystallize after being heated and cooled. After the covering layer of an OLED device is applied with the compound of the present invention, the service life and luminous efficiency of the OLED device can be effectively improved. The compound of the present invention has good application effects and industrial prospects in OLED light-emitting devices. DETAILED DESCRIPTION

[0022] The following will be described clearly and completely in conjunction with the technical solutions of the embodiments of the present invention. Obviously, the described embodiments are only 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 those skilled in the art without creative work are within the scope of protection of the present invention.

[0023] In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes the atom in both its natural isotopic abundance and unnatural abundance.

[0024] In the present invention, "" means a part connected to another substituent. "" can be connected to any optional position of the connected group / fragment. For example express And so on.

[0025] The halogen described in the present invention includes fluorine, chlorine, bromine and iodine.

[0026] In the present invention, the alkyl group may be linear or branched, preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. The alkyl group may be substituted or unsubstituted. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 2-ethylbutyl, 1-methylhexyl, n-octyl, etc., but are not limited thereto.

[0027] In the present invention, the cycloalkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and further preferably 3 to 6 carbon atoms. The cycloalkyl group may be substituted or unsubstituted. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, cycloheptyl, norbornyl, adamantyl, etc., but are not limited thereto.

[0028] In the present invention, the aryl group may be a monocyclic aryl group, a polycyclic aryl group, a condensed aryl group or a combination thereof, preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, further preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The aryl group may be substituted or unsubstituted. When the aryl group is a monocyclic aryl group, specific examples include phenyl and the like, but are not limited thereto; when the aryl group is a polycyclic aryl group, specific examples include biphenyl, terphenyl and the like, but are not limited thereto; when the aryl group is a condensed aryl group, specific examples include naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyrenyl, perylenyl, indenyl, fluoranthenyl, fluorenyl and the like, but are not limited thereto.

[0029] In the present invention, the heteroaryl group contains one or more heteroatoms other than carbon, and the specific heteroatoms may include one or more atoms selected from O, S, N, Se and Si, etc., preferably having 2 to 30 carbon atoms, more preferably having 2 to 10 carbon atoms, and further preferably having 2 to 7 carbon atoms. The heteroaryl group may be substituted or unsubstituted. The heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, a condensed ring heteroaryl group or a combination thereof. When the heteroaryl group is a monocyclic heteroaryl group, specific examples include thienyl, furanyl, pyrrolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, oxazolyl, thiazolyl, etc., but are not limited thereto; when the heteroaryl group is a polycyclic heteroaryl group, specific examples include bipyridyl, etc., but are not limited thereto; when the heteroaryl group is a condensed ring heteroaryl group, specific examples include acridinyl, phenanthridinyl, phenazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridine The invention also includes but is not limited to benzophenone, benzoxazolyl, benzoimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, benzofuranyl, phenothiazinyl, dibenzothiophenyl, dibenzofuranyl, benzonaphthofuranyl, benzonaphthothiophenyl, azabenzoxazolyl, azabenzimidazolyl, azabenzothiazolyl, azabenzothiophenyl, azabenzofuranyl, azacarbazolyl, azafluorenyl, carbolinyl, phenanthroline and the like, but are not limited thereto.

[0030] In the present invention, the arylene group refers to a divalent group obtained by removing two hydrogen atoms from the parent nucleus of an aromatic hydrocarbon molecule. The arylene group includes a monocyclic arylene group, a polycyclic arylene group, a condensed ring arylene group or a combination thereof, preferably C6 to C30 carbon atoms, more preferably C6 to C20 carbon atoms, and more preferably C6 to C12 carbon atoms. The aryl group may be substituted or unsubstituted. When the arylene group is a monocyclic arylene group, specific examples include phenylene, but not limited thereto; when the arylene group is a polycyclic arylene group, specific examples include biphenylene, terphenylene, quaterphenylene, etc., but not limited thereto; when the arylene group is a condensed ring arylene group, specific examples include naphthylene, anthrylene, phenanthrenyl, triphenylene, pyrenyl, fluorenyl, benzofluorenyl, spirobifluorenyl, benzospirobifluorenyl, etc., but not limited thereto.

[0031] In the present invention, the sub-heteroaryl group refers to a divalent group obtained by removing two hydrogen atoms from the parent nucleus of the heterocyclic aromatic hydrocarbon molecule. The heteroatom may include one or more atoms selected from O, S, N, Se and Si, etc., preferably having 2 to 30 carbon atoms, more preferably having 2 to 10 carbon atoms, and further preferably having 2 to 7 carbon atoms. The sub-heteroaryl group may be substituted or unsubstituted. The sub-heteroaryl group may be a monocyclic sub-heteroaryl group, a polycyclic sub-heteroaryl group, a condensed ring sub-heteroaryl group or a combination thereof. Specific examples of the sub-heteroaryl group include pyridinyl, pyrimidinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, indolyl, indazolyl, carbazolyl, dibenzothienyl, dibenzofuranyl, etc., but are not limited thereto.

[0032] The substituents in the "substituted or unsubstituted" of the present invention are selected from one or more of the following groups: deuterium, halogen atoms, cyano, amino, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl. In the case of being substituted by multiple substituents, the multiple substituents may be the same or different, or adjacent substituents may be bonded to form a ring; preferably, the substituents in the "substituted or unsubstituted" are selected from the following groups One or more of the following: deuterium, a halogen atom, a cyano group, an amino group, a nitro group, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group; the phenyl group, the biphenyl group, the terphenyl group, the naphthyl group, the pyridyl group, the pyrimidyl group may be further substituted by deuterium, a halogen atom, a cyano group, a C1-C12 alkyl group, a C3-C12 cycloalkyl group; when substituted by multiple substituents, the multiple substituents may be the same or different from each other, or adjacent substituents may be bonded to form a ring.

[0033] The term "connected to form a ring" used in the present invention refers to two groups connected to each other by a chemical bond and optionally aromatized. For example:

[0034]

[0035] In the present invention, the ring formed by bonding can be an aromatic ring system, an aliphatic ring system or a ring system formed by condensing the two, and the ring formed by connecting can be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring or a condensed ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentane acene, cyclohexene, cyclohexane, cyclohexane acene, fluorene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, phenanthrene or pyrene, but not limited thereto. The formed ring can be substituted or unsubstituted.

