Condensed ring compound and application thereof

Abstract

The invention relates to the technical field of organic electroluminescence, in particular to a fused ring compound and application thereof.The fused ring compound has the structure shown in the formula (1), and an organic electroluminescence device containing the organic electroluminescence compound can have low driving voltage, high current efficiency and long service life.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic electroluminescence, and particularly relates to a fused ring compound and application thereof. BACKGROUND

[0002] Organic light-emitting materials can be roughly divided into light-emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials, etc. according to functions. An organic light-emitting diode (OLED) is a device driven by electric current to achieve light-emitting purposes, which has the advantages of lightness, flexibility, high contrast, wide color gamut, etc. Due to high current efficiency and long service life, a stacked OLED has gradually become a research direction, which mainly includes a first light-emitting stack, a second light-emitting stack, and a charge generation layer (CGL) disposed between the first light-emitting stack and the second light-emitting stack to ensure that charges are effectively distributed to the light-emitting stack and improve the current efficiency in each light-emitting layer. However, most of the existing stacked materials have a low matching degree of the charge generation layer, resulting in problems of high driving voltage, low luminous efficiency, and short service life of the organic electroluminescent device containing the organic electroluminescent material, which seriously limits the application of the organic electroluminescent device.

[0003] Therefore, further research in this field is needed to improve the performance of the organic electroluminescent device. SUMMARY

[0004] The present application aims to overcome the problems of high driving voltage, low service life, and low current efficiency of the organic electroluminescent device caused by the application of the existing organic electroluminescent compound in the organic electroluminescent device, thereby improving a fused ring compound and application thereof.

[0005] In a first aspect, the present application provides a fused ring compound having the structure shown in the following formula (1):

[0006]

[0007] In the formula,

[0008] R 1 , R 2 , and R 3 are the same or different and each is independently selected from hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C1-C60 heteroaryl group;

[0009] a, b, and c are the same or different and are integers, and satisfy: 0≤a≤7 and 0≤b≤3 and 0≤c≤2;

[0010] and the substituents in the substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amidino, hydrazino, C1-C60 alkyl, C2-C60 alkenyl, C3-C60 cycloalkyl, C2-C60 alkynyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C3-C60 cycloalkenyl, C1-C60 heterocycloalkenyl, C6-C60 aryl, C1-C60 heteroaryl.

[0011] In a second aspect, the present application provides an n-type charge generation layer, wherein the n-type charge generation layer material comprises any one or a combination of at least two of the fused ring compounds described above.

[0012] In a third aspect, the present application provides an electron transport layer, wherein the electron transport layer material comprises any one or a combination of at least two of the fused ring compounds described above.

[0013] In a fourth aspect, the present application provides an organic electroluminescent device, comprising a cathode, an anode, and an organic layer between the cathode and the anode, wherein the organic layer comprises any one or a combination of at least two of the fused ring compounds described above.

[0014] Advantages of the present application:

[0015] The compound of the present application has a structure of formula (1), comprising a quinoxaline and phenanthroline parent nucleus structure, and limiting other substituent groups. On the one hand, the exposed N on the quinoxaline and the two Ns on the phenanthroline in the compound having the structure of formula (1) coordinate better to fix the metal, which can improve the lifetime and current efficiency of the organic electroluminescent device when applied to the organic electroluminescent device. On the other hand, the planar structure of the quinoxaline and the phenanthroline in the compound having the structure of formula (1) can enhance the packing and the charge transport, thereby improving the current efficiency and significantly improving the lifetime of the organic electroluminescent device.

[0016] Further, in the present application, when R1, R2, and R3 are aryl or heteroaryl, the high coordination of the nitrogen atom on the phenanthroline group is utilized, so that when used in a metal-doped layer, the metal coordination is higher, and thus a stable layer can be formed, thereby further reducing the driving voltage and further improving the device lifetime. Further, when the compound has aryl or heteroaryl at least in R1 and R3, the heat resistance of the compound can be further improved, i.e., the compound has a higher glass transition temperature, thereby synergistically improving the lifetime of the organic electroluminescent device. BRIEF DESCRIPTION OF DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the specific embodiments of the present application or the prior art, the accompanying drawings needed to be used in the specific embodiments or prior art description will be briefly introduced as follows. Obviously, the accompanying drawings in the following description are some embodiments of the present application, and for those skilled in the art, other drawings can also be obtained without creative labor based on these drawings.

[0018] Figure 1 Structure diagram of the stacked organic electroluminescent device in the device embodiment of the present application;

[0019] 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 DESCRIPTION

[0020] The following embodiments are provided in order to better further understand the present application, and are not limited to the best embodiments, and do not limit the content and protection scope of the present application, and any person under the inspiration of the present application or the combination of the present application with other prior art features, any product same or similar to the present application, falls within the protection scope of the present application.

[0021] In a first aspect, the embodiments of the present application provide a fused ring compound having the structure shown in the following formula (1):

[0022]

[0023] In the formula, R

[0024] R 1 , R 2 , R 3 are the same or different and each is independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C1-C60 heteroaryl;

[0025] a, b, and c are the same or different and are integers, and satisfy: 0≤a≤7 and 0≤b≤3 and 0≤c≤2;

[0026] and the substituents in the substituted C6-C60aryl, substituted C1-C60heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amidino, hydrazino, C1-C60alkyl, C2-C60alkenyl, C3-C60cycloalkyl, C2-C60alkynyl, C3-C60cycloalkyl, C1-C60heterocycloalkyl, C3-C60cycloalkenyl, C1-C60heterocycloalkenyl, C6-C60aryl, C1-C60heteroaryl.

[0027] In the present application, the term "substituent" has its generally accepted meaning in the art and refers to a chemical moiety covalently attached to or, where appropriate, fused to a parent core group.

[0028] In the present application, the term "substituted or unsubstituted" means that the functional group recited after this term can or can not have a substituent (hereinafter, the substituents will be collectively referred to as Rcfor the sake of convenience of description). For example, "substituted or unsubstituted aryl" means aryl having a substituent Rc, or non-substituted aryl. The aforementioned substituent Rc, for example, can be one or a combination of at least two of deuterium, halogen, cyano, C1-C12alkyl, C3-C12cycloalkyl, C6-C30aryl, C1-C60heteroaryl, C6-C60arylamino, C3-C60heteroarylamino, for example, deuterium, halogen, cyano, alkyl, haloalkyl, trialkylsilyl, deuterated alkyl, aryl, heteroaryl, and the like. Of course, the number of substituents Rcmay be one or more. When two substituents Rcare attached to the same atom, the two substituents Rcmay exist independently or be connected to each other to form a ring with the atom; when two substituents Rcexist adjacently on a functional group, the two adjacent substituents Rcmay exist independently or be fused to the functional group to which they are attached to form a ring.

[0029] In the present application, the term "alkyl" whether used alone or as part of another term, refers to a saturated hydrocarbon group, which can be straight or branched. The term "C1-C60alkyl" is derived from a monovalent substituent of a straight or branched saturated hydrocarbon having from 1 to 60 carbon atoms, preferably from 1 to 40 carbon atoms, and more preferably from 1 to 20 carbon atoms, and examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, and hexyl.

