A fused ring compound and use thereof

Abstract

The present application relates to the technical field of display, in particular to a fused ring compound and application thereof. The present application provides a fused ring compound with structure of formula (1), which presents excellent thermal stability characteristics by limiting L and Ar groups to specific structures; when applied as a charge generation material, the N atom on the aromatic heterocycle in the structure of formula (1) can form a multi-coordination structure with a metal atom. Meanwhile, the compound exhibits good energy level matching characteristics with organic electroluminescent materials of adjacent functional layers. When such a fused ring compound is used as a charge generation layer, the corresponding stacked organic electroluminescent device has higher current efficiency, lower driving voltage and longer service life.

Description

Technical Field

[0001] This invention relates to the field of display technology, and more specifically to a fused ring compound and its applications. Background Technology

[0002] Organic light-emitting materials can be broadly categorized by function into light-emitting materials, hole-injection materials, hole-transport materials, electron-transport materials, and electron-injection materials. Organic light-emitting diodes (OLEDs) are devices that emit light through current-driven processes, offering advantages such as thinness, flexibility, high contrast, and wide color gamut. Due to their high current efficiency and long lifetime, stacked OLEDs have gradually become a research focus. These mainly consist of a first light-emitting layer, a second light-emitting layer, and a charge generation layer (CGL) positioned between the first and second light-emitting layers to ensure effective charge distribution across the light-emitting layers while improving the current efficiency of each layer. However, existing charge generation layer materials suffer from poor stability and low compatibility with other stacked organic light-emitting materials, resulting in high driving voltage, low luminous efficiency, and short lifetime in current organic light-emitting devices, severely limiting their applications.

[0003] Therefore, there is an urgent need in related technologies for charge-generating materials with high material stability and a higher degree of compatibility with existing multilayer materials. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of poor stability of charge generation layer materials and low matching degree with other stacked organic electroluminescent materials in related technologies, which result in high driving voltage, low luminous efficiency and short lifespan of existing organic electroluminescent devices. In this way, a fused ring compound and its application are provided.

[0005] In this invention, Indicates a connection key.

[0006] In this invention, the term "single bond" refers to the connection between two adjacent groups.

[0007] In this invention, the term "substituent" has its usual meaning as known in the art, referring to a chemical moiety covalently attached to or, where appropriate, fused to a parent nucleus group.

[0008] In this invention, the term "substituted or unsubstituted" means that the functional group described after the term may or may not have substituents (hereinafter, for ease of description, substituents are collectively referred to as Rc). For example, "substituted or unsubstituted aryl" refers to an aryl group having a substituent Rc or an unsubstituted aryl group. The substituent Rc mentioned above can be, for example, one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamine, and C3-C60 heteroarylamine. Optionally, it can be, for example, deuterium, halogen group, cyano, alkyl, haloalkyl, trialkylsilyl, deuterated alkyl, aryl, heteroaryl, etc. Of course, the number of substituents Rc can be one or more. When two substituents Rc are attached to the same atom, the two substituents Rc can exist independently or be connected to each other to form a ring with the atom; when two adjacent substituents Rc exist on a functional group, the adjacent substituents Rc can exist independently or fuse with the functional group to which they are attached to form a ring.

[0009] In this invention, the term "halogen" refers to an atom selected from fluorine, chlorine, bromine, and iodine.

[0010] In this invention, the term "alkyl" refers, whether as part of other terms or used alone, to a saturated hydrocarbon group, which may be straight-chain or branched. The term "C1-C60 alkyl" is derived from a monovalent substituent of a straight-chain or branched saturated hydrocarbon having 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and more preferably 1 to 20 carbon atoms. Examples of such substituents include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0011] In this invention, the term "cycloalkyl" refers to a cyclic alkyl group consisting of at least 3 atoms. More specifically, it refers to a monocyclic or polycyclic hydrocarbon derived from a main chain of 3 to 60 carbon atoms, preferably 3 to 40 carbon atoms, and even more preferably 3 to 20 carbon atoms. Of course, the cycloalkyl group includes, but is not limited to, cyclopropyl, cyclobutyl, adamantyl, etc.

[0012] In this invention, the term "heterocyclic alkyl" includes one or more of O, S, Se, N, and Si as heteroatoms, and is a monocyclic or polycyclic ring having 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and even more preferably 1 to 20 carbon atoms. Here, the polycyclic refers to a group in which a heterocyclic alkyl group is directly attached to or fused with another cyclic group. Here, the other cyclic group can also be a heterocyclic alkyl group, but it can also be another type of cyclic group, such as cycloalkyl, aryl, heteroaryl, etc.

[0013] In this invention, the terms "aryl" and "arylene" include monocyclic, polycyclic, or fused-ring aryl groups, wherein the rings may be interrupted by short non-aromatic units and may contain spiro structures. Aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracene, fluorene, and spirodifluorene. Arylene groups include, but are not limited to, phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthraceneene, fluorene, and spirodifluorene. Arylene refers to a divalent or polyvalent group formed by the further loss of one or more hydrogen atoms from an aryl group.

[0014] In this invention, the terms "heteroaryl" and "hybridoaryl" include monocyclic, polycyclic, or fused-ring heteroaryl groups, wherein the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen, and sulfur. Heteroaryl groups include, but are not limited to, furanyl, phenylthio, pyrroleyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetraazinyl, triazolyl, tetraazolyl, furazolidyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, dibenzofuranyl, dibenzothiopheneyl, benzimidazolyl, and benzyl. Benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazoleyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxalinyl, carbazoleyl, phenoxazinyl, phenthiazinyl, phenanthidyl, benzo[m]dioxacyclopentenyl, dihydroacridyl, and their derivatives; heteroaryl groups include, but are not limited to, furanyl, phenylthio, and pyrroleyl. Imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl Azolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, ininazole, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxolinyl, carbazolyl, phenoxazinyl, phenthiazinyl, phenanthridyl, phenanthridyl, benzo[m]dioxacyclopentenyl, dihydroacridyl, and their derivatives, etc. As used herein, the term "substituted" means that a hydrogen atom in the compound is replaced by another substituent. This position is not limited to a specific position, as long as the hydrogen at that position can be replaced by a substituent. When two or more substituents are present, the two or more substituents can be the same or different.

[0015] In this invention, "C1-C60, C3-C60, C6-C60, C1-C30, C3-C30, C6-C30" defines the range of carbon atoms, indicating that the number of carbon atoms is any integer within the defined range. C1-C60 represents any integer from 1 to 60, for example: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49. 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60; C3-C60 represents any integer number of carbon atoms within the range of 3-60, for example: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60; C6-C60 represents any integer number of carbon atoms within the range of 6- Any integer within the range of 60, for example: 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60; C1-C30 represents any integer from 1 to 30 representing the number of carbon atoms, for example: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30; C3-C30 represents any integer number of carbon atoms in the range of 3-30, for example: 3, 4, 56, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30; C6-C30 represents any integer number of carbon atoms in the range of 3-30, for example: 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30;For example, C6-C60 aryl groups represent any integer number of carbon atoms within the range of 6-60, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60.