[0036] The present invention provides an amine compound based on a heteroaryl group, characterized in that the structure of the compound is as shown in Chemical Formula 1,

[0037]

[0038] In formula 1,

[0039] Ar1 is selected from the structure shown in Chemical Formula 2; Ar2 is selected from the structure shown in Chemical Formula 2 or Chemical Formula 3; Ar3 is selected from any one of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C2-C30 heteroaryl groups, provided that when Ar3 is an N-containing heteroaryl group, the number of N atoms does not exceed 2;

[0040]

[0041] Said X, X1, X2, X3, X4 are independently selected from any one of N and CR1, provided that at least one of X1, X2, X3, X4 is selected from N;

[0042] Said Y is selected from O or S;

[0043] Said Z is selected from CR2;

[0044] The R1 and R2 are independently selected from any one of a connecting bond, hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C2-C30 heteroaryl group, or two adjacent R1 groups may be bonded to form a ring;

[0045] The ring A and the ring B are independently selected from any one of a substituted or unsubstituted benzene ring and a substituted or unsubstituted naphthalene ring;

[0046] The L1, L2, and L3 are independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted pyrimidylene group, a substituted or unsubstituted pyridazinylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted quinazolinylene group, and a substituted or unsubstituted quinoxalylene group;

[0047] Said n1, n2, n3 are independently selected from 0, 1, 2 or 3;

[0048] The substituent group in the "substituted or unsubstituted" is selected from one or more of the following groups: deuterium, halogen atoms, cyano, amino, nitro, C1-C12 alkyl, C3-C12 cycloalkyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidyl; the phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidyl may be further substituted by deuterium, halogen atoms, cyano, C1-C12 alkyl, C3-C12 cycloalkyl; in the case of being substituted by multiple substituents, the multiple substituents may be the same or different, or adjacent substituents may be bonded to form a ring.

[0049] Preferably, the chemical formula 2 is selected from any one of the following structures,

[0050]

[0051] Said Y is selected from O or S;

[0052] The R3 is independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, or two adjacent R3 may be bonded to form a ring;

[0053] a1 is selected from 0, 1, 2 or 3; a2 is selected from 0, 1 or 2; a3 is selected from 0 or 1; a4 is selected from 0, 1, 2, 3 or 4.

[0054] Preferably, two adjacent R3 groups may be bonded to form a substituted or unsubstituted benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrazine ring or pyridazine ring.

[0055] Preferably, the chemical formula 2 is selected from any one of the following structures,

[0056]

[0057] The above groups may be further substituted by one or more deuterium, halogen, cyano, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, naphthyl, deuterated naphthyl, pyridyl, pyrimidyl, or adjacent substituents may be bonded to form a ring.

[0058] Preferably, adjacent substituents in the above Chemical Formula 2 may be bonded to form a substituted or unsubstituted benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrazine ring or pyridazine ring.

[0059] Preferably, the chemical formula 3 is selected from any one of the following structures,

[0060]

[0061] Preferably, Ar3 is selected from any one of the following groups,

[0062]

[0063] Said T is selected from N or CR4;

[0064] The R4 is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or two adjacent R4s may be bonded to form a ring;

[0065] The E is selected from O, S, N, CR a R b or NR c Any of the following:

[0066] The R a , R b , R c R is independently selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, a and R b They can be bonded to form a ring.

[0067] Preferably, Ar3 is selected from any one of the following groups,

[0068]

[0069] The R5 is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, or two adjacent R5 can be bonded to form a ring;

[0070] The b1 is selected from 0, 1, 2, 3, 4 or 5; the b2 is selected from 0, 1, 2, 3 or 4; the b3 is selected from 0, 1, 2 or 3; and the b4 is selected from 0, 1 or 2.

[0071] Preferably, two adjacent R5 groups may be bonded to form a substituted or unsubstituted benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrazine ring or pyridazine ring.

[0072] Preferably, L1, L2, and L3 are independently selected from any one of a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted pyridylene, a substituted or unsubstituted pyrimidylene, a substituted or unsubstituted pyridazinylene, a substituted or unsubstituted pyrazinylene, a substituted or unsubstituted quinolylene, a substituted or unsubstituted isoquinolylene, a substituted or unsubstituted quinazolinylene, and a substituted or unsubstituted quinoxalylene.

[0073] Preferably, L1, L2, and L3 are independently selected from a single bond or any one of the following groups:

[0074]

[0075] The above groups may be further substituted by one or more deuterium, cyano, halogen, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl.

[0076] Most preferably, the chemical formula 1 is selected from any one of the following structures,

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096] Some specific structures of the heteroaryl-based amine compounds of Chemical Formula 1 of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and all heteroaryl-based amine compounds based on Chemical Formula 1 and substituents as defined above should be included.

[0097] The present invention also provides an organic electroluminescent device, comprising a substrate, an anode, an organic layer, and a cathode, wherein the organic layer comprises at least one of the heteroaryl-based amine compounds of the present invention.

[0098] Preferably, the organic layer includes a covering layer, the covering layer is located outside the cathode, and the covering layer contains at least one of the heteroaryl-based amine compounds described in the present invention.

[0099] The structure of the organic electroluminescent device described in the present invention is preferably as follows:

[0100] Anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode / covering layer;

[0101] Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / electron transport layer / electron injection layer / cathode / covering layer;

[0102] Anode / hole injection layer / hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode / covering layer;

[0103] Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode / covering layer;

[0104] Anode / hole injection layer / hole transport layer / luminescence auxiliary layer / luminescent layer / electron transport layer / electron injection layer / cathode / covering layer;

[0105] Anode / hole injection layer / hole transport layer / luminescence auxiliary layer / luminescence layer / hole blocking layer / electron transport layer / electron injection layer / cathode / covering layer.

[0106] The structure of the organic electroluminescent device of the present invention is not limited to the above structure, and multiple organic layers can be omitted or simultaneously provided if necessary. For example, an electron blocking layer can be provided between the hole transport layer and the light-emitting layer, and a hole blocking layer can be provided between the electron transport layer and the light-emitting layer; organic layers having the same function can also be made into a stacked structure of more than two layers, and each organic layer can contain one material or multiple materials.

[0107] The light emitting device of the present invention is usually formed on a substrate. The substrate may be any substrate as long as it does not change when forming the electrode or the organic layer, for example, a substrate of glass, plastic, polymer film, silicon, etc. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.