[0030] In the present application, the term "alkenyl" whether used alone or as part of another term, refers to a saturated hydrocarbon group that can be straight-chain or branched and has at least one carbon-carbon double bond. The term "C2-C60alkenyl" refers to an alkenyl group having from 2 to 60 carbon atoms, preferably from 1 to 40 carbon atoms, and more preferably from 1 to 20 carbon atoms, of course, the alkenyl group includes but is not limited to ethenyl, n-propenyl, iso-propenyl, n-butenyl, sec-butenyl, and the like.

[0031] In the present application, the term "alkynyl" whether used alone or as part of another term, refers to a saturated alkynyl group that can be straight-chain or branched and has at least one carbon-carbon triple bond. The term "C2-C60alkynyl" refers to an alkynyl group having from 2 to 60 carbon atoms, preferably from 2 to 40 carbon atoms, and more preferably from 2 to 20 carbon atoms, of course, the alkynyl group includes but is not limited to ethynyl, propynyl, and the like.

[0032] In the present application, the term "C3-C60cycloalkyl" refers to a cyclic ring system alkyl group consisting of at least 3 atoms, further, refers to a monocyclic or polycyclic hydrocarbon having from 3 to 60 ring backbone carbon atoms, preferably from 3 to 40 carbon atoms, and more preferably from 3 to 20 carbon atoms, of course, the cycloalkyl group includes but is not limited to cyclopropyl, cyclobutyl, adamantyl, and the like.

[0033] In the present application, the term "C1-C60heterocycloalkyl" includes one or more of O, S, Se, N, and Si as a heteroatom, and a monocyclic or polycyclic ring having from 1 to 60 carbon atoms, preferably from 1 to 40 carbon atoms, and more preferably from 1 to 20 carbon atoms, here, the polycyclic ring refers to a group in which the heterocycloalkyl group is directly connected to another ring group or fused with another ring group. Here, the other ring group can also be a heterocycloalkyl group, but can also be another ring group, for example, a cycloalkyl group, an aryl group, a heteroaryl group, and the like.

[0034] In the present application, the term "C3-C60cycloalkenyl" refers to a cyclic ring system alkenyl group consisting of at least 3 atoms, further, refers to a monocyclic or polycyclic hydrocarbon having from 3 to 60 ring backbone carbon atoms, preferably from 3 to 40 carbon atoms, and more preferably from 3 to 20 carbon atoms.

[0035] In the present application, the term "C1-C60heterocycloalkenyl" includes one or more of O, S, Se, N, and Si as a heteroatom, and a monocyclic or polycyclic ring having from 1 to 60 carbon atoms, preferably from 1 to 40 carbon atoms, and more preferably from 1 to 20 carbon atoms, here.

[0036] In the present application, the term "aryl" and "arylene" includes monocyclic, polycyclic or fused ring aryl, which can be interrupted by short non-aromatic units between the rings, and can contain a spiro structure, aryl includes but is not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, spirobifluorenyl, etc., arylene includes but is not limited to phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthrylene, fluorenylene, spirobifluorenylene, etc., wherein arylene refers to a divalent or multivalent group formed by further losing one or more hydrogen atoms from aryl.

[0037] In the present application, the term "heteroaryl" includes monocyclic, polycyclic or fused ring heteroaryl, which can be interrupted by short non-aromatic units between the rings, and the heteroatom includes nitrogen, oxygen, sulfur. Heteroaryl includes but is not limited to furanyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoaxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof, etc.; heteroarylene includes but is not limited to furanylene, thiophenylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, tetrazolylene, furazanylene, pyridylene, pyrazinylyene, pyrimidinylyene, pyridazinylyene, benzofuranylene, benzothiophenylene, isobenzofuranylene, dibenzofuranylene, dibenzothiophenylene, benzimidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoaxazolylene, isoindolylene, indolylene, indazolylene, benzothiadiazolylene, quinolinylene, isoquinolinylene, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, phenoxazinylene, phenothiazinylene, phenanthridinylene, benzodioxolylyene, dihydroacridinylene, and derivatives thereof, etc. As used in the present application, the term "substituted" means that a hydrogen atom in the compound is substituted by another substituent. The position is not limited to a specific position, as long as the hydrogen at the position can be substituted by the substituent. When two or more substituents appear, the two or more substituents can be the same or different.

[0038] In the present application, fluorenyl can be substituted by one or more substituents, and when the above-mentioned fluorenyl is substituted, the substituted fluorenyl can be: etc., but not limited thereto.

[0039] In the present application, the term "halogen" means an atom selected from fluorine, chlorine, bromine, iodine.

[0040] In the present application, unless otherwise specified, a hydrogen atom includes protium, deuterium and tritium.

[0041] In the present application, in the definition of the number of carbon atoms of a group, the number of carbon atoms is any integer within the defined range, for example, C6-C60 aryl, the number of carbon atoms of the aryl group can be any integer within the range of 6-60, 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.

[0042] In the present application, unless otherwise specified, a group that is not defined as substituted or unsubstituted means unsubstituted.

[0043] In the present application, 0≤a≤7 means that a is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7; 0≤b≤3 means that b is an integer selected from 0, 1, 2, 3; 0≤c≤2 means that a is an integer selected from 0, 1, 2.

[0044] In some alternative embodiments, the compound has a structure represented by the following formula (1-1), formula (1-2):

[0045]

[0046] In some alternative embodiments, the compound has a structure represented by the following formula (1-3) to formula (1-12):

[0047]

[0048]

[0049] In some preferred embodiments, the compound has a structure represented by the following formula (2-1) to formula (2-10):

[0050]

[0051]

[0052] In some alternative embodiments, R 1 , R 2 , R 3the same or different, and each independently selected from the group consisting of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C6-C50 aryl, substituted or unsubstituted C1-C50 heteroaryl; wherein substituted or unsubstituted C6-C50 aryl represents a substituted or unsubstituted aryl group having 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, or 50 carbon atoms, substituted or unsubstituted C1-C50 heteroaryl represents a substituted or unsubstituted heteroaryl group having 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, or 50 carbon atoms;

[0053] wherein the substituents in the substituted C6-C50 aryl, substituted C1-C50 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amidine, hydrazine, C1-C50 alkyl, C2-C50 alkenyl, C3-C50 cycloalkyl, C2-C50 alkynyl, C3-C50 cycloalkyl, C1-C50 heterocycloalkyl, C3-C50 cycloalkenyl, C1-C50 heterocycloalkenyl, C6-C50 aryl, C1-C50 heteroaryl.

[0054] In some alternative embodiments, R 1 , R 2 , R 3 are each independently selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amidine, hydrazine, C1-C50 alkyl, C2-C50 alkenyl, C3-C50 cycloalkyl, C2-C50 alkynyl, C3-C50 cycloalkyl, C1-C50 heterocycloalkyl, C3-C50 cycloalkenyl, C1-C50 heterocycloalkenyl, C6-C50 aryl, C1-C50 heteroaryl.

[0055] In some alternative embodiments, R 1 , R 2 , R 3 are the same or different, and each independently selected from the group consisting of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 heteroaryl.