[0016] The solution adopted in this invention is as follows:

[0017] This invention provides a fused-ring compound having the structure shown in formula (1):

[0018]

[0019] In equation (1),

[0020] L is selected from single bond, substituted or unsubstituted C6-C60 arylene, or substituted or unsubstituted C1-C60 heteroarylene;

[0021] Ar is selected from the structure shown in formula A:

[0022]

[0023] In formula A, X1 is selected from N or CR 1 X2 is selected from N or CR 2 X3 is selected from N or CR 3 X4 is selected from N or CR 4 X5 is selected from N or CR 5 ;

[0024] R 1 R 2 R 3 R 4 R 5 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0025] R 1 R 2 R 3 R 4 R 5 They exist independently, or adjacent pairs are connected to form substituted or unsubstituted C6-C60 aromatic rings, or substituted or unsubstituted C3-C60 heteroaromatic rings;

[0026] The substituents of the substituted C6-C60 arylene, substituted C1-C60 heteroarylene, substituted C1-C60 alkyl, substituted C3-C60 cycloalkyl, substituted C6-C60 aryl, substituted C3-C60 heteroarylene, substituted C6-C60 aromatic ring, and substituted C3-C60 heteroarylene ring are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroarylene.

[0027] Preferred, R 1 R 2 R 3 R 4 R 5 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0028] The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl groups are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl.

[0029] Preferred, R 1 R 2 R 3 R 4 R 5 They exist independently, or adjacent pairs are connected to form substituted or unsubstituted C6-C30 aromatic rings or substituted or unsubstituted C3-C30 heteroaromatic rings;

[0030] The substituents of the substituted C6-C30 aromatic ring and the substituted C3-C30 heteroaromatic ring are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl.

[0031] Understandable, "R" 1 R 2 R 3 R 4R 5 "Each exists independently, or two adjacent members are connected to form a substituted or unsubstituted C6-C60 aromatic ring, or a substituted or unsubstituted C3-C60 heteroaromatic ring" means that when R 1 R 2 R 3 R 4 R 5 At least two of them exist, and two of them are adjacent in formula (A). The two adjacent ones can exist independently or can be connected to form a substituted or unsubstituted C6-C60 aromatic ring or a substituted or unsubstituted C3-C60 heteroaromatic ring.

[0032] Preferably, the structure shown in formula A is selected from one of formulas A-1, A-2, and A-3:

[0033]

[0034] In formula A-1:

[0035] Ar 1 Ar 2 Each is independently selected from substituted or unsubstituted C6-C60 aryl groups, or substituted or unsubstituted C3-C60 heteroaryl groups;

[0036] L 1 L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C60 arylene, or substituted or unsubstituted C3-C60 heteroarylene;

[0037] Preferably, when formula A is selected from formula A-1, L is selected from substituted or unsubstituted C6-C60 arylene or substituted or unsubstituted C1-C60 heteroarylene;

[0038] Wherein, the substituents in the substituted C6-C60 arylene and the substituted C1-C60 heteroarylene are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroarylene.

[0039] More preferably, when formula A is selected from formula A-1, L is selected from substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C1-C30 heteroarylene;

[0040] The substituents in the substituted C6-C30 arylene and substituted C1-C30 heteroarylene are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl.

[0041] In formula A-2:

[0042] R 6 Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0043] n1 is any integer from 0 to 7, and when n1 is equal to or greater than 2, R 6 They are the same or different;

[0044] Preferably, when formula A is selected from formula A-2, L is selected from substituted or unsubstituted C6-C60 arylene or substituted or unsubstituted C1-C60 heteroarylene;

[0045] Wherein, the substituents in the substituted C6-C60 arylene and the substituted C1-C60 heteroarylene are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroarylene.

[0046] Preferably, when formula A is selected from formula A-2, L is selected from substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C1-C30 heteroarylene;

[0047] Wherein, the substituents in the substituted C6-C30 arylene and the substituted C1-C30 heteroarylene are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl.

[0048] In formula A-3:

[0049] Z 1 -Z 4 Each is independently selected from N or CR 8 ;

[0050] R 7 R8 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0051] The substituents of the substituted C1-C60 alkyl, substituted C3-C60 cycloalkyl, substituted C6-C60 aryl, and substituted C3-C60 heteroaryl are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl.

[0052] n2 is any integer from 0 to 4, and when n2 is equal to or greater than 2, R 7 They are the same or different;

[0053] Preferably, Z in formula A-3 1 -Z 4 At least one of them is selected from N;

[0054] Preferably, Z in formula A-3 1 -Z 4 One or both of them are selected from N;

[0055] Preferably, formula A-3 is selected from any one of formulas A-3-1 to A-3-3:

[0056]

[0057] R 9 Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0058] n3 is any integer from 0 to 7, and when n3 is equal to or greater than 2, R 9 They are the same or different;

[0059] The substituents of the substituted C6-C60 arylene, substituted C1-C60 heteroarylene, substituted C1-C60 alkyl, substituted C3-C60 cycloalkyl, substituted C6-C60 aryl, and substituted C3-C60 heteroarylene are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroarylene.

[0060] Preferably, in formula A-1, Ar 1 Ar 2 Each is independently selected from substituted or unsubstituted C6-C30 aryl groups or substituted or unsubstituted C3-C30 heteroaryl groups;

[0061] The substituents in the substituted C6-C30 aryl and substituted C3-C30 heteroaryl are selected from one or a combination of two or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl.

[0062] Preferably, in formula A-1, L 1 L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C30 arylene, or substituted or unsubstituted C3-C30 heteroarylene;

[0063] The substituents in the substituted C6-C30 arylene and substituted C3-C30 heteroarylene are selected from one or a combination of two or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl.

[0064] Preferably, in formula A-2, R 6 Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0065] The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl groups are selected from one or a combination of two or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl.

[0066] Preferably, in formula A-3, R 7 R 8 Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0067] The substituents in the substituted C6-C30 arylene, substituted C1-C30 heteroarylene, substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, and substituted C3-C30 heteroarylene are selected from one or a combination of two or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroarylene.

[0068] Preferably, in formulas A-3-1 to A-3-3, R 9 Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0069] The substituents in the substituted C6-C30 arylene, substituted C1-C30 heteroarylene, substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, and substituted C3-C30 heteroarylene are selected from one or a combination of two or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroarylene.