[0108] Anode material, usually selected from materials with high work function to facilitate hole injection. The anode can be a reflective electrode or a transmissive electrode. The material used for the anode can be a transparent and highly conductive material, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2) and zinc oxide (ZnO), and the structure of the anode material is not limited thereto. When the anode is a semi-transmissive electrode or a reflective electrode, as for the material used to form the anode, at least one selected from magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In) and magnesium-silver (Mg-Ag) can be used. The anode can have a single-layer structure, or a multilayer structure including two or more layers. For example, the anode can have a three-layer structure of ITO / Ag / ITO, but the structure of the anode is not limited thereto. Preferably, the anode of the present invention adopts a transparent ITO substrate. The anode can be formed by depositing or spraying the material used to form the anode on a substrate.

[0109] The hole transport zone may include a single-layer structure of multiple different materials, a hole injection layer / hole transport layer structure, a hole injection layer / hole transport layer / buffer layer structure, a hole injection layer / buffer layer structure, a hole transport layer / buffer layer structure, or a hole injection layer / hole transport layer / electron blocking layer structure, wherein the layers of each structure are stacked successively from the anode in the order described, but the structure of the hole transport zone is not limited thereto.

[0110] The hole injection material is a material having the function of promoting hole injection from the anode. The hole injection layer can be formed at a thickness in the range of 10nm to 150nm. The material of the hole injection layer may include triphenylamine-containing polyetherketone (TPAPEK), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (PPBI), N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine (DNTPD), copper phthalocyanine (II) (abbreviation: CuPc), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (abbreviation: HAT-CN), 4,4',4"-tri{N ,N-diphenylamino}triphenylamine (TDATA), 4,4',4"-tri(N,N-2-naphthylphenylamino)triphenylamine (2-TNATA), polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA) or polyaniline / poly(4-styrenesulfonate (PANI / PSS), etc. It can be a single structure composed of a single substance or a single-layer or multi-layer structure formed by different substances. In addition to the above materials and their combinations, other known materials suitable for the hole injection layer can also be selected.

[0111] The hole transport material is a material with good hole transport performance. The hole transport layer may include one or more layers of material deposited, for example, the hole transport layer may include a first hole transport layer and a second hole transport layer. The hole transport layer may form a layer thickness of 10nm to 150nm (for example, the total layer thickness of the multilayer structure). The hole transport layer material can be selected from small molecule materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and polymer materials such as polyparaphenylene derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polyvinylcarbazole and its derivatives, polysilane and its derivatives, but is not limited thereto. Examples of hole transport materials may include 1,1-bis[(di-4-methylphenylamino)phenyl]cyclohexane (TAPC), carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD), 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPB), 2,2,7,7-tetrakis(diphenylamino)-9,9-spirobifluorene (abbreviated as: Spiro-TAD), and the like.

[0112] The light-emitting layer is a layer having a light-emitting function, and the light-emitting layer includes a host material and a dopant material, and emits light via fluorescence or phosphorescence. The light-emitting layer can be formed with a layer thickness in the range of 10nm to 60nm. The light-emitting layer can be formed as a layer having a specific color of light emitted. For example, the light-emitting layer can be formed as a red light-emitting layer, a green light-emitting layer, or a blue light-emitting layer.

[0113] The host material is selected from 4,4'-di(9-carbazole)biphenyl (CBP), 9,10-di(2-naphthyl)anthracene (ADN), 4,4-di(9-carbazolyl)biphenyl (CPB), 9,9'-(1,3-phenyl)di-9H-carbazole (mCP), 4,4',4"-tri(carbazole-9-yl)triphenylamine (TCTA), 9,10-di(1-naphthyl)anthracene (α-AND), N,N'-di-(1-naphthyl)-N,N'-diphenyl-[1,1':4',1":4",1"'-tetraphenyl]-4,4"'-diamine (4PNPB), 1,3,5-tri(9-carbazolyl)benzene (TCP), etc. In addition to the above materials and combinations thereof, the host material of the light-emitting layer can also select other known materials suitable for the light-emitting layer.

[0114] When the light-emitting layer is a blue light-emitting layer, a suitable blue dopant can be used. For example, perylene and its derivatives, iridium (Ir) complexes such as bis[2-(4,6-difluorophenyl)pyridine (pyridinate)] picolinate iridium (III) (FIrpic) can be used as blue dopants. When the light-emitting layer is a red light-emitting layer, a suitable red dopant can be used. For example, rubrene and its derivatives, 4-dicyanomethylene-2-(p-dimethylaminophenylvinyl)-6-methyl-4H-pyran (DCM) and its derivatives, iridium complexes such as bis(1-phenylisoquinoline) (acetylacetonate) iridium (III) (Ir(piq)2(acac), osmium (Os) complexes, platinum complexes, etc. can be used as red dopants. When the light-emitting layer is a green light-emitting layer, a suitable green dopant can be used. For example, coumarin and its derivatives, iridium complexes such as tris(2-phenylpyridine) iridium (III) (Ir(ppy)3) and the like can be used.

[0115] The optimal doping ratio of the main material and the guest material of the light-emitting layer may vary depending on the materials used. Usually, the doping mass percentage of the guest material of the light-emitting layer is 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.

[0116] The electron transport layer is a layer having an electron transport function, and the electron transport layer may include a first electron transport layer material and a second electron transport layer material. The electron transport layer may be formed to have a layer thickness in the range of 15 nm to 50 nm. The electron transport layer material can be selected from quinoline derivatives such as tris(8-hydroxyquinoline)aluminum (Alq3), 1,2,4-triazole derivatives (TAZ), bis(2-methyl-8-hydroxyquinoline)-(p-phenylphenol)-aluminum (BAlq), bis(10-hydroxybenzoquinoline)beryllium (BeBq2), Li complexes such as 8-hydroxyquinoline lithium (LiQ), nitrogen-containing aromatic rings, etc. Examples of nitrogen-containing aromatic rings may include pyridine ring-containing materials such as 1,3,5-tris[(3-pyridyl)-phenyl-3-yl]benzene, triazine ring-containing materials such as 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine, imidazole derivative-containing materials such as 2-(4-(N-phenylbenzimidazol-1-ylphenyl)-9,10-dinaphthylanthracene), etc. It can be a single structure composed of a single substance, or a single-layer structure or a multi-layer structure formed by different substances. In addition to the above materials, other known materials suitable for the electron transport layer can also be selected.