[0056] In some alternative embodiments, R 1 , R2 each of the substituents of R 3 are each independently selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amidino, hydrazino, C1-C30alkyl, C2-C30alkenyl, C3-C30cycloalkyl, C2-C30alkynyl, C3-C30cycloalkyl, C1-C30heterocycloalkyl, C3-C30cycloalkenyl, C1-C30heterocycloalkenyl, C6-C30aryl, C1-C30heteroaryl.

[0057] In some alternative embodiments, R 1 each of the substituents of R 2 each of the substituents of R 3 are the same or different and each is independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C6-C25aryl, substituted or unsubstituted C1-C25heteroaryl.

[0058] In some alternative embodiments, R 1 each of the substituents of R 2 each of the substituents of R 3 are each independently selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amidino, hydrazino, C1-C25alkyl, C2-C25alkenyl, C3-C25cycloalkyl, C2-C25alkynyl, C3-C25cycloalkyl, C1-C25heterocycloalkyl, C3-C25cycloalkenyl, C1-C25heterocycloalkenyl, C6-C25aryl, C1-C25heteroaryl.

[0059] In some alternative embodiments, R 1 each of the substituents of R 2 each of the substituents of R 3the same or different, and each independently selected from deuterium, halogen, cyano, hydroxyl, nitro, amidino, hydrazino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted binaphthyl, substituted or unsubstituted phenylnaphthyl, substituted or unsubstituted naphthylphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenylfluorenyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted dibenzofluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted phenylphenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted indenyl, substituted or unsubstituted naphthacenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted tetracenyl, substituted or unsubstituted chrysenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted isothiazolyl, substituted or unsubstituted isoxazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted triazinyl, substituted or unsubstituted tetrazinyl, substituted or unsubstituted triazolyl, substituted or unsubstituted tetrazolyl, substituted or unsubstituted furazanyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzopyridyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzoimidazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzoisothiazolyl, substituted or unsubstituted benzoisoxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted isoindolyl, substituted or unsubstituted indolyl, substituted or unsubstituted indazolyl, substituted or unsubstituted benzothiadiazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted cinnolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenanthridinyl, substituted or unsubstituted bipyridinyl, substituted or unsubstituted terpyridinyl, substituted or unsubstituted phenylterpyridinyl, substituted or unsubstituted dibenzazolyl, or substituted or unsubstituted phenanthrolinyl.

[0060] In some optional embodiments, the substituents in the substituted groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amidino, hydrazino, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trideuteromethyl, trimethylsilyl, phenyl, naphthyl, biphenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl.

[0061] The substituents in the substituted groups that can be understood refer to substituted phenyl, substituted biphenyl, substituted triphenyl, substituted naphthyl, substituted binaphthyl, substituted phenylnaphthyl, substituted naphthylphenyl, substituted fluorenyl, substituted phenylfluorenyl, substituted benzo[a]fluorenyl, substituted dibenzo[a]fluorenyl, substituted phenanthryl, substituted phenylphenanthryl, substituted anthraceneyl, substituted indene, substituted tetraphenyl, substituted perylene, and substituted chloroform. Substituted tetraphenyl, substituted fluoranyl, substituted spirodifluorenyl, substituted furanyl, substituted phenylthio, substituted pyrroleyl, substituted imidazolyl, substituted pyrazolyl, substituted thiazolyl, substituted thiadiazolyl, substituted isothiazolyl, substituted isoxazolyl, substituted oxazolyl, substituted oxadiazolyl, substituted triazinyl, substituted tetraazinyl, substituted triazolyl, substituted tetrazolyl, substituted furazolidone, Substituted pyridyl, substituted pyrazinyl, substituted pyrimidinyl, substituted pyridazinyl, substituted benzofuranyl, substituted benzopyridyl, substituted benzothiopheneyl, substituted isobenzofuranyl, substituted dibenzofuranyl, substituted dibenzothiopheneyl, substituted benzimidazolyl, substituted benzothiazolyl, substituted benzoisothiazolyl, substituted benzoisooxazolyl, substituted benzooxazolyl, substituted isoindolyl, etc. The substituents in the following groups: substituted indolyl, substituted indazole, substituted benzothiadiazolyl, substituted quinolinyl, substituted isoquinolinyl, substituted cyclolinyl, substituted quinazolinyl, substituted quinoxalinyl, substituted carbazolyl, substituted phenoxazinyl, substituted phenthiazinyl, substituted phenanthidyl, substituted dipyridyl, substituted terpyridyl, substituted phenyl terpyridyl, substituted diazafluorenyl, or substituted phenanthrolinel.

[0062] In some alternative implementations, R 1 R 2 R 3 They may be the same or different, and each is independently selected from hydrogen, deuterium, or the group consisting of the following groups:

[0063]

[0064]

[0065] In some alternative implementations, R 1 R 2 R 3 The substituents are selected from one or more of deuterium, phenyl, naphthyl, biphenyl, and fluorenyl.

[0066] In some alternative implementations, R 1R is selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted binaphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenylfluorenyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted dibenzofluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted benzopyridyl, R 2 R is selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted binaphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenylfluorenyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted dibenzofluorenyl, substituted or unsubstituted phenanthrolinyl, R 3 R is selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted binaphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenylfluorenyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted dibenzofluorenyl, substituted or unsubstituted phenanthrolinyl, R

[0067] In some alternative embodiments, c = 2, and 0 < a < 2 and 0 < b < 2.

[0068] In some alternative embodiments, c = 2, and 0 < a < 2 and 0 < b < 1.

[0069] In some alternative embodiments, the fused ring compound is selected from the group consisting of the following structures:

[0070]

[0071]

[0072]

[0073]

[0074] Exemplary, the synthesis of the above-mentioned fused ring compound is specially described, but the actual synthesis process of the present disclosure is not limited by this.

[0075] For example, the synthesis route of the compound represented by formula (1-1) is designed as follows:

[0076] 1. Synthesis of intermediate 1-n

[0077]

[0078] 2. Synthesis of intermediate 2-n

[0079]

[0080] or:

[0081]

[0082] 3. Synthesis of the compound represented by formula (1-1)

[0083]

[0084] The synthetic route of the compound shown in formula (1-2) is designed as follows:

[0085]

[0086] In a second aspect, the present application provides an n-type charge generation material, which comprises any one or a combination of at least two of the above-mentioned fused ring compounds.

[0087] Preferably, the n-type charge generation material further comprises a metal material.

[0088] Preferably, the metal material comprises at least one of alkali metal, alkaline earth metal, transition metal.

[0089] Preferably, the metal material comprises at least one of lithium, ytterbium, silver.

[0090] Preferably, the mass ratio of the total mass of the fused ring compound to the mass of the metal material is (80-99):(1-10).

[0091] In a third aspect, the present application provides an electron transport layer, which comprises any one or a combination of at least two of the above-mentioned fused ring compounds.

[0092] In a fourth aspect, the present application provides an organic electroluminescent device, which comprises a cathode, an anode and an organic layer between the cathode and the anode, and the organic layer comprises any one or a combination of at least two of the above-mentioned fused ring compounds.

[0093] In some optional embodiments, the organic layer comprises the above-mentioned n-type charge generation layer and / or the above-mentioned electron transport layer.