[0070] Preferably, in formula A-1, Ar 1 Ar 2 Each group is independently selected from substituted or unsubstituted A groups, wherein the A group is selected from: phenyl, naphthyl, phenanthryl, anthracene, fluoranyl, pyrene, biphenyl, binatyl, terphenyl, phenylnaphthyl, naphthylphenyl, triphenylene, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirodifluorenyl, 9,9-dimethylbenzofluorenyl, 9,9-diphenylbenzofluorenyl, benzospirodifluorenyl, benzofuranyl, etc. Dibenzofuranyl, naphthobenzofuranyl, dinaphthofuranyl, benzothiophenyl, dibenzothiophenyl, naphthobenzothiophenyl, carbazoyl, N-phenylcarbazoyl, benzocarbazoyl, N-phenylbenzocarbazoyl, dibenzocarbazoyl, N-biphenylcarbazoyl, benzoxazoleyl, naphthoxazoleyl, phenanthrenexazoleyl, phenanthrenebenzofuranyl, benzofuran-benzofuranyl, N-phenylbenzofuran-carbazoyl;

[0071] Wherein, the substituents in the substituted A group are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl; and / or;

[0072] Preferably, in formula A-1, L 1 L 2 Whether the groups are the same or different, each group is independently selected from single-bonded, substituted or unsubstituted B groups, wherein the B groups are selected from: phenylene, naphthylene, phenanthrene, binatrimethylene, dibenzofuranyl, dibenzothiophene, benzonaphthiophene, and benzonaphthiophene.

[0073] Wherein, the substituents in the substituted B group are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 arylamine, and C3-C60 heteroarylamine; and / or,

[0074] Preferred, R 6 R 7 R 8 R 9 Each group is independently selected from deuterium, halogen, cyano, substituted or unsubstituted C groups; wherein the C group is selected from: phenyl, naphthyl, pyridyl, quinolinyl, isoquinolinyl, phenanthrene, anthracene, fluoranyl, pyrene, biphenyl, binatyl, terphenyl, phenylnaphthyl, naphthylphenyl, triphenylene, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirodifluorenyl, 9,9-dimethylbenzofluorenyl, 9,9-diphenylbenzofluorenyl, benzene Spirodifluorenyl, benzofuranyl, dibenzofuranyl, naphthobenzofuranyl, dinaphthofuranyl, benzothiophenyl, dibenzothiophenyl, naphthobenzothiophenyl, carbazoyl, N-phenylcarbazoyl, benzocarbazoyl, N-phenylbenzocarbazoyl, dibenzocarbazoyl, biphenylcarbazoyl, benzoxazoleyl, naphthoxazoleyl, phenanthrenexazoleyl, phenanthrenebenzofuranyl, benzofuranobenzofuranyl, N-phenylbenzofuranocarbazoyl;

[0075] Wherein, the substituents in the substituted C group are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl.

[0076] More preferably, the substituents of the substituted A group, substituted B group, and substituted C group are each independently selected from one or a combination of at least two of the following: deuterium, halogen, cyano, methyl, ethyl, propyl, adamantyl, cyclopropane, cyclohexyl, cyclopentyl, phenyl, naphthyl, phenanthryl, phenylnaphthyl, naphthylphenyl, biphenyl, anthracene, fluorenyl, pyrene, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, benzonaphthiofuranyl, benzonaphthiophene, carbazole, and benzocarbazole.

[0077] Preferably, n1 and n3 are each independently selected from integers from 0 to 6.

[0078] Preferably, n1 and n3 are each independently selected from integers between 0 and 5.

[0079] Preferably, n1, n2, and n3 are each independently selected from integers between 0 and 4.

[0080] Preferably, n1, n2, and n3 are each independently selected from integers between 0 and 3.

[0081] Preferably, n1, n2, and n3 are each independently selected from 0, 1, or 2.

[0082] Preferably, the fused-ring compound has the following structure:

[0083]

[0084]

[0085]

[0086]

[0087] The present invention also provides a method for synthesizing the compound shown in formula (1), the specific synthetic route of which is shown below:

[0088]

[0089] The present invention also provides an n-type charge generating material, which includes any one or a combination of at least two of the fused ring compounds described above.

[0090] The present invention also provides an electron transport material comprising any one or a combination of at least two of the fused ring compounds described above.

[0091] The present invention also provides a hole-blocking material, wherein the hole-blocking material comprises any one or a combination of at least two of the fused ring compounds described above.

[0092] The present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising a cathode, an anode, and an organic layer located between the cathode and the anode, the organic layer comprising any one or a combination of at least two of the fused ring compounds described above, the n-type charge generating material described above, the electron transport material described above, or the hole blocking material described above.

[0093] Preferably, the organic layer includes an n-type charge generation layer, which includes an n-type charge generation material as described above.

[0094] Preferably, the organic layer includes an electron transport layer, which includes an electron transport material as described above;

[0095] Preferably, the organic layer includes a hole-blocking layer, which includes a hole-blocking material as described above.

[0096] Preferably, the organic layer comprises one or more of a hole injection layer, a first organic light-emitting layer, a second organic light-emitting layer, and an electron injection layer;

[0097] Wherein, when the organic electroluminescent device includes an n-type charge generation layer, the n-type charge generation layer is located between the first organic light-emitting layer and the second organic light-emitting layer.

[0098] Preferably, the organic electroluminescent device may include an anode, a hole injection layer, a first hole transport layer, a first electron blocking layer, a first organic light-emitting layer, a first hole blocking layer, a first electron transport layer, an n-type charge generation layer, a p-type charge generation layer, a second hole transport layer, a second electron blocking layer, a second organic light-emitting layer, a second hole blocking layer, a second electron transport layer, an electron injection layer, and a cathode, all stacked together.

[0099] Preferably, the anode comprises an anode material, preferably a material with a large work function that facilitates hole injection into the first hole transport layer. For example, the anode material may include: metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline, but is not limited thereto.

[0100] More preferably, the anode is selected as indium tin oxide (ITO).

[0101] Preferably, the hole injection layer is used to enhance the ability to inject holes into the first hole transport layer. The hole injection layer can be selected from benzidine derivatives, starburst-like aryl amine compounds, phthalocyanine derivatives, or other materials; this application does not impose any special limitations on this. The material of the hole injection layer can, for example, be selected from the following compounds or any combination thereof:

[0102]

[0103]

[0104] Optionally, the first hole transport layer may include one or more hole transport materials. The first hole transport layer is a layer that receives holes from the first hole injection layer and transports the holes to the light-emitting layer. The hole transport layer material may be selected from carbazole polymers, carbazole-linked triarylamine compounds, or other types of compounds. This application does not impose any special limitations on this. The material of the first hole transport layer may, for example, be selected from the following compounds or any combination thereof:

[0105]

[0106]

[0107] More preferably, the first hole transport layer may be composed of HT-1.