[0117] The electron injection layer is a layer having the function of promoting electron injection from the cathode. The electron injection layer can form a layer thickness in the range of 0.3nm to 9nm. The electron injection layer material can be selected from lithium fluoride (LiF), sodium chloride (NaCl), cesium fluoride (CsF), lithium oxide (Li2O), barium oxide (BaO), 8-hydroxyquinoline lithium (LiQ), etc. In addition to the above materials, the electron injection layer material can also select other known materials suitable for electron injection layer.

[0118] The cathode is used to inject electrons into the electron injection / transport layer or the light-emitting layer, and can be formed as a reflective electrode using metals, alloys, conductive compounds, etc. with a low work function. The cathode can be formed using, for example, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The cathode can be formed into a thin film of a material having a thickness of about 20nm or less, and can be formed as a transmissive electrode using ITO, IZO, etc. It can be prepared by forming a thin film by a method such as evaporation or sputtering, and the film thickness is usually 10nm to 1μm, preferably 50 to 200nm.

[0119] The purpose of the cover layer material is to reduce the total emission loss and waveguide loss in the OLED device and improve the light extraction efficiency. The cover layer material of the present invention can be selected from Alq3, TPBi, etc., and other known materials suitable for the cover layer can also be selected. The heteroaryl-based amine compounds described in the present invention are preferred.

[0120] There is no particular limitation on the method for preparing and forming each layer in the organic light-emitting device, and any one of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray coating, slit coating, and dip coating can be used. In the present invention, vacuum evaporation is preferably used.

[0121] The organic light-emitting device of the present invention can be widely used in the fields of panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, signboard, signal lamp, etc.

[0122] The present invention is described in more detail with reference to the following examples. However, the following examples are only used to illustrate the present description, and the scope of the present description is not limited to these examples.

[0123] Synthesis Example

[0124] There is no particular limitation on the preparation method of the compound represented by Chemical Formula 1 of the present invention, and the compound can be prepared by methods well known to those skilled in the art. The compound represented by Chemical Formula 1 of the present invention can be prepared by the following synthetic routes. (1)

[0126] (2)

[0128] (3)

[0130]

[0131] wherein each Xn is the same or different and is selected from Cl, Br, I;

[0132] Raw materials and reagents: The present invention has no particular limitations on the raw materials or reagents used in the following synthesis examples. They may be commercially available products or prepared by preparation methods well known to those skilled in the art. All raw materials and reagents are of reagent grade.

[0133] Instruments: The mass spectrometer is a G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer produced by Waters, UK; the element analyzer is a Vario EL cube organic element analyzer produced by Elementar, Germany.

[0134] Synthesis Example 1: Preparation of Intermediate c-327

[0135]

[0136] Under nitrogen protection, b-327 (11.88 g, 60.00 mmol), b'-327 (9.38 g, 60.00 mmol), K2CO3 (16.58 g, 120.00 mmol), Pd(PPh3)4 (0.75 g, 0.65 mmol), 120 ml of ethanol and 120 ml of water were added to 360 ml of toluene, and the mixture was stirred. The mixed solution of the above reactants was heated to reflux for 4 h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized with toluene / methanol (volume ratio 9:1) to obtain intermediate c-327 (11.71 g). The solid purity was ≥99.76% by HPLC. Mass spectrum m / z: 229.0281 (theoretical value: 229.0294).

[0137] Synthesis Example 2: Preparation of Intermediate b-351

[0138]

[0139] According to the same preparation method as the intermediate c-327 in Synthesis Example 1, b-327 was replaced by an equal mole of a'-351, and b'-327 was replaced by an equal mole of b'-351 to obtain intermediate b-351 (15.41 g), and the solid purity was ≥99.87% as determined by HPLC. Mass spectrum m / z: 305.0620 (theoretical value: 305.0607).

[0140] Synthesis Example 3: Preparation of Intermediate b-371

[0141]

[0142] According to the same preparation method as the intermediate c-327 in Synthesis Example 1, b-327 was replaced by an equal mole of a'-371, and b'-327 was replaced by an equal mole of b'-371 to obtain intermediate b-371 (12.04 g), and the solid purity was ≥99.89% as determined by HPLC. Mass spectrum m / z: 230.0234 (theoretical value: 230.0247).

[0143] Synthesis Example 4: Preparation of Intermediate a-401

[0144]

[0145] According to the same preparation method as the intermediate c-327 in Synthesis Example 1, b-327 was replaced by an equal mole of a'-401, and b'-327 was replaced by an equal mole of b'-401 to obtain intermediate a-401 (10.47 g), and the solid purity was ≥99.84% by HPLC. Mass spectrum m / z: 210.0782 (theoretical value: 210.0793).

[0146] Synthesis Example 5: Preparation of Intermediate b-401

[0147]

[0148] According to the same preparation method of intermediate c-327 in Synthesis Example 1, b-327 was replaced by an equal mole of a'-401, and b'-327 was replaced by an equal mole of b'-327 to obtain intermediate b-401 (11.71 g), and the solid purity was ≥99.79% as determined by HPLC. Mass spectrum m / z: 229.0280 (theoretical value: 229.0294).

[0149] Synthesis Example 6: Preparation of Intermediate a-455

[0150]

[0151] According to the same preparation method as the intermediate c-327 in Synthesis Example 1, b-327 was replaced by an equal mole of a'-455, and b'-327 was replaced by an equal mole of b'-401 to obtain intermediate a-455 (10.22 g), and the solid purity was ≥99.83% as determined by HPLC. Mass spectrum m / z: 210.0807 (theoretical value: 210.0793).

[0152] Synthesis Example 7: Preparation of Intermediate b-455

[0153]

[0154] According to the same preparation method as the intermediate c-327 in Synthesis Example 1, b-327 was replaced by an equal mole of a'-455, and b'-327 was replaced by an equal mole of b'-455 to obtain intermediate b-455 (12.18 g), and the solid purity was ≥99.80% by HPLC. Mass spectrum m / z: 230.0261 (theoretical value: 230.0247).