[0094] In some optional embodiments, 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.

[0095] In some optional embodiments, 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.

[0096] In some specific embodiments, as Figure 1As shown, the organic electroluminescent device is a stacked organic electroluminescent device can include anode 1, hole injection layer 2, first hole transport layer 3, first electron blocking layer 4, first organic light emitting layer 5, first hole blocking layer 6, first electron transport layer 7, n-type charge generation layer 8, p-type charge generation layer 9, second hole transport layer 10, second electron blocking layer 11, second organic light emitting layer 12, second hole blocking layer 13, second electron transport layer 14, electron injection layer 15, cathode 16, which are arranged in a stack.

[0097] In an optional embodiment, the anode 1 comprises an anode material, which is preferably a material with a large work function that facilitates hole injection into the first hole transport layer 3. For example, the anode material can comprise a metal such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); a combination of a metal and an oxide such as ZnO:Al or SnO2:Sb; or a conductive polymer such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole and polyaniline, but is not limited thereto.

[0098] In a preferred embodiment, the anode 1 is selected to be indium tin oxide (ITO).

[0099] In an optional embodiment, the hole injection layer 2 is used to enhance the ability to inject holes into the first hole transport layer 3, and the hole injection layer 2 can be selected from a benzidine derivative, a starburst arylamine compound, a phthalocyanine derivative or other materials, which are not particularly limited in the present application. The material of the hole injection layer 2 can be selected from the following compounds or any combination thereof, for example:

[0100]

[0101]

[0102] Optionally, the first hole transport layer 3 can comprise one or more hole transport materials. The first hole transport layer 3 is a layer that receives holes from the first hole injection layer 2 and transports the holes to the light emitting layer. The hole transport layer material can be selected from a carbazole polymer, a carbazole-linked triarylamine compound or other types of compounds, which are not particularly limited in the present application. The material of the first hole transport layer 3 can be selected from the following compounds or any combination thereof, for example:

[0103]

[0104] In a preferred embodiment, the first hole transport layer 3 can consist of HT-1.

[0105] In an optional embodiment, the material of the first electron blocking layer 4 is selected from the conventional setting in the art, and the electron blocking layer means a layer arranged between the light-emitting auxiliary layer and the light-emitting layer to prevent the electrons injected from the cathode from being transferred to the light-emitting auxiliary layer without recombination in the light-emitting layer, which can also be referred to as an electron stopping layer or an electron inhibiting layer. The electron blocking layer is preferably a material having a smaller electron affinity than the electron transport layer. The present application does not make special limitations on this.

[0106] In a preferred embodiment, the first electron blocking layer 4 can be composed of mCP.

[0107]

[0108] In an optional embodiment, the first organic light-emitting layer 5 can include a blue light-emitting layer, a red light-emitting layer, or a green light-emitting layer, and is preferably a blue light-emitting layer. The present application does not make special limitations on the blue light-emitting layer, and a conventional blue light-emitting layer material in the art can be used, for example, the blue light-emitting host material can be selected from anthracene derivatives, and the guest material can be selected from B-N resonance type fluorescent materials.

[0109] In a preferred embodiment, the first organic light-emitting layer 5 is composed of the following materials:

[0110]

[0111] In an optional embodiment, the material of the first hole blocking layer 6 is selected from the conventional setting in the art, and the hole blocking layer is a layer arranged between the electron transport layer and the light-emitting layer to prevent the holes injected from the anode from being transferred to the electron transport layer without recombination in the light-emitting layer, which can also be referred to as a hole inhibiting layer or a hole stopping layer. The hole blocking layer is preferably a material having a high ionization energy. The present application does not make special limitations on this.

[0112] In a preferred embodiment, the material of the first hole blocking layer 6 is selected from BCP.

[0113]

[0114] In an optional embodiment, the first electron transport layer 7 can be a single-layer structure or a multi-layer structure, and can include one or more electron transport materials, which can be selected from, but not limited to, benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials, and the present application does not make special limitations on this.

[0115] In a preferred embodiment, the first electron transport layer 7 can be composed of 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBI) and lithium octahydroquinoline (LiQ).

[0116]

[0117] In an optional embodiment, the n-type charge generation layer 8 can be composed of one or more of the compounds represented by formula (1), the compounds represented by formula (1-1), the compounds represented by formula (1-2), and the compounds represented by N1 to N74.

[0118] In an optional embodiment, the p-type charge generation layer 9 is not particularly limited, and can be set according to the conventional setting in the art and matched with the n-type charge generation layer 8 described above.

[0119] In a preferred embodiment, the p-type charge generation layer 9 can be composed of HAT-CN and TCTA, and the proportion thereof is not particularly limited in the present application.

[0120] In an optional embodiment, the second hole transport layer 10 is not particularly limited, and can be set according to the conventional setting in the art, for example, can be set with reference to the first hole transport layer 3.

[0121] In an optional embodiment, the second electron blocking layer 11 is not particularly limited, and can be set according to the conventional setting in the art, for example, can be set with reference to the first electron blocking layer 4.

[0122] In an optional embodiment, the second organic light-emitting layer 12 can include a blue light-emitting layer, a red light-emitting layer, or a green light-emitting layer, and is preferably a blue light-emitting layer. The blue light-emitting layer is not particularly limited in the present application, and can be set according to the conventional blue light-emitting layer material in the art, for example, can be set with reference to the first organic light-emitting layer 5.

[0123] In an optional embodiment, the second hole blocking layer 13 is not particularly limited, and can be set according to the conventional setting in the art, for example, can be set with reference to the first hole blocking layer 6.

[0124] In an optional embodiment, the second electron transport layer 14 is not particularly limited, and can be set according to the conventional setting in the art, for example, can be set with reference to the first electron transport layer 7.

[0125] In an optional embodiment, the electron injection layer 15 is used to enhance the ability of injecting electrons into the second electron transport layer 14. The electron injection layer 15 can include inorganic materials such as alkali metal sulfides and alkali metal halides, or can include complexes of alkali metals and organic substances.

[0126] In a preferred embodiment, the electron injection layer 15 can include ytterbium (Yb).

[0127] In optional embodiments, the cathode 16 can include a cathode material that is a material with a small work function that facilitates the injection of electrons into the functional layer. 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 an alloy thereof; or multilayered materials such as LiF / Al, Liq / Al, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca.

[0128] In a preferred embodiment, the cathode 16 can include a metal electrode containing magnesium and silver as the cathode, and the present application does not set special proportion for it.

[0129] It should be noted that the above-mentioned organic electroluminescent device is prepared by conventional means in the art, for example, each layer can be deposited on a substrate.

[0130] In a fifth aspect, the present application provides an organic electroluminescent product, which comprises the above-mentioned organic electroluminescent device.

[0131] In a sixth aspect, the present application provides an electronic device, which comprises the above-mentioned fused ring compound.

[0132] In some optional embodiments, the electronic device includes a perovskite photovoltaic device, a perovskite light-emitting device, a display device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic photo detector, an organic photoreceptor, an organic quenching device, a light-emitting electrochemical cell, and an organic laser diode.

[0133] The fused ring compound of the present application will be specifically described below in combination with specific examples, but the present disclosure is not limited in any way by this.