[0108] Preferably, the material of the first electron blocking layer is selected from conventional materials used in the art. An electron blocking layer is a layer disposed between the light-emitting auxiliary layer and the light-emitting layer to prevent electrons injected from the cathode from transferring to the light-emitting auxiliary layer and recombinating in the light-emitting layer; it can also be called an electron blocking layer or an electron suppression layer. The electron blocking layer is preferably a material with a lower electron affinity than the electron transport layer. This application does not impose any special limitations in this regard.

[0109] More preferably, the first electron blocking layer may be composed of mCP.

[0110]

[0111] Preferably, the first organic light-emitting layer may include a blue light-emitting layer, a red light-emitting layer, or a green light-emitting layer, with a blue light-emitting layer being the most preferred. This application does not impose any special limitations on the blue light-emitting layer; conventional blue light-emitting layer materials in the art can be used. For example, the host material for blue light emission can be an anthracene derivative, and the guest material can be a boron nitride (BN) resonant fluorescent material.

[0112] More preferably, the first organic light-emitting layer is composed of the following materials:

[0113]

[0114] Preferably, the material of the first hole blocking layer is selected from conventional materials in the art. The hole blocking layer is a layer disposed between the electron transport layer and the light-emitting layer to prevent holes injected by the anode from being transferred to the electron transport layer and recombination in the light-emitting layer; it can also be referred to as a hole suppression layer or a hole blocking layer. The hole blocking layer is preferably made of a material with high ionization energy. This application does not impose any special limitations in this regard.

[0115] More preferably, the material of the first hole-blocking layer shown is selected from BCP or the fused ring compound described above.

[0116]

[0117] Preferably, the first electron transport layer can be a single-layer structure or a multi-layer structure, and it can include one or more electron transport materials. The first electron transport layer can be selected from, but is not limited to, benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives or other electron transport materials. This application does not impose any special restrictions on this.

[0118] More preferably, the first electron transport layer is composed of 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBI) and lithium octahydroxyquinoline (LiQ) or the fused-ring compound described above and lithium octahydroxyquinoline (LiQ).

[0119]

[0120] Preferably, the n-type charge generation layer may be composed of one or more of the compounds shown in formula (1) and the compounds shown in C-1-C-135.

[0121] Preferably, the p-type charge generation layer is not subject to any special restrictions and can be set in a conventional manner in the art and matched with the above-mentioned n-type charge generation layer.

[0122] More preferably, the p-type charge generation layer may be composed of HAT-CN and TCTA, and the ratio of them is not specially set in this application.

[0123] Preferably, the second hole transport layer is not subject to any special restrictions and can adopt conventional settings in the field, such as referring to the settings of the first hole transport layer.

[0124] Preferably, the second electron blocking layer is not subject to any special restrictions and can be set in a conventional manner in the art, such as referring to the setting of the first electron blocking layer.

[0125] Preferably, the second organic light-emitting layer may include a blue light-emitting layer, a red light-emitting layer, or a green light-emitting layer, with a blue light-emitting layer being the most preferred. This application does not impose any special limitations on the blue light-emitting layer; conventional blue light-emitting layer materials in the art can be used, for example, it can be configured similarly to the first organic light-emitting layer.

[0126] Preferably, the second hole blocking layer is not subject to any special restrictions and can adopt conventional settings in the field, such as referring to the settings of the first hole blocking layer.

[0127] Preferably, the second electron transport layer is not subject to any special restrictions and can adopt conventional settings in the field, such as referring to the settings of the first electron transport layer.

[0128] Preferably, the electron injection layer is used to enhance the ability to inject electrons into the second electron transport layer. The electron injection layer may include inorganic materials such as alkali metal sulfides and alkali metal halides, or may include complexes of alkali metals and organic materials.

[0129] More preferably, the electron-injected layer may include ytterbium (Yb).

[0130] Preferably, the cathode may comprise a cathode material that has a small work function and facilitates electron injection into the functional layers. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or multilayer materials such as LiF / Al, Liq / Al, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca.

[0131] More preferably, the cathode may include a metal electrode containing magnesium and silver as the cathode, and the ratio of these components is not specifically set in this application.

[0132] It should be noted that the above-mentioned organic electroluminescent devices are fabricated using conventional methods in the art, such as depositing layers on a substrate.

[0133] The present invention also provides an organic electroluminescent product, which includes the above-described organic electroluminescent device.

[0134] The present invention also provides an electronic device comprising the above-described fused ring compound.

[0135] Preferably, the electronic devices include perovskite photovoltaic devices, perovskite light-emitting devices, display devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic photodetectors, organic photoreceptors, organic field quenching devices, luminescent electrochemical cells, and organic laser diodes.

[0136] The above can be combined freely.

[0137] The beneficial effects of this invention are:

[0138] This invention provides a fused-ring compound with the structure of formula (1), which exhibits excellent thermal stability by defining the L and Ar groups as specific structures. When used as a charge-generating material, the N atom on the aromatic heterocycle in formula (1) can form a multi-coordinate structure with the metal atom. Simultaneously, this compound exhibits good energy level matching characteristics with the organic electroluminescent material of the adjacent functional layer. When such a fused-ring compound is used as a charge-generating layer, the corresponding stacked organic electroluminescent device exhibits high current efficiency, low driving voltage, and long lifetime. Attached Figure Description

[0139] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0140] Figure 1 This is a structural diagram of the stacked organic electroluminescent device in the device embodiment of the present invention;

[0141] 1-Anode, 2-Hole injection layer, 3-First hole transport layer, 4-First electron blocking layer, 5-First organic light-emitting layer, 6-First hole blocking layer, 7-First electron transport layer, 8-n-type charge generation layer, 9-p-type charge generation layer, 10-Second hole transport layer, 11-Second electron blocking layer, 12-Second organic light-emitting layer, 13-Second hole blocking layer, 14-Second electron transport layer, 15-Electron injection layer, 16-Cathode. Detailed Implementation

[0142] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0143] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0144] Synthesis of intermediates 1-3:

[0145]

[0146] Synthesis of intermediate 1-1: In a 2L single-necked flask, raw material a-1 (50.00 g, 0.19 mol), potassium hydroxide (31.98 g, 0.57 mol), and water (300 mL) were added. After reacting at 100 °C for 6 h, potassium permanganate aqueous solution (9.01 g, 57.0 mmol, dissolved in 600 mL of water) was added, and the reaction was carried out overnight at 100 °C. After the reaction was completed, dichloromethane (300 mL) was added. The reaction solution was filtered with diatomaceous earth to remove insoluble solids. The crude product was extracted with dichloromethane and evaporated to dryness to obtain intermediate 1-1 (yield 91.5%).