[0155] Synthesis Example 8: Preparation of Compound 10

[0156]

[0157] Preparation of intermediate A-10:

[0158] Under nitrogen protection, a-10 (11.17 g, 50.00 mmol), b-10 (17.51 ​​g, 50.00 mmol), sodium tert-butoxide (8.65 g, 90.00 mmol) were added to 200 ml of toluene, and Pd(OAc)2 (0.13 g, 0.60 mmol) and P(t-Bu)3 (2.40 mL of 0.50 M toluene solution, 1.20 mmol) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 5 h. After the reaction was completed, the reaction solution was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure, cooled and crystallized, and filtered by suction. The obtained solid was recrystallized with toluene / methanol (volume ratio 10:1) to obtain intermediate A-10 (20.20 g). The solid purity was ≥99.67% by HPLC. Mass spectrum m / z: 492.2131 (theoretical value: 492.2140).

[0159] Preparation of compound 10:

[0160] Under nitrogen protection, intermediate A-10 (17.24 g, 35.00 mmol), c-10 (9.82 g, 35.00 mmol), sodium tert-butoxide (6.25 g, 65.00 mmol) were added to 200 ml of toluene, and Pd2(dba)3 (0.37 g, 0.40 mmol) and X-Phos (0.43 g, 0.50 mmol) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 6 h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation, cooled and crystallized, and filtered by suction. The obtained solid was recrystallized with toluene to obtain compound 10 (17.54 g). The solid purity was ≥99.93% detected by HPLC. Mass spectrum m / z: 736.2791 (theoretical value: 736.2776). Theoretical element content (%) C 51 H 28 D4N4O2: C, 83.13; H, 4.92; N, 7.60. Measured element content (%): C, 83.17; H, 4.89; N, 7.65.

[0161] Synthesis Example 9: Preparation of Compound 34

[0162]

[0163] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-34, b-10 was replaced by an equal mole of b-34, and c-10 was replaced by an equal mole of b-34 to obtain compound 34 (14.48 g). The solid purity was ≥99.92% as determined by HPLC. Mass spectrum m / z: 523.1380 (theoretical value: 523.1393). Theoretical element content (%) C 30 H 17 N7O3: C, 68.83; H, 3.27; N, 18.73. Measured element content (%): C, 68.87; H, 3.24; N, 18.77.

[0164] Synthesis Example 10: Preparation of Compound 38

[0165]

[0166] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-38, b-10 was replaced by an equal mole of b-38, and c-10 was replaced by an equal mole of b-38 to obtain compound 38 (16.16 g). The solid purity detected by HPLC was ≥99.96%. Mass spectrum m / z: 599.1722 (theoretical value: 599.1706). Theoretical element content (%) C 36 H 21 N7O3: C, 72.11; H, 3.53; N, 16.35. Measured element content (%): C, 72.15; H, 3.50; N, 16.39.

[0167] Synthesis Example 11: Preparation of Compound 59

[0168]

[0169] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-59, b-10 was replaced by an equal mole of b-59, and c-10 was replaced by an equal mole of c-59 to obtain compound 59 (17.83 g). The solid purity was ≥99.91% as determined by HPLC. Mass spectrum m / z: 717.1723 (theoretical value: 717.1736). Theoretical element content (%) C 41 H 22 F3N7O3: C, 68.62; H, 3.09; N, 13.66. Measured element content (%): C, 68.65; H, 3.05; N, 13.62.

[0170] Synthesis Example 12: Preparation of Compound 70

[0171]

[0172] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-70, b-10 was replaced by an equal mole of b-70, and c-10 was replaced by an equal mole of b-70 to obtain compound 70 (16.45 g). The solid purity was ≥99.94% as determined by HPLC. Mass spectrum m / z: 602.1577 (theoretical value: 602.1563). Theoretical element content (%) C 33 H 18 N 10 O3: C, 65.78; H, 3.01; N, 23.25. Measured element content (%): C, 65.74; H, 3.05; N, 23.29.

[0173] Synthesis Example 13: Preparation of Compound 125

[0174]

[0175] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-38, b-10 was replaced by an equal mole of b-38, and c-10 was replaced by an equal mole of c-125 to obtain compound 125 (14.77 g). The solid purity was ≥99.96% as determined by HPLC. Mass spectrum m / z: 562.2180 (theoretical value: 562.2166). Theoretical element content (%) C 36 H 18 D5N5O2: C, 76.85; H, 5.01; N, 12.45. Measured element content (%): C, 76.89; H, 5.05; N, 12.41.

[0176] Synthesis Example 14: Preparation of Compound 128

[0177]

[0178] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-128, b-10 was replaced by an equal mole of b-128, and c-10 was replaced by an equal mole of c-128 to obtain compound 128 (16.95 g). The solid purity was ≥99.90% as determined by HPLC. Mass spectrum m / z: 691.2960 (theoretical value: 691.2947). Theoretical element content (%) C 46 H 37 N5O2: C, 79.86; H, 5.39; N, 10.12. Measured element content (%): C, 79.83; H, 5.43; N, 10.08.

[0179] Synthesis Example 15: Preparation of Compound 134

[0180]

[0181] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-134, b-10 was replaced by an equal mole of b-134, and c-10 was replaced by an equal mole of c-134 to obtain compound 134 (15.94 g). The solid purity was ≥99.93% as determined by HPLC. Mass spectrum m / z: 632.1975 (theoretical value: 632.1961). Theoretical element content (%) C 41 H 24 N6O2: C, 77.84; H, 3.82; N, 13.28. Measured element content (%): C, 77.88; H, 3.85; N, 13.24.

[0182] Synthesis Example 16: Preparation of Compound 150

[0183]

[0184] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-150, b-10 was replaced by an equal mole of b-150, and c-10 was replaced by an equal mole of b-150 to obtain compound 150 (17.71 g). The solid purity was ≥99.97% as determined by HPLC. Mass spectrum m / z: 665.2655 (theoretical value: 665.2667). Theoretical element content (%) C 44 H 19 D8N5O2: C, 79.38; H, 5.30; N, 10.52. Measured element content (%): C, 79.35; H, 5.34; N, 10.56.

[0185] Synthesis Example 17: Preparation of Compound 164

[0186]

[0187] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-164, b-10 was replaced by an equal mole of b-34, and c-10 was replaced by an equal mole of c-164 to obtain compound 164 (17.41 g). The solid purity was ≥99.92% as determined by HPLC. Mass spectrum m / z: 621.1817 (theoretical value: 621.1801). Theoretical element content (%) C 40 H 23 N5O3: C, 77.28; H, 3.73; N, 11.27. Measured element content (%): C, 77.24; H, 3.76; N, 11.22.