[0134] Synthesis Example of Compound

[0135] Synthesis Example 1

[0136] This synthesis example provides a fused ring compound N-1, and the specific synthesis process is as shown below:

[0137]

[0138] In a 250 mL three-necked flask, under nitrogen, was placed intermediate 1-1 (8.00 g, 23.87 mmol), intermediate 2-1 (10.72 g, 26.25 mmol), dioxane: water = 4: 1 (80:20 mL), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (87 mg, 0.12 mmol), potassium carbonate (8.25 g, 59.68 mmol), and the reaction was carried out at 95 °C overnight. After the reaction was completed, the reaction was quenched with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 3 / 1) to give N-1 (7.31 g, 57.1% yield). Elemental analysis: C38H24N4. Theory: C, 85.05; H, 4.51; N, 10.44. Found: C, 85.09; H, 4.49; N, 10.42. HRMS (ESI) m / z (M+): Theory: 536.6380, Found: 536.6311.

[0139] Synthesis Example 2-9

[0140] Referring to the method of Synthesis Example 1, the compound shown in Synthesis Example 2-9 was obtained by using the compound shown in Table 1 instead of intermediate 1-n and intermediate 2-n.

[0141] Table 1

[0142]

[0143]

[0144] The details are as follows:

[0145]

[0146] Synthesis of N-6: In a 250 mL three-necked flask, under nitrogen atmosphere, intermediate 1-6 (8.00 g, 17.72 mmol), intermediate 2-6 (7.96 g, 19.50 mmol), dioxane:water = 4:1 (80:20 mL), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (65 mg, 0.09 mmol), potassium carbonate (6.11 g, 44.3 mmol) were added and the reaction was carried out at 95 °C overnight. After the reaction was completed, the reaction was quenched with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 8 / 1) to give N-6 (4.90 g, 42.4% yield). Elemental analysis: C47H32N4. Theory: C, 86.48; H, 4.94; N, 8.58. Found: C, 86.50; H, 4.93; N, 8.57. HRMS (ESI) m / z (M+): Theory: 652.8010, Found: 652.8097.

[0147]

[0148] Synthesis of N-13: In a 250 mL three-necked flask, under nitrogen atmosphere, intermediate 1-13 (7.00 g, 18.17 mmol), intermediate 2-13 (10.56 g, 21.80 mmol), dioxane:water = 4:1 (80:20 mL), tetrakis(triphenylphosphine)palladium (105 mg, 0.09 mmol), potassium carbonate (6.27 g, 45.43 mmol) were added and the reaction was carried out at 95 °C overnight. After the reaction was completed, the reaction was quenched with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 5 / 1) and recrystallized from chlorobenzene to give N-13 (4.91 g, 40.8% yield). Elemental analysis: C48H30N4. Theory: C, 86.98; H, 4.56; N, 8.45. Found: C, 86.99; H, 4.57; N, 8.43. HRMS (ESI) m / z (M+): Theory: 662.7960, Found: 662.7892.

[0149]

[0150] Synthesis of N-19: In a 250 mL three-necked flask, under nitrogen atmosphere, intermediate 1-19 (9.30 g, 16.22 mmol), intermediate 2-19 (8.64 g, 17.84 mmol), dioxane:water = 4:1 (80:20 mL), tetrakis(triphenylphosphine)palladium (94 mg, 0.08 mmol), potassium carbonate (5.60 g, 40.55 mmol) were added and the reaction was carried out at 95 °C overnight. After completion of the reaction, the reaction was quenched with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 5 / 1) and recrystallized from chlorobenzene to give N-19 (8.71 g, 63.1 % yield). Elemental analysis: C63H38N4. Theory: C, 88.92; H, 4.50; N, 6.58. Found: C, 88.95; H, 4.51; N, 6.54. HRMS (ESI) m / z (M+): Theory: 851.0250, Found: 851.0369.

[0151]

[0152] Synthesis of N-28: In a 250 mL three-necked flask, under nitrogen atmosphere, intermediate 1-28 (10.60 g, 18.48 mmol), intermediate 2-28 (10.87 g, 20.33 mmol), dioxane:water = 4:1 (80:20 mL), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (68 mg, 0.09 mmol), potassium carbonate (6.38 g, 46.2 mmol) were added and the reaction was carried out at 95 °C overnight. After completion of the reaction, the reaction was quenched with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 8 / 1) and recrystallized from toluene to give N-28 (7.47 g, 44.9 % yield). Elemental analysis: C67H40N4. Theory: C, 89.31; H, 4.47; N, 6.22. Found: C, 89.31; H, 4.49; N, 6.20. HRMS (ESI) m / z (M+): Theory: 901.0850, Found: 901.2033.

[0153]

[0154] Synthesis of N-44: In a 250 mL three-necked flask, under nitrogen atmosphere, intermediate 1-44 (8.40 g, 21.75 mmol), intermediate 2-44 (14.03 g, 23.92 mmol), dioxane:water = 4:1 (80:20 mL), [l,l'-bis(diphenylphosphino)ferrocene]dichloropalladium (79 mg, 0.11 mmol), potassium carbonate (7.50 g, 54.38 mmol) were added and the reaction was carried out at 95 °C overnight. After completion of the reaction, the reaction was quenched with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 1 / 1) and recrystallized from o-dichlorobenzene to give N-44 (6.43 g, 38.6% yield). Elemental analysis: C53H31N7. Theory: C, 83.12; H, 4.08; N, 12.80. Found: C, 83.16; H, 4.07; N, 12.77. HRMS (ESI) m / z (M+): Theory: 765.8800, Found: 765.8248.

[0155]

[0156] Synthesis of N-55: In a 250 mL three-necked flask, under nitrogen atmosphere, intermediate 1-55 (4.58 g, 13.62 mmol), intermediate 2-55 (9.93 g, 14.99 mmol), dioxane:water = 4:1 (80:20 mL), [l,l'-bis(diphenylphosphino)ferrocene]dichloropalladium (50 mg, 0.07 mmol), potassium carbonate (4.70 g, 34.05 mmol) were added and the reaction was carried out at 95 °C overnight. After completion of the reaction, the reaction was quenched with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 1 / 1) and recrystallized from o-dichlorobenzene to give N-55 (4.60 g, 42.6% yield). Elemental analysis: C55H33N7. Theory: C, 83.42; H, 4.20; N, 12.38. Found: C, 83.43; H, 4.20; N, 12.37. HRMS (ESI) m / z (M+): Theory: 791.9180, Found: 791.7333.

[0157]

[0158] Synthesis of N-57: In a 250 mL three-necked flask, under nitrogen atmosphere, intermediate 1-57 (5.00 g, 10.17 mmol), intermediate 2-57 (7.08 g, 10.68 mmol), dioxane: water = 4: 1 (80:20 mL), [l,l'-bis(diphenylphosphino)ferrocene]dichloropalladium (37 mg, 0.05 mmol), potassium carbonate (3.51 g, 25.43 mmol), 95 °C overnight, after completion of the reaction, quenched with water, extracted with dichloromethane, dried the organic layer over anhydrous magnesium sulfate, removed the organic solvent, the crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 1 / 1), recrystallized from o-dichlorobenzene to give N-57 (4.88 g, 50.6% yield). Elemental analysis: C68H46N6. Theory: C, 86.23; H, 4.90; N, 8.87; Found: C, 86.25; H, 4.91; N, 8.84. HRMS (ESI) m / z (M+): Theory: 947.1580, Found: 947.4231.