[0147] Synthesis of Intermediate 1-2: In a 1L three-necked flask, 2-bromobiphenyl (42.19 g, 0.18 mol) and tetrahydrofuran (200 mL) were added under nitrogen protection. Then, 75.84 mL of n-butyllithium-hexane solution (2.5 M, 0.19 mol) was added at -78°C. After restoring to 25°C, the reaction was allowed to proceed for 1 hour. Subsequently, Intermediate 1-1 (45.00 g, 0.17 mol) was added at -78°C, and the reaction was allowed to proceed overnight after restoring to 25°C. After the reaction was complete, saturated ammonium chloride aqueous solution was added to quench the reaction. The mixture was extracted with dichloromethane, and the organic layer was dried over anhydrous magnesium sulfate to remove the organic solvent, yielding the crude product Intermediate 1-2 (for direct use).

[0148] Synthesis of intermediates 1-3: In a 2L single-necked flask, crude intermediate 1-2 (60.00g), glacial acetic acid (300mL), and concentrated hydrochloric acid (30mL) were added. The mixture was reacted at 90℃ for 8 hours. After the reaction was completed, the mixture was cooled to precipitate a large amount of solid. The solid was then filtered to obtain intermediate 1-3 (two-step yield 66.2%).

[0149] 1.2 Synthesis of intermediate 36-3:

[0150]

[0151] Synthesis of intermediate 36-1: The synthesis method of intermediate 36-1 is the same as that of intermediate 1-1, except that the raw material a-1 is replaced with the raw material a-2, thus obtaining product intermediate 36-1 (yield 91.9%).

[0152] Synthesis of intermediate 36-2: The synthesis method of intermediate 36-2 is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced with intermediate 36-1, which yields crude product intermediate 36-2 (for direct use).

[0153] Synthesis of intermediate 36-3: The synthesis method of intermediate 36-3 is the same as that of intermediate 1-3, except that intermediate 1-2 is replaced with intermediate 36-2, thus obtaining intermediate 36-3 (two-step yield 65.9%).

[0154] Synthesis Examples

[0155] This embodiment provides the synthesis of compound C-1, specifically including the following steps.

[0156]

[0157] Synthesis of compound C-1: In a 250 mL three-necked flask under nitrogen protection, intermediate 1-3 (10.00 g, 25.17 mmol), starting material b-1 (11.51 g, 26.43 mmol), dioxane:water = 4:1 (120 mL: 30 mL), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (92 mg, 0.126 mmol), and potassium carbonate (8.68 g, 62.93 mmol) were added. The reaction was carried out overnight at 95 °C. After the reaction was completed, sufficient water was added to quench the reaction. The crude product solid was filtered and passed through a fast column chromatography with o-dichlorobenzene. Recrystallization from the column chromatography solution gave product C-1 (yield 53.5%).

[0158] Elemental analysis: C 44 H 27 Theoretical N5 values: C, 84.46; H, 4.35; N, 11.19; Measured values: C, 84.43; H, 4.36; N, 11.21; HRMS(ESI) m / z(M+): Theoretical value: 625.74, Measured value: 626.81.

[0159] The compounds shown in Table 1 were prepared using the same synthetic method as compound C-1, except that the starting material bx was replaced. Their elemental analysis is shown in Table 2.

[0160] Table 1 Synthesis of compound Cn

[0161]

[0162]

[0163] Table 2

[0164]

[0165] Device Example

[0166] The materials used to fabricate the following device embodiments or device comparative examples are shown in Table 3 below:

[0167] Table 3

[0168]

[0169] Device Example 1

[0170] This embodiment provides an organic electroluminescent device, such as... Figure 1As shown, it includes, in sequence, an anode 1, a hole injection layer 2, a first hole transport layer 3, a first electron blocking layer 4, a first organic light-emitting layer 5, a first hole blocking layer 6, a first electron transport layer 7, an n-type charge generation layer 8, a p-type charge generation layer 9, a second hole transport layer 10, a second electron blocking layer 11, a second organic light-emitting layer 12, a second hole blocking layer 13, a second electron transport layer 14, an electron injection layer 15, and a cathode 16. Its device structure is as follows: anode (indium tin oxide (ITO)), hole injection layer (HIL), first hole transport layer (HTL-1), first electron blocking layer (EBL-1), first organic light-emitting layer (EML-1), first hole blocking layer (HBL-1), first electron transport layer (ETL-1), n-type charge generation layer (CGL-n), p-type charge generation layer (CGL-p), second hole transport layer (HTL-2), second electron blocking layer (EBL-2), second organic light-emitting layer (EML-2), second hole blocking layer (HBL-2), second electron transport layer (ETL-2), electron injection layer (EIL), and cathode.

[0171] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0172] 1) Substrate cleaning:

[0173] The glass substrate coated with transparent ITO was ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤10wt%, triethanolamine ≤1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio of acetone and ethanol 1:1), baked in a clean environment until all moisture was removed, and then cleaned with ultraviolet light and ozone.

[0174] 2) Preparation of organic layer:

[0175] The ITO transparent substrate was transferred to an evaporation equipment and vacuumed to 1×10⁻⁶. -6 Up to 2×10 -4 Pa, in sequence, deposited on the ITO anode film the following layers: hole injection layer (HIL) / first hole transport layer (HTL-1) / first electron blocking layer (EBL-1) / first organic light-emitting layer (EML-1) / first hole blocking layer (HBL-1) / first electron transport layer (ETL-1) / n-type charge generation layer (CGL-n) / p-type charge generation layer (CGL-p) / second hole transport layer (HTL-2) / second electron blocking layer (EBL-2) / second organic light-emitting layer (EML-2) / second hole blocking layer (HBL-2) / second electron transport layer (ETL-2) / electron injection layer (EIL) / cathode (Mg:Ag mass ratio is 1:9).

[0176] in:

[0177] The anode is indium tin oxide (ITO, 10 nm thick);

[0178] The hole injection layer (HIL) is made of HAT-CN:TCTA (10 nm thick); the mass ratio of HATCN to TCTA is 3:97.

[0179] The material of the first hole transport layer (HTL-1) is TCTA (20nm thick);

[0180] The material of the first electron blocking layer (EBL-1) is mCP (5nm thick);

[0181] The first organic light-emitting layer (EML-1) is made of D and E in a mass ratio of 95:5 (thickness 20nm);

[0182] The material of the first hole blocking layer (HBL-1) is BCP (5nm thick);

[0183] The first electron transport layer (ETL-1) is made of TPBI and LiQ in a mass ratio of 1:1 (thickness 25nm);

[0184] The material of the n-type charge generation layer (CGL-n) is composed of compounds C-1 and Yb in the synthesis examples, and its specific ratio and thickness are shown in Table 4.