[0188] Synthesis Example 18: Preparation of Compound 170

[0189]

[0190] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-164, b-10 was replaced by an equal mole of b-170, and c-10 was replaced by an equal mole of c-170 to obtain compound 170 (16.34 g). The solid purity detected by HPLC was ≥99.91%. Mass spectrum m / z: 666.2040 (theoretical value: 666.2028). Theoretical element content (%) C 43 H 22 D4N4O2S: C, 77.46; H, 4.53; N, 8.40. Measured element content (%): C, 77.41; H, 4.57; N, 8.35.

[0191] Synthesis Example 19: Preparation of Compound 176

[0192]

[0193] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-176, b-10 was replaced by an equal mole of b-176, and c-10 was replaced by an equal mole of b-176 to obtain compound 176 (16.80 g). The solid purity was ≥99.90% as determined by HPLC. Mass spectrum m / z: 648.2040 (theoretical value: 648.2022). Theoretical element content (%) C 40 H 24 N8O2: C, 74.06; H, 3.73; N, 17.27. Measured element content (%): C, 74.11; H, 3.77; N, 17.24.

[0194] Synthesis Example 20: Preparation of Compound 190

[0195]

[0196] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-190, b-10 was replaced by an equal mole of b-190, and c-10 was replaced by an equal mole of c-190 to obtain compound 190 (18.70 g). The solid purity was ≥99.95% as determined by HPLC. Mass spectrum m / z: 785.2778 (theoretical value: 785.2791). Theoretical element content (%) C 54 H 35 N5O2: C, 82.53; H, 4.49; N, 8.91. Measured element content (%): C, 82.55; H, 4.47; N, 8.94.

[0197] Synthesis Example 21: Preparation of Compound 202

[0198]

[0199] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-202, b-10 was replaced by an equal mole of b-202, and c-10 was replaced by an equal mole of c-202 to obtain compound 202 (14.60 g). The solid purity detected by HPLC was ≥99.96%. Mass spectrum m / z: 508.1974 (theoretical value: 508.1981). Theoretical element content (%) C 34 H 16 D5N3O2: C, 80.30; H, 5.15; N, 8.26. Measured element content (%): C, 80.32; H, 5.13; N, 8.22.

[0200] Synthesis Example 22: Preparation of Compound 209

[0201]

[0202] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-209, b-10 was replaced by an equal mole of b-209, and c-10 was replaced by an equal mole of c-209 to obtain compound 209 (16.94 g). The solid purity was ≥99.92% as determined by HPLC. Mass spectrum m / z: 636.2511 (theoretical value: 636.2525). Theoretical element content (%) C 43 H 32 N4O2: C, 81.11; H, 5.07; N, 8.80. Measured element content (%): C, 81.14; H, 5.05; N, 8.82.

[0203] Synthesis Example 23: Preparation of Compound 239

[0204]

[0205] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-239, b-10 was replaced by an equal mole of b-239, and c-10 was replaced by an equal mole of b-239 to obtain compound 239 (17.30 g). The solid purity was ≥99.94% as determined by HPLC. Mass spectrum m / z: 726.1561 (theoretical value: 726.1548). Theoretical element content (%) C 47 H 26 N4OS2: C, 77.66; H, 3.61; N, 7.71. Measured element content (%): C, 77.62; H, 3.64; N, 7.66.

[0206] Synthesis Example 24: Preparation of Compound 253

[0207]

[0208] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-253, b-10 was replaced by an equal mole of b-253, and c-10 was replaced by an equal mole of b-253 to obtain compound 253 (16.75 g). The solid purity was ≥99.91% as determined by HPLC. Mass spectrum m / z: 629.2115 (theoretical value: 629.2103). Theoretical element content (%) C 44 H 27 N3O2: C, 83.92; H, 4.32; N, 6.67. Measured element content (%): C, 83.95; H, 4.30; N, 6.64.

[0209] Synthesis Example 25: Preparation of Compound 276

[0210]

[0211] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-106, b-10 was replaced by an equal mole of b-106, and c-10 was replaced by an equal mole of b-106 to obtain compound 276 (17.00 g). The solid purity was ≥99.97% as determined by HPLC. Mass spectrum m / z: 647.1036 (theoretical value: 647.1021). Theoretical element content (%) C 36 H 21 N7S3: C, 66.75; H, 3.27; N, 15.14. Measured element content (%): C, 66.79; H, 3.22; N, 15.17.

[0212] Synthesis Example 26: Preparation of Compound 294

[0213]

[0214] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-294, b-10 was replaced by an equal mole of b-294, and c-10 was replaced by an equal mole of c-294 to obtain compound 294 (15.90 g). The solid purity was ≥99.92% as determined by HPLC. Mass spectrum m / z: 639.1537 (theoretical value: 639.1551). Theoretical element content (%) C 40 H 25 N5S2: C, 75.09; H, 3.94; N, 10.95. Measured element content (%): C, 75.13; H, 3.89; N, 10.99.

[0215] Synthesis Example 27: Preparation of Compound 320

[0216]

[0217] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-320, b-10 was replaced by an equal mole of b-320, and c-10 was replaced by an equal mole of b-320 to obtain compound 320 (17.35 g). The solid purity was ≥99.91% as determined by HPLC. Mass spectrum m / z: 739.2418 (theoretical value: 739.2406). Theoretical element content (%) C 49 H 33 N5OS: C, 79.54; H, 4.50; N, 9.47. Measured element content (%): C, 81.55; H, 5.09; N, 9.15.

[0218] Synthesis Example 28: Preparation of Compound 327

[0219]

[0220] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-327, b-10 was replaced by an equal mole of b-327, and c-10 was replaced by an equal mole of c-327 to obtain compound 327 (12.76 g). The solid purity was ≥99.95% as determined by HPLC. Mass spectrum m / z: 444.1238 (theoretical value: 444.1222). Theoretical element content (%) C 27 H 16 N4O3: C, 72.97; H, 3.63; N, 12.61. Measured element content (%): C, 72.93; H, 3.68; N, 12.57.