[0159]

[0160] Synthesis of N-72: In a 250 mL three-necked flask, under nitrogen atmosphere, intermediate 1-72 (5.00 g, 13.63 mmol), intermediate 2-72 (6.12 g, 14.99 mmol), dioxane: water = 4: 1 (80:20 mL), [l,l'-bis(diphenylphosphino)ferrocene]dichloropalladium (50 mg, 0.07 mmol), potassium carbonate (4.70 g, 34.08 mmol), 95 °C overnight, after completion of the reaction, quenched with water, extracted with dichloromethane, dried the organic layer over anhydrous magnesium sulfate, removed the organic solvent, the crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 5 / 1), recrystallized from chlorobenzene to give N-72 (4.79 g, 57.4% yield). Elemental analysis: C44H28N4. Theory: C, 86.25; H, 4.61; N, 9.14; Found: C, 86.24; H, 4.66; N, 9.10. HRMS (ESI) m / z (M+): Theory: 612.7360, Found: 612.8745.

[0161] For example, the synthesis of intermediate 1-6 in synthesis example 2 is shown below:

[0162] For example, the synthesis of intermediate 1-6 in synthesis example 2 is shown below:

[0163]

[0164] Synthesis of intermediate 1-6: In a two liter three necked flask, under nitrogen atmosphere, was placed starting material b-6 (7.75 g, 32.54 mmol), starting material a-6 (10.00 g, 29.59 mmol), dioxane: water = 4: 1 (360:90 mL), tetrakis(triphenylphosphine)palladium (171 mg, 0.15 mmol), potassium carbonate (10.22 g, 73.96 mmol), and the reaction mixture was stirred at 60 °C overnight. After the reaction was completed, water was added to quench the reaction, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and the organic solvent was removed. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 8 / 1) to give 1-6 (8.13 g, 60.9% yield). Elemental analysis: C27H19BrN2. Theory: C, 71.85; H, 4.24; Br, 17.70; N, 6.21. Found: C, 71.80; H, 4.25; Br, 17.70; N, 6.25. HRMS (ESI) m / z (M+): Theory: 451.3670, Found: 451.3711.

[0165] Following the procedure for the synthesis of intermediate 1-6 in Synthesis Example 2, the corresponding step was performed using the compounds b-n shown in Table 2 to give the intermediates 1-n of Synthesis Examples 3-8.

[0166] Table 2

[0167]

[0168]

[0169] For example, the synthesis of intermediate 2-13 in Synthesis Example 3 is shown below:

[0170]

[0171] Synthesis of intermediate d-13: In a 2L three-necked flask, under nitrogen protection, was added starting material c-13 (80.00 g, 0.18 mol), phenylboronic acid (24.38 g, 0.20 mol), dioxane: water = 4: 1 (800:200 mL), tetrakis(triphenylphosphine)palladium (1.04 g, 0.9 mmol), potassium carbonate (62.80 g, 0.45 mol), and the reaction mixture was heated at 95 °C overnight. After the reaction was completed, the reaction mixture was quenched with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed. The crude product was purified by chromatography (n-hexane / dichloromethane, 3 / 1) to give intermediate d-13 (31.4 g, 39.5% yield). Elemental analysis: C26H17BrN2. Theory: C, 71.41; H, 3.92; Br, 18.27; N, 6.41; Found: C, 71.45; H, 3.91; Br, 18.25; N, 6.40. HRMS (ESI) m / z (M+): Theory: 437.3400, Found: 437.3328.

[0172] Synthesis of intermediate 2-13: In a 2L three-necked flask, under nitrogen protection, was added intermediate d-13 (20.00 g, 45.73 mmol), bis(pinacolato)diboron (13.94 g, 54.88 mmol), dioxane (200 mL), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (167 mg, 0.23 mmol), potassium acetate (13.44 g, 0.14 mol), and the reaction mixture was heated at 100 °C overnight. After the reaction was completed, the reaction mixture was dried in vacuo and dissolved in toluene and passed through a flash column. The organic solvent was removed to give 2-13 (21.13 g, 95.4% yield). Elemental analysis: C32H29BN2O2. Theory: C, 79.35; H, 6.03; B, 2.23; N, 5.78; O, 6.61; Found: C, 79.36; H, 6.04; B, 2.21; N, 5.79; O, 6.60. HRMS (ESI) m / z (M+): Theory: 484.4060, Found: 484.4093.

[0173] For example, the synthesis of intermediate 2-28 in Example 5 is shown below:

[0174]

[0175] Synthesis of intermediate e-28: In a 2L three-necked flask, under nitrogen protection, was added starting material c-28 (70.00 g, 0.16 mol), bis(pinacolato)diboron (100.99 g, 0.40 mol), dioxane (1200 mL), [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride (581 mg, 0.80 mmol), potassium acetate (38.96 g, 0.40 mol), and the reaction was carried out at 100 °C overnight. After the reaction was completed, the solvent was removed and the residue was dissolved in toluene and purified by flash column. The organic solvent was removed to give intermediate d-28 (75.77 g, yield 89.2%). Elemental analysis: C32H36B2N2O4. Theor. C, 71.94; H, 6.79; B, 4.05; N, 5.24; O, 11.98. Found C, 71.99; H, 6.77; B, 4.04; N, 5.23; O, 11.97. HRMS (ESI) m / z (M+): Theor. 534.2700, Found 534.2621.

[0176] Synthesis of intermediate 2-28: In a 500 mL three-necked flask, under nitrogen protection, was added intermediate e-28 (12.00 g, 22.46 mmol), 2-bromonaphthalene (5.12 g, 24.71 mmol), dioxane: water = 4:1 (80:20 mL), tetrakis(triphenylphosphine)palladium (130 mg, 0.11 mmol), potassium carbonate (7.75 g, 56.15 mmol), and the reaction was carried out at 100 °C overnight. After the reaction was completed, the reaction was quenched with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 8 / 1) and recrystallized from toluene to give intermediate 2-28 (7.68 g, yield 64.0%). Elemental analysis: C36H31BN2O2. Theor. C, 80.90; H, 5.85; B, 2.02; N, 5.24; O, 5.99. Found C, 80.93; H, 5.84; B, 2.00; N, 5.25; O, 5.98. HRMS (ESI) m / z (M+): Theor. 534.4660, Found 534.4912.

[0177] Further, the synthesis of intermediates 2 in the remaining synthesis examples is shown in the above-described synthesis example 5, except that 2-bromonaphthalene in the second step is replaced with the corresponding compound, as shown in Table 3.

[0178] Table 3

[0179]

[0180] Device Examples

[0181] The materials used to prepare the following device examples or device comparative examples are shown in Table 4 below.

[0182] Table 4

[0183]

[0184] Device Example 1

[0185] This example provides an organic electroluminescent device, such as Figure 1 as shown, including 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, a cathode 16, which are sequentially stacked. The device structure is: 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), cathode.