[0185] The p-type charge generation layer (CGL-p) is made of HAT-CN and TCTA in a mass ratio of 8:2 (thickness 10nm);

[0186] The material of the second hole transport layer (HTL-2) is TCTA (20nm thick);

[0187] The material of the second electron blocking layer (EBL-2) is mCP (5nm thick);

[0188] The second organic light-emitting layer (EML-2) is made of D and E in a mass ratio of 95:5 (thickness 20nm);

[0189] The material of the second hole blocking layer (HBL-2) is BCP (5nm thick);

[0190] The second electron transport layer (ETL-2) is made of TPBI and LiQ in a mass ratio of 1:1 (thickness 25nm);

[0191] The electron injection layer (EIL) is made of Yb (1 nm thick);

[0192] The cathode is made of Mg and Ag in a mass ratio of 1:9 (thickness 11 nm).

[0193] Device Example 2

[0194] Similar to Device Example 1, the difference is that compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-2.

[0195] Device Example 3

[0196] Similar to Device Example 1, the difference is that compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-3.

[0197] Device Example 4

[0198] Similar to Device Example 1, the difference is that compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-6.

[0199] Device Example 5

[0200] Similar to Device Example 1, the difference is that compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-8.

[0201] Device Example 6

[0202] Similar to Device Example 1, the difference is that compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-10.

[0203] Device Example 7

[0204] Similar to Device Example 1, the difference is that compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-36.

[0205] Device Example 8

[0206] Similar to Device Example 1, the difference is that compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-49.

[0207] Device Example 9

[0208] Similar to Device Example 1, the difference is that compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-53.

[0209] Device Comparison Example 1

[0210] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with the compound REF-1 shown below.

[0211]

[0212] Device Comparison Example 2

[0213] Similar to Device Example 1, the difference is that compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound REF-2 as shown below.

[0214]

[0215] Table 4. Composition and thickness of n-type charge generation layer

[0216] Example n-type charge generation layer / thickness Device Example 1 C-1:Yb (mass ratio 95:5) / 10nm Device Example 2 C-2:Yb (mass ratio 95:5) / 10nm Device Example 3 C-3:Yb (mass ratio 95:5) / 10nm Device Example 4 C-6:Yb (mass ratio 95:5) / 10nm Device Example 5 C-8:Yb (mass ratio 95:5) / 10nm Device Example 6 C-10: Yb (mass ratio 95:5) / 10nm Device Example 7 C-36:Yb (mass ratio 95:5) / 10nm Device Example 8 C-49: Yb (mass ratio 95:5) / 10nm Device Example 9 C-53: Yb (mass ratio 95:5) / 10nm Device Comparison Example 1 REF-1: Yb (mass ratio 95:5) / 10nm Device Comparison Example 2 REF-2: Yb (mass ratio 95:5) / 10nm

[0217] The organic electroluminescent devices obtained in Device Examples 1-9 and Device Comparative Examples 1-2 in the device examples were tested.

[0218] Instruments: The current, voltage, brightness, emission spectrum and other characteristics of the device were tested simultaneously using a PR 650 spectral scanning luminance meter and a Keithley K 2400 digital source meter system;

[0219] Photoelectric property test conditions: current density 10 mA / cm² 2 , room temperature.

[0220] Lifetime test conditions: current density 10 mA / cm² 2 The recording time (in hours) is when the device brightness drops to 95% of its original brightness.

[0221] In Table 5, the lifetime T95 and current efficiency of device comparative example 1 are set to 100. The lifetime T95 and current efficiency of the other device embodiments and device comparative examples in Table 5 are relative values ​​to these values.

[0222] Table 5. Device performance parameters for Device Examples 1-9 and Device Comparative Examples 1 and 2.

[0223]

[0224]

[0225] Device Example 10

[0226] This embodiment provides an organic electroluminescent device, comprising, in sequence, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode. The device structure is as follows: anode (indium tin oxide (ITO)), hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), emissive layer (EML), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL), and cathode.

[0227] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0228] 1) Substrate cleaning:

[0229] The glass substrate coated with transparent ITO was ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤10wt%, triethanolamine ≤1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio of acetone and ethanol 1:1), baked in a clean environment until all moisture was removed, and then cleaned with ultraviolet light and ozone.

[0230] 2) Preparation of organic layer:

[0231] The ITO transparent substrate was transferred to an evaporation equipment and vacuumed to 1×10⁻⁶. -6 Up to 2×10 -4 Pa, hole injection layer (HIL) / hole transport layer (HTL-1) / electron blocking layer (EBL-1) / light emitting layer (EML-1) / hole blocking layer (HBL-1) / electron transport layer (ETL-1) / electron injection layer (EIL) / cathode are sequentially deposited on the ITO anode film.

[0232] in:

[0233] The anode is indium tin oxide (ITO, 10 nm thick);

[0234] The hole injection layer (HIL) is made of HAT-CN:TCTA (10 nm thick); the mass ratio of HATCN to TCTA is 3:97.

[0235] The hole transport layer (HTL) is made of TCTA (20 nm thick);

[0236] The electron blocking layer (EBL) is made of mCP (5 nm thick);

[0237] The materials of the light-emitting layer (EML) are D and E, with a mass ratio of 95:5 (thickness 20nm);

[0238] The hole blocking layer (HBL) is made of compound C-1 (5 nm thick) from synthesis example 1;

[0239] The electron transport layer (ETL) is made of TPBI and LiQ in a mass ratio of 1:1 (thickness 25nm);

[0240] The electron injection layer (EIL) is made of Yb (1 nm thick);

[0241] The cathode is made of Mg and Ag in a mass ratio of 1:9 (thickness 11 nm).

[0242] Device Example 11

[0243] Similar to Device Example 10, the difference is that compound C-1 in the hole blocking layer of Device Example 10 is replaced with compound C-3.

[0244] Device Example 12

[0245] Similar to Device Example 10, the difference is that compound C-1 in the hole blocking layer of Device Example 10 is replaced with compound C-8.

[0246] Device Example 13

[0247] Similar to Device Example 10, the difference is that compound C-1 in the hole blocking layer of Device Example 10 is replaced with compound C-36.

[0248] Device Comparison Example 3

[0249] Similar to Device Example 10, the difference is that compound C-1 in the hole blocking layer of Device Example 10 is replaced with compound BCP.

[0250] The organic electroluminescent devices obtained in Device Examples 10-13 and Device Comparative Example 3 were tested.

[0251] Instruments: The current, voltage, brightness, emission spectrum and other characteristics of the device were tested simultaneously using a PR 650 spectral scanning luminance meter and a Keithley K2400 digital source meter system;

[0252] Photoelectric property test conditions: current density 10 mA / cm² 2 , room temperature.