[0221] Synthesis Example 29: Preparation of Compound 335

[0222]

[0223] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-335, b-10 was replaced by an equal mole of b-335, and c-10 was replaced by an equal mole of b-335 to obtain compound 335 (16.03 g). The solid purity was ≥99.94% as determined by HPLC. Mass spectrum m / z: 594.1957 (theoretical value: 594.1943). Theoretical element content (%) C 41 H 26N2O3: C, 82.81; H, 4.41; N, 4.71. Measured element content (%): C, 82.86; H, 4.37; N, 4.74.

[0224] Synthesis Example 30: Preparation of Compound 351

[0225]

[0226] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-351, b-10 was replaced by an equal mole of b-351, and c-10 was replaced by an equal mole of b-351 to obtain compound 351 (17.19 g). The solid purity was ≥99.92% as determined by HPLC. Mass spectrum m / z: 672.2149 (theoretical value 672.2161). Theoretical element content (%) C 45 H 28 N4O3: C, 80.34; H, 4.20; N, 8.33. Measured element content (%): C, 80.39; H, 4.16; N, 8.37.

[0227] Synthesis Example 31: Preparation of Compound 371

[0228]

[0229] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-371, b-10 was replaced by an equal mole of b-371, and c-10 was replaced by an equal mole of b-371 to obtain compound 371 (16.19 g). The solid purity detected by HPLC was ≥99.93%. Mass spectrum m / z: 600.1642 (theoretical value 600.1658). Theoretical element content (%) C 35 H 20 N8O3: C, 69.99; H, 3.36; N, 18.66. Measured element content (%): C, 69.94; H, 3.32; N, 18.69.

[0230] Synthesis Example 32: Preparation of Compound 401

[0231]

[0232] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-401, b-10 was replaced by an equal mole of b-401, and c-10 was replaced by an equal mole of b-401 to obtain compound 401 (15.66 g). The solid purity detected by HPLC was ≥99.90%. Mass spectrum m / z: 596.1861 (theoretical value 596.1848). Theoretical element content (%) C 39 H24 N4O3: C, 78.51; H, 4.05; N, 9.39. Measured element content (%): C, 78.56; H, 4.01; N, 9.42.

[0233] Synthesis Example 33: Preparation of Compound 455

[0234]

[0235] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-455, b-10 was replaced by an equal mole of b-455, and c-10 was replaced by an equal mole of b-455 to obtain compound 455 (16.34 g). The solid purity was ≥99.93% as determined by HPLC. Mass spectrum m / z: 598.1770 (theoretical value 598.1753). Theoretical element content (%) C 37 H 22 N6O3: C, 74.24; H, 3.70; N, 14.04. Measured element content (%): C, 74.29; H, 3.66; N, 14.07.

[0236] Synthesis Example 34: Preparation of Compound 470

[0237]

[0238] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-470, b-10 was replaced by an equal mole of b-470, and c-10 was replaced by an equal mole of c-470 to obtain compound 470 (16.75 g). The solid purity was ≥99.96% as determined by HPLC. Mass spectrum m / z: 605.2121 (theoretical value: 605.2103). Theoretical element content (%) C 42 H 27 N3O2: C, 83.29; H, 4.49; N, 6.94. Measured element content (%): C, 83.32; H, 4.45; N, 6.99.

[0239] Synthesis Example 35: Preparation of Compound 475

[0240]

[0241] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-475, b-10 was replaced by an equal mole of b-475, and c-10 was replaced by an equal mole of b-475 to obtain compound 475 (15.92 g). The solid purity was ≥99.97% as determined by HPLC. Mass spectrum m / z: 631.2021 (theoretical value: 631.2008). Theoretical element content (%) C42 H 25 N5O2: C, 79.86; H, 3.99; N, 11.09. Measured element content (%): C, 79.90; H, 3.96; N, 11.12.

[0242] Synthesis Example 36: Preparation of Compound 528

[0243]

[0244] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-528, b-10 was replaced by an equal mole of b-528, and c-10 was replaced by an equal mole of b-528 to obtain compound 528 (17.01 g). The solid purity was ≥99.94% as determined by HPLC. Mass spectrum m / z: 684.1283 (theoretical value: 684.1295). Theoretical element content (%) C 41 H 21 F5N2OS: C, 71.72; H, 3.09; N, 4.09. Measured element content (%): C, 71.75; H, 3.04; N, 4.08.

[0245] Synthesis Example 37: Preparation of Compound 535

[0246]

[0247] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-535, b-10 was replaced by an equal mole of b-535, and c-10 was replaced by an equal mole of c-535 to obtain compound 535 (17.02 g). The solid purity was ≥99.91% as determined by HPLC. Mass spectrum m / z: 694.2269 (theoretical value: 694.2256). Theoretical element content (%) C 49 H 30 N2O3: C, 84.71; H, 4.35; N, 4.03. Measured element content (%): C, 84.75; H, 4.30; N, 4.06.

[0248] Synthesis Example 38: Preparation of Compound 566

[0249]

[0250] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-566, b-10 was replaced by an equal mole of b-566, and c-10 was replaced by an equal mole of b-566 to obtain compound 566 (17.60 g). The solid purity was ≥99.92% as determined by HPLC. Mass spectrum m / z: 644.1181 (theoretical value: 644.1163). Theoretical element content (%) C 39 H 24 N4S3: C, 72.64; H, 3.75; N, 8.69. Measured element content (%): C, 72.68; H, 3.72; N, 8.74.

[0251] Synthesis Example 39: Preparation of Compound 607

[0252]

[0253] According to the same preparation method as in Synthesis Example 8, a-10 was replaced by an equal mole of a-607, b-10 was replaced by an equal mole of b-607, and c-10 was replaced by an equal mole of b-607 to obtain compound 607 (15.63 g). The solid purity was ≥99.93% as determined by HPLC. Mass spectrum m / z: 587.1477 (theoretical value: 587.1490). Theoretical element content (%) C 38 H 25 N3S2: C, 77.65; H, 4.29; N, 7.15. Measured element content (%): C, 77.69; H, 4.24; N, 7.18.

[0254] Device Embodiment

[0255] The ITO / Ag / ITO glass substrate was cleaned by ultrasonic cleaning twice with 5% glass cleaning solution for 20 minutes each time, and then ultrasonic cleaning twice with deionized water for 10 minutes each time. Then, ultrasonic cleaning was performed with acetone and isopropyl ketone for 20 minutes in sequence, and then dried at 120°C.