[0186] The preparation of the above organic electroluminescent device includes the following steps:

[0187] 1) Substrate cleaning:

[0188] The transparent ITO-coated glass substrate is ultrasonically treated in an aqueous cleaning agent (composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10 wt%, triethanolamine ≤ 1 wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio of acetone to ethanol 1:1), baked in a clean environment until the water is completely removed, and then cleaned with ultraviolet light and ozone.

[0189] 2) Organic layer preparation:

[0190] The ITO transparent substrate is transferred to the evaporation equipment and vacuumed to 1 x 10 -6 to 2 x 10 -4Pa, sequentially evaporating a hole injection layer (HIL) / a first hole transport layer (HTL-1) / a first electron blocking layer (EBL-1) / a first organic light-emitting layer (EML-1) / a first hole blocking layer (HBL-1) / a first electron transport layer (ETL-1) / an n-type charge generation layer (CGL-n) / a p-type charge generation layer (CGL-p) / a second hole transport layer (HTL-2) / a second electron blocking layer (EBL-2) / a second organic light-emitting layer (EML-2) / a second hole blocking layer (HBL-2) / a second electron transport layer (ETL-2) / an electron injection layer (EIL) / a cathode (Mg:Ag mass ratio of 1:9) on an ITO anode film.

[0191] wherein:

[0192] The anode is indium tin oxide (ITO, thickness 10 nm);

[0193] The material of the hole injection layer (HIL) is HAT-CN:TCTA (mass ratio of 3:97) (thickness 10 nm);

[0194] The material of the first hole transport layer (HTL-1) is TCTA (thickness 20 nm);

[0195] The material of the first electron blocking layer (EBL-1) is mCP (thickness 5 nm);

[0196] The material of the first organic light-emitting layer (EML-1) is compound D and E in Table 4, mass ratio of 95:5 (thickness 20 nm);

[0197] The material of the first hole blocking layer (HBL-1) is BCP (thickness 5 nm);

[0198] The material of the first electron transport layer (ETL-1) is TPBI and LiQ, mass ratio of 9:1 (thickness 25 nm);

[0199] The material of the n-type charge generation layer (CGL-n) is compound N-1 and Yb obtained from Synthesis Example 1, and the specific ratio and thickness are shown in Table 5;

[0200] The material of the p-type charge generation layer (CGL-p) is HAT-CN and TCTA, mass ratio of 8:2 (thickness 10 nm);

[0201] The material of the second hole transport layer (HTL-2) is TCTA (thickness 20 nm);

[0202] The material of the second electron blocking layer (EBL-2) is mCP (thickness 5 nm);

[0203] The material of the second organic light emitting layer (EML-2) is compound D and E in Table 4, with a mass ratio of 95:5 (thickness 20 nm);

[0204] The material of the second hole blocking layer (HBL-2) is BCP (thickness 5 nm);

[0205] The material of the second electron transport layer (ETL-2) is TPBI and LiQ, with a mass ratio of 9:1 (thickness 25 nm);

[0206] The material of the electron injection layer (EIL) is Yb (thickness 1 nm);

[0207] The material of the cathode is Mg and Ag, with a mass ratio of 1:9 (thickness 11 nm).

[0208] Device Example 2

[0209] Most of the same as Device Example 1, except that the compound N-1 obtained in Synthesis Example 1 in the n-type charge layer in Device Example 1 is replaced by the compound N-6 obtained in Synthesis Example 2.

[0210]

[0211] Device Example 3

[0212] Most of the same as Device Example 1, except that the compound N-1 obtained in Synthesis Example 1 in the n-type charge layer in Device Example 1 is replaced by the compound N-13 obtained in Synthesis Example 3.

[0213]

[0214] Device Example 4

[0215] Most of the same as Device Example 1, except that the compound N-1 obtained in Synthesis Example 1 in the n-type charge layer in Device Example 1 is replaced by the compound N-19 obtained in Synthesis Example 4.

[0216]

[0217] Device Example 5

[0218] Most of the same as Device Example 1, except that the compound N-1 obtained in Synthesis Example 1 in the n-type charge layer in Device Example 1 is replaced by the compound N-28 obtained in Synthesis Example 5.

[0219]

[0220] Device Example 6

[0221] Most of the same as in Device Example 1 except that the compound N-1 obtained in Synthesis Example 1 is replaced by the compound N-44 obtained in Synthesis Example 6 in the n-type charge transport layer in Device Example 1.

[0222]

[0223] Device Example 7

[0224] Most of the same as in Device Example 1 except that the compound N-1 obtained in Synthesis Example 1 is replaced by the compound N-55 obtained in Synthesis Example 7 in the n-type charge transport layer in Device Example 1.

[0225]

[0226] Device Example 8

[0227] Most of the same as in Device Example 1 except that the compound N-1 obtained in Synthesis Example 1 is replaced by the compound N-57 obtained in Synthesis Example 8 in the n-type charge transport layer in Device Example 1.

[0228]

[0229] Device Example 9

[0230] Most of the same as in Device Example 1 except that the compound N-1 obtained in Synthesis Example 1 is replaced by the compound N-72 obtained in Synthesis Example 9 in the n-type charge transport layer in Device Example 1.

[0231]

[0232] Device Example 10

[0233] Most of the same as in Device Example 1 except that the compound N-1 obtained in Synthesis Example 1 is replaced by the following compound in the n-type charge transport layer in Device Example 1.

[0234]

[0235] Device Comparative Example 1

[0236] Most of the same as in Device Example 1 except that the compound N-1 obtained in Synthesis Example 1 is replaced by the following compound REF-1 in the n-type charge transport layer in Device Example 1.

[0237]

[0238] Device Comparative Example 2

[0239] Most of the same as device example 1, except that the compound N-1 in device example 1 in the n-type charge layer is replaced by the compound REF-2 shown below.

[0240]

[0241] Device comparative example 3

[0242] Most of the same as device example 1, except that the compound N-1 in device example 1 in the n-type charge layer is replaced by the compound REF-3 shown below.

[0243]

[0244] The partial layers of the organic electroluminescent device and the materials and thicknesses thereof are shown in Table 5.

[0245] Table 5

[0246]

[0247]

[0248] Test example:

[0249] 1. Compound heat resistance test

[0250] The heat resistance of the compounds used in the device examples and the compounds used in the device comparative examples was tested: after the HPLC purity of the compound was determined (area% at a wavelength of 254 nm was determined), it was sealed in a bottle and vacuumed, and then kept in an oven at 385°C for 150 hours. Then it was restored to room temperature, and the HPLC purity of the sample was analyzed again, and the results are shown in Table 6.

[0251] Table 6

[0252] Compound Purity before heat resistance test (%) Purity after heat resistance test (%) N-1 99 99 N-6 99 99 N-13 99 99 N-19 99 99 N-28 99 99 N-44 99 99 N-55 99 99 N-57 99 99 N-72 99 99 N-75 99 99 REF-1 99 97 REF-2 99 95 REF-3 99 94

[0253] 2. Device test example

[0254] The organic electroluminescent devices obtained in device examples 1-10 in the device examples and device comparative examples 1-3 were tested.