[0253] Lifetime test conditions: current density 10 mA / cm² 2 The recording time (in hours) is when the device brightness drops to 95% of its original brightness.

[0254] The test results are shown in Table 6.

[0255] In Table 6, the lifetime T95 and current efficiency of the device comparative example 3 are set to 100. The lifetime T95 and current efficiency of the other device examples in Table 6 are relative values ​​to it.

[0256] Table 6. Device performance parameters for Device Examples 10-13 and Device Comparative Example 3.

[0257] Example Drive voltage (V) Current efficiency Relative lifespan T95 Device Example 10 3.52 107.97 112.7 Device Example 11 3.50 107.81 111.6 Device Example 12 3.57 105.52 109.3 Device Example 13 3.58 105.07 107.2 Device Comparison Example 3 4.41 100 100

[0258] Device Example 14

[0259] This embodiment provides an organic electroluminescent device, comprising, in sequence, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode. The device structure is as follows: anode (indium tin oxide (ITO)), hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), emissive layer (EML), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL), and cathode.

[0260] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0261] 1) Substrate cleaning:

[0262] The glass substrate coated with transparent ITO was ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤10wt%, triethanolamine ≤1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio of acetone and ethanol 1:1), baked in a clean environment until all moisture was removed, and then cleaned with ultraviolet light and ozone.

[0263] 2) Preparation of organic layer:

[0264] The ITO transparent substrate was transferred to an evaporation equipment and vacuumed to 1×10⁻⁶. -6 Up to 2×10 -4 Pa, hole injection layer (HIL) / hole transport layer (HTL-1) / electron blocking layer (EBL-1) / light emitting layer (EML-1) / hole blocking layer (HBL-1) / electron transport layer (ETL-1) / electron injection layer (EIL) / cathode are sequentially deposited on the ITO anode film.

[0265] in:

[0266] The anode is indium tin oxide (ITO, 10 nm thick);

[0267] The hole injection layer (HIL) is made of HAT-CN:TCTA (10 nm thick); the mass ratio of HAT-CN to TCTA is 3:97.

[0268] The hole transport layer (HTL) is made of TCTA (20 nm thick);

[0269] The electron blocking layer (EBL) is made of mCP (5 nm thick);

[0270] The materials of the light-emitting layer (EML) are D and E, with a mass ratio of 95:5 (thickness 20nm);

[0271] The hole blocking layer (HBL) is made of BCP (5nm thick);

[0272] The electron transport layer (ETL) is made of compounds C-1 and LiQ in the synthesis example, with a mass ratio of 1:1 (thickness 25 nm).

[0273] The electron injection layer (EIL) is made of Yb (1 nm thick);

[0274] The cathode is made of Mg and Ag in a mass ratio of 1:9 (thickness 11 nm).

[0275] Device Example 15

[0276] Similar to Device Example 14, except that compound C-1 in the electron transport layer of Device Example 14 is replaced with compound C-6.

[0277] Device Example 16

[0278] Similar to Device Example 14, except that compound C-1 in the electron transport layer of Device Example 14 is replaced with compound C-53.

[0279] Device Comparison Example 4

[0280] Similar to Device Example 14, the difference is that compound C-1 in the electron transport layer of Device Example 14 is replaced with compound TPBI.

[0281] The organic electroluminescent devices obtained in Device Examples 14-16 and Device Comparative Example 4 were tested.

[0282] Instruments: The current, voltage, brightness, emission spectrum and other characteristics of the device were tested simultaneously using a PR 650 spectral scanning luminance meter and a Keithley K 2400 digital source meter system;

[0283] Photoelectric property test conditions: current density 10 mA / cm² 2 , room temperature.

[0284] Lifetime test conditions: current density 10 mA / cm² 2 The recording time (in hours) is when the device brightness drops to 95% of its original brightness.

[0285] The test results are shown in Table 7:

[0286] In Table 7, the lifetime T95 and current efficiency of device embodiments 14-16 relative to device comparative example 4 are set to 100. The lifetime T95 and current efficiency of the other device embodiments in Table 7 are relative values.

[0287] Table 7. Device performance parameters for Device Examples 14-16 and Device Comparative Example 4.

[0288] Example Drive voltage (V) Current efficiency (cd / A) Relative lifespan T95(h) Device Example 14 3.53 108.67 114.9 Device Example 15 3.51 108.27 112.3 Device Example 16 3.72 105.21 107.1 Device Comparison Example 4 4.32 100 100

[0289] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A fused-ring compound, characterized in that, It has the structure shown in equation (1): In equation (1), L is selected from single bond, substituted or unsubstituted C6-C60 arylene, or substituted or unsubstituted C1-C60 heteroarylene; Ar is selected from the structure shown in formula A: In formula A, X1 is selected from N or CR 1 X2 is selected from N or CR 2 X3 is selected from N or CR 3 X4 is selected from N or CR 4 X5 is selected from N or CR 5 ; R 1 R 2 R 3 R 4 R 5 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; R 1 R 2 R 3 R 4 R 5 They exist independently, or adjacent pairs are connected to form substituted or unsubstituted C6-C60 aromatic rings, or substituted or unsubstituted C3-C60 heteroaromatic rings; The substituents of the substituted C6-C60 arylene, substituted C1-C60 heteroarylene, substituted C1-C60 alkyl, substituted C3-C60 cycloalkyl, substituted C6-C60 aryl, substituted C3-C60 heteroarylene, substituted C6-C60 aromatic ring, and substituted C3-C60 heteroarylene ring are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroarylene.

2. The organic compound according to claim 1, characterized in that, Formula A is selected from one of Formula A-1, Formula A-2, and Formula A-3: In formula A-1: Ar 1 Ar 2 Each is independently selected from substituted or unsubstituted C6-C60 aryl groups, or substituted or unsubstituted C3-C60 heteroaryl groups; L 1 L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C60 arylene, or substituted or unsubstituted C3-C60 heteroarylene; In formula A-2: R 6 Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; n1 is any integer from 0 to 7, and when n1 is equal to or greater than 2, R 6 They are the same or different; In formula A-3: Z 1 -Z 4 Each is independently selected from N or CR 8 ; R 7 R 8 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; The substituents of the substituted C1-C60 alkyl, substituted C3-C60 cycloalkyl, substituted C6-C60 aryl, and substituted C3-C60 heteroaryl are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl. n2 is any integer from 0 to 4, and when n2 is equal to or greater than 2, R 7 They are the same or different; Preferably, Z in formula A-3 1 -Z 4 At least one of them is selected from N; Preferably, formula A-3 is selected from any one of formulas A-3-1 to A-3-3: R 9 Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; n3 is any integer from 0 to 7, and when n3 is equal to or greater than 2, R 9 They are the same or different; The substituents of the substituted C6-C60 arylene, substituted C1-C60 heteroarylene, substituted C1-C60 alkyl, substituted C3-C60 cycloalkyl, substituted C6-C60 aryl, and substituted C3-C60 heteroarylene are selected from one or a combination of at least two of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroarylene.