[0256] Device Example 1: On the prepared ITO / Ag / ITO glass electrode, HI:p-1=97%:3% (mass ratio) with a thickness of 10 nm is evaporated as a hole injection layer, HT1 with a thickness of 90 nm is evaporated as a hole transport layer, GH-1:GD-1=95%:5% (mass ratio) with a thickness of 30 nm is evaporated as a light-emitting layer, ET with a thickness of 25 nm is evaporated as an electron transport layer, LiF with a thickness of 1 nm is evaporated as an electron injection layer, Mg:Ag=1:9 (mass ratio) with a thickness of 12 nm is evaporated as a cathode, and the compound 10 of the present invention with a thickness of 80 nm is evaporated as a covering layer to prepare an organic electroluminescent device.

[0257] After completing the production of the organic light-emitting device according to the above steps, the photoelectric performance of the device is measured. The molecular structure formula of the relevant materials is as follows:

[0258]

[0259] Device Examples 2 to 32: The preparation methods of Device Examples 2 to 32 are the same as the preparation method of Device Example 1, except that the compound in the cover layer is replaced with the following compound:

[0260] Compound 34, compound 38, compound 59, compound 70, compound 125, compound 128, compound 134, compound 150, compound 164, compound 170, compound 176, compound 190, compound 202, compound 209, compound 239, compound 253, compound 276, compound 294, compound 320, compound 327, compound 335, compound 351, compound 371, compound 401, compound 455, compound 470, compound 475, compound 528, compound 535, compound 566, and compound 607.

[0261] Comparative Examples 1-2: The preparation methods of Comparative Examples 1-2 are the same as the preparation method of Device Example 1, except that the compound in the covering layer is replaced with the following compounds: CP-1, CP-2.

[0262] The test software, computer, K2400 digital source meter produced by Keithley Company of the United States and PR788 spectrum scanning luminance meter of PhotoResearch Company of the United States are combined into a joint IVL test system to test the luminous efficiency of organic electroluminescent devices. The life test adopts the M6000 OLED life test system of McScience Company. The test environment is the atmospheric environment and the temperature is room temperature. The test results of the luminous characteristics of the obtained organic light-emitting device are shown in Table 1:

[0263] [Table 1] Luminescence characteristics test of organic electroluminescent devices

[0264]

[0265]

[0266] Note: T98 refers to the current density of 10mA / cm 2 Under the condition of , the time taken by the device brightness to decay to 98%;

[0267] It can be seen from Table 1 that, compared with Comparative Examples 1-2, the luminous efficiency and service life of the organic electroluminescent device of the present invention are further improved, indicating that the heteroaryl-based amine compound of Structural Formula 1 of the present invention is a covering layer material with good performance.

[0268] Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the claims. Any technical personnel in this field may make several possible changes and modifications without departing from the concept of the present application. Therefore, the scope of protection of the present application shall be based on the scope defined by the claims of the present application.

Claims

1. A heteroaryl-based amine compound, characterized in that: The structure of the compound is shown in Chemical Formula 1, In formula 1, Ar1 is selected from the structure shown in Chemical Formula 2; Ar2 is selected from the structure shown in Chemical Formula 2 or Chemical Formula 3; The chemical formula 2 is selected from any one of the following structures, Said Y is selected from O or S; The R3 is independently selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted phenyl, or two adjacent R3 are bonded to form a benzene ring; the substituent group in the "substituted or unsubstituted methyl" is selected from one or more of the following groups: deuterium, halogen atom; the substituent group in the "substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted phenyl" is selected from: deuterium; a1 is selected from 0, 1, 2 or 3; a2 is selected from 0, 1 or 2; a4 is selected from 0, 1, 2, 3 or 4; The ring A and the ring B are independently selected from any one of a substituted or unsubstituted benzene ring and a substituted or unsubstituted naphthalene ring; the substituent group in the "substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring" is selected from one or more of the following groups: deuterium, C1-C6 alkyl, phenyl; the phenyl group is optionally substituted with deuterium; The Ar3 is selected from any one of the following groups: The R 5a Any one selected from hydrogen, deuterium, halogen, substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl; the substituent in the "substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl" is selected from: deuterium; The R 5b is selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted phenyl, or two adjacent R 5b The substituents in the "substituted or unsubstituted methyl" are selected from one or more of the following groups: deuterium, halogen atoms; the substituents in the "substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted phenyl" are selected from: deuterium; The R5 is selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, and substituted or unsubstituted phenyl; the substituent in the "substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, and substituted or unsubstituted phenyl" is selected from: deuterium; b1 is selected from 0, 1, 2, 3, 4 or 5; b2 is selected from 0, 1, 2, 3 or 4; b3 is selected from 0, 1, 2 or 3; b4 is selected from 0, 1 or 2; The L1, L2, and L3 are independently selected from any one of a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted pyridylene, a substituted or unsubstituted quinolylene, and a substituted or unsubstituted isoquinolylene; the substituent in the "substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted pyridylene, a substituted or unsubstituted quinolylene, and a substituted or unsubstituted isoquinolylene" is selected from deuterium and cyano; The n1, n2, and n3 are independently selected from 1; Provided that the compound is not 2. The heteroaryl-based amine compound according to claim 1, characterized in that The chemical formula 2 is selected from any one of the following structures, The above groups are optionally substituted with one or more deuterium, trifluoromethyl, isopropyl, tert-butyl, phenyl, deuterated phenyl, or adjacent substituents are bonded to form a benzene ring.

3. The heteroaryl-based amine compound according to claim 1, characterized in that The chemical formula 3 is selected from any one of the following structures, 4. The heteroaryl-based amine compound according to claim 1, characterized in that The L1, L2, and L3 are independently selected from any one of a single bond, a substituted or unsubstituted phenylene group.

5. A heteroaryl-based amine compound, characterized in that: The compound is selected from any one of the following structures, 6. An organic electroluminescent device comprising a substrate, an anode, an organic layer, and a cathode, characterized in that: The organic layer contains at least one of the heteroaryl-based amine compounds according to any one of claims 1 to 5.

7. An organic electroluminescent device according to claim 6, characterized in that: The organic layer comprises a covering layer, the covering layer is located outside the cathode, and the covering layer comprises at least one of the heteroaryl-based amine compounds according to any one of claims 1 to 5.

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