[0255] Instrument: the current, voltage, brightness, and emission spectrum of the device were tested simultaneously using a PR 650 spectral scanning luminance meter and a Keithley K2400 digital source meter system;

[0256] Test conditions: current density of 10 mA / cm2, room temperature.

[0257] Lifetime test: record the time (in hours) when the luminance of the device decreases to 95% of the original luminance. The lifetime T95 of the device of Comparative Example 1 is set to 100, and the lifetime of other devices is the relative value of the lifetime of the device of Comparative Example 1. The device performance test results are shown in Table 7:

[0258] Table 7

[0259] Example Driving voltage (V) Current efficiency (cd / A) Relative lifetime T95 Device Example 1 7.39 15.34 110 Device Example 2 7.34 15.42 112 Device Example 3 7.42 15.21 108 Device Example 4 7.03 15.89 128 Device Example 5 7.12 15.81 124 Device Example 6 7.19 15.67 119 Device Example 7 7.23 15.54 116 Device Example 8 7.48 15.12 107 Device Example 9 7.51 14.96 105 Device Example 10 7.53 14.88 103 Device Comparative Example 1 7.71 14.36 100 Device Comparative Example 2 7.81 14.12 94 Device Comparative Example 3 7.84 14.01 90

[0260] As can be seen from Table 6, under the same current density, compared with the CGL layer in the prior art device of Comparative Example 3, the organic electroluminescent device of the application has a longer lifetime, a lower driving voltage, and a good current efficiency.

[0261] This is mainly because the exposed N on the quinoxaline and the two Ns on the phenanthroline in the compound of formula (1) of the application coordinate synergistically, better fixing the metal Yb, which can improve the lifetime and current efficiency of the organic electroluminescent device when applied to the organic electroluminescent device. In addition, the planar structure of the quinoxaline and the phenanthroline in the compound of formula (1) of the application can enhance the stacking and strengthen the charge transport, thereby improving the current efficiency.

[0262] Obviously, the above examples are only examples for clarity and are not limitations on the embodiments. Based on the above description, other different forms of changes or variations can also be made by those of ordinary skill in the art. It is not necessary and impossible to enumerate all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A fused-ring compound, characterized in that, It has the structure shown in equation (1): In the formula, R 1 R 2 R 3 They may be the same or different, and each is independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C1-C60 heteroaryl; a, b, and c are the same or different and are integers, and satisfy: 0 ≤ a ≤ 7, 0 ≤ b ≤ 3, and 0 ≤ c ≤ 2; Furthermore, the substituents in the substituted C6-C60 aryl group and the substituted C1-C60 heteroaryl group are selected from one or more of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C60 alkyl, C2-C60 alkenyl, C3-C60 cycloalkyl, C2-C60 alkynyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C3-C60 cycloalkenyl, C1-C60 heterocycloalkenyl, C6-C60 aryl, and C1-C60 heteroaryl.

2. The fused-ring compound according to claim 1, characterized in that, The fused-ring compound has the structures represented by formulas (1-1) and (1-2) as follows:

3. The fused-ring compound according to claim 1 or 2, characterized in that, R 1 R 2 R 3 They may be the same or different, and each is independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C6-C50 aryl, substituted or unsubstituted C1-C50 heteroaryl; The substituents in the substituted C6-C50 aryl and substituted C1-C50 heteroaryl are selected from one or more of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C2-C50 alkenyl, C3-C50 cycloalkyl, C2-C50 alkynyl, C3-C50 cycloalkyl, C1-C50 heterocycloalkyl, C3-C50 cycloalkenyl, C1-C50 heterocycloalkenyl, C6-C50 aryl, and C1-C50 heteroaryl. Preferred, R 1 R 2 R 3 They may be the same or different, and each is independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C1-C25 heteroaryl; The substituents in the substituted C6-C25 aryl and substituted C1-C25 heteroaryl are selected from one or more of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C2-C25 alkenyl, C3-C25 cycloalkyl, C2-C25 alkynyl, C3-C25 cycloalkyl, C1-C25 heterocyclic alkyl, C3-C25 cycloalkenyl, C1-C25 heterocyclic alkenyl, C6-C25 aryl, and C1-C25 heteroaryl.

4. The fused-ring compound according to any one of claims 1-3, characterized in that, R 1 R 2 R 3 The same or different, and each independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, nitro, amidine, hydrazine, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted triphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted binaphthyl, substituted or unsubstituted phenylnaphthyl, substituted or unsubstituted naphthylphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenylfluorenyl, substituted or unsubstituted benzo[a]fluorenyl, substituted or unsubstituted dibenzo[a]fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted phenylphenanthryl, substituted or unsubstituted anthrayl, substituted or unsubstituted indene, substituted or unsubstituted tetraphenyl, Substituted or unsubstituted perylene, substituted or unsubstituted trefyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted fluoranyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted phenylthio, substituted or unsubstituted pyrroleyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted isothiazolyl, substituted or unsubstituted isoxazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted triazine, substituted or unsubstituted tetraazine, substituted or unsubstituted triazolyl, substituted Or unsubstituted tetrazolyl, substituted or unsubstituted furazolidone, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzopyridyl, substituted or unsubstituted benzothiopheneyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiopheneyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzoisothiazolyl, substituted or unsubstituted benzoisoxazoleyl, substituted or unsubstituted benzoxazoleyl, substituted or Unsubstituted isoindolyl, substituted or unsubstituted indolyl, substituted or unsubstituted indazole, substituted or unsubstituted benzothiadiazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted cyclolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted phenthiazinyl, substituted or unsubstituted phenanthinyl, substituted or unsubstituted dipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted phenylterpyridyl, substituted or unsubstituted diazafluorenyl, or substituted or unsubstituted phenanthrolinel; The substituents in the substituted groups are selected from one or more of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trideuterated methyl, trimethylsilyl, phenyl, naphthyl, biphenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, or carbazoyl. Preferred, R 1 R 2 R 3 They may be the same or different, and each is independently selected from hydrogen, deuterium, or the group consisting of:

5. The fused-ring compound according to any one of claims 1-4, characterized in that, c = 2, and 0 ≤ a ≤ 2 and 0 ≤ b ≤ 2; Preferably, c = 2, and 0 ≤ a ≤ 2 and 0 ≤ b ≤ 1.

6. The fused-ring compound according to any one of claims 1-5, characterized in that, The fused-ring compound is selected from the following structures:

7. 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 described in any one of claims 1-6.

8. 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 described in any one of claims 1-6.

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, wherein the organic layer includes any one or a combination of at least two of the fused-ring compounds according to any one of claims 1-6; Preferably, the organic layer comprises an n-type charge generation layer and / or an electron transport layer; The material of the n-type charge generation layer is the n-type charge generation material as described in claim 7; The electron transport layer is made of the electron transport material as described in claim 8.

10. An organic electroluminescent device according to claim 9, characterized in that, The organic layer further includes one or more of the following: a hole injection layer, a first organic light-emitting layer, a second organic light-emitting layer, and an electron injection layer; Preferably, the organic light-emitting device comprises a first organic light-emitting layer, an n-type charge-generating layer, and a second organic light-emitting layer stacked sequentially.

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