3. The fused-ring compound according to claim 2, characterized in that, Ar 1 Ar 2 Each is independently selected from substituted or unsubstituted C6-C30 aryl groups or substituted or unsubstituted C3-C30 heteroaryl groups; The substituents of the substituted C6-C30 aryl and substituted C3-C30 heteroaryl are selected from one or a combination of two or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl. Preferably, L 1 L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C30 arylene, or substituted or unsubstituted C3-C30 heteroarylene; The substituents in the substituted C6-C30 arylene and substituted C3-C30 heteroarylene are selected from one or more combinations of deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroarylene. Preferred, R 6 R 7 R 8 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from one or a combination of two or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl.

4. The fused-ring compound according to any one of claims 1-3, characterized in that, Ar 1 Ar 2 Each group is independently selected from substituted or unsubstituted A groups, wherein the A group is selected from: phenyl, naphthyl, phenanthryl, anthracene, fluoranyl, pyrene, biphenyl, binatyl, terphenyl, phenylnaphthyl, naphthylphenyl, triphenylene, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirodifluorenyl, 9,9-dimethylbenzofluorenyl, 9,9-diphenylbenzofluorenyl, benzospirodifluorenyl, benzofuranyl, etc. Dibenzofuranyl, naphthobenzofuranyl, dinaphthofuranyl, benzothiophenyl, dibenzothiophenyl, naphthobenzothiophenyl, carbazoyl, N-phenylcarbazoyl, benzocarbazoyl, N-phenylbenzocarbazoyl, dibenzocarbazoyl, N-biphenylcarbazoyl, benzoxazoleyl, naphthoxazoleyl, phenanthrenexazoleyl, phenanthrenebenzofuranyl, benzofuran-benzofuranyl, N-phenylbenzofuran-carbazoyl; Wherein, the substituents in the substituted A group are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl. More preferably, each substituent in the substituted A group is independently selected from one or a combination of at least two of the following: deuterium, halogen, cyano, methyl, ethyl, propyl, adamantyl, cyclopropane, cyclohexyl, cyclopentyl, phenyl, naphthyl, phenanthryl, phenylnaphthyl, naphthylphenyl, biphenyl, anthracene, fluorenyl, pyrene, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, benzonaphthiofuranyl, benzonaphthiophene, carbazole, and benzocarbazole. Preferred, L 1 L 2 Whether the groups are the same or different, each group is independently selected from single-bonded, substituted or unsubstituted B groups, wherein the B groups are selected from: phenylene, naphthylene, phenanthrene, binatrimethylene, dibenzofuranyl, dibenzothiophene, benzonaphthiophene, and benzonaphthiophene. Wherein, the substituents in the substituted B group are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl. More preferably, the substituents in the substituted B group are each independently selected from one or a combination of at least two of the following: deuterium, halogen, cyano, methyl, ethyl, propyl, adamantyl, cyclopropane, cyclohexyl, cyclopentyl, phenyl, naphthyl, phenanthryl, phenylnaphthyl, naphthylphenyl, biphenyl, anthracene, fluorenyl, pyrene, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, benzonaphthiofuranyl, benzonaphthiophene, carbazole, and benzocarbazole. Preferred, R 6 R 7 R 8 R 9 Each group is independently selected from deuterium, halogen, cyano, substituted or unsubstituted C groups; wherein the C group is selected from: phenyl, naphthyl, pyridyl, quinolinyl, isoquinolinyl, phenanthrene, anthracene, fluoranyl, pyrene, biphenyl, binatyl, terphenyl, phenylnaphthyl, naphthylphenyl, triphenylene, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirodifluorenyl, 9,9-dimethylbenzofluorenyl, 9,9-diphenylbenzofluorenyl, benzene Spirodifluorenyl, benzofuranyl, dibenzofuranyl, naphthobenzofuranyl, dinaphthofuranyl, benzothiophenyl, dibenzothiophenyl, naphthobenzothiophenyl, carbazoyl, N-phenylcarbazoyl, benzocarbazoyl, N-phenylbenzocarbazoyl, dibenzocarbazoyl, biphenylcarbazoyl, benzoxazoleyl, naphthoxazoleyl, phenanthrenexazoleyl, phenanthrenebenzofuranyl, benzofuranobenzofuranyl, N-phenylbenzofuranocarbazoyl; Wherein, the substituents in the substituted C group are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl. More preferably, the substituents in the substituted A group are each independently selected from one or a combination of at least two of the following: deuterium, halogen, cyano, methyl, ethyl, propyl, adamantyl, cyclopropane, cyclohexyl, cyclopentyl, phenyl, naphthyl, phenanthryl, phenylnaphthyl, naphthylphenyl, biphenyl, anthracene, fluorenyl, pyrene, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, benzonaphthiofuranyl, benzonaphthiophene, carbazole, and benzocarbazole.

5. The fused-ring compound according to any one of claims 1-4, characterized in that, The compound has the following structure:

6. An n-type charge-generating material, characterized in that, The n-type charge-generating material includes any one or a combination of at least two of the fused-ring compounds as described in any one of claims 1-5.

7. An electron transport material, characterized in that, The electron transport material comprises any one or a combination of at least two of the fused ring compounds as described in any one of claims 1-5.

8. A hole-blocking material, characterized in that, The hole-blocking material comprises any one or a combination of at least two of the fused ring compounds as described in any one of claims 1-5.

9. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a cathode, an anode, and an organic layer located between the cathode and the anode. The organic layer includes any one or a combination of at least two of the fused ring compounds according to any one of claims 1-5, the n-type charge generating material according to claim 6, the electron transport material according to claim 7, or the hole blocking material according to claim 8. Preferably, the organic layer includes an n-type charge generation layer, and the n-type charge generation layer includes the n-type charge generation material as described in claim 6; Preferably, the organic layer includes an electron transport layer, and the electron transport layer includes the electron transport material as described in claim 7; Preferably, the organic layer includes a hole-blocking layer, which includes the hole-blocking material as described in claim 8.

10. The application of a fused ring compound as described in any one of claims 1-5, an n-type charge-generating material as described in claim 6, an electron transport material as described in claim 7, a hole-blocking material as described in claim 8, or an organic electroluminescent device as described in claim 9 in optical fiber equipment, lighting equipment, electrophotographic photosensitive equipment, photoelectric converters, organic solar cells, switching element equipment, organic light-emitting field-effect transistors, image sensors, or dye lasers.

Images