Nitrogen-containing compounds and organic electroluminescent devices and electronic devices

Abstract

This application relates to the technical field of organic electroluminescent materials and provides a nitrogen-containing compound, an organic electroluminescent device, and an electronic device containing the same. The compound of the present application comprises an indolecarbazole group fused to cyclohexane as the core structure of the compound. When used as the host material for the light-emitting layer, the compound of the present application can improve carrier balance in the light-emitting layer, broaden the carrier recombination zone, increase the efficiency of exciton generation and utilization, and enhance the luminous efficiency and life of the device.

Description

Technical Field

[0001] The present application relates to the technical field of organic electroluminescent materials, and in particular to nitrogen-containing compounds and organic electroluminescent devices and electronic devices containing the same. Background Art

[0002] With the development of electronic technology and the progress of materials science, the application scope of electronic components for realizing electroluminescence or photoelectric conversion is becoming more and more extensive. Organic electroluminescent devices (OLEDs) generally include a cathode and an anode arranged relatively to each other, and a functional layer arranged between the cathode and the anode. The functional layer is composed of multiple organic or inorganic film layers, and generally includes an organic light-emitting layer, a hole transport layer, an electron transport layer, etc. When a voltage is applied to the anode and the cathode, the two electrodes generate an electric field. Under the action of the electric field, the electrons on the cathode side move toward the electroluminescent layer, and the holes on the anode side also move toward the light-emitting layer. The electrons and holes combine in the electroluminescent layer to form excitons. The excitons are in an excited state and release energy outward, thereby causing the electroluminescent layer to emit light outward.

[0003] The main problems with existing organic electroluminescent devices are lifespan and efficiency. As displays become larger, the driving voltage also increases, and the luminous efficiency and current efficiency also need to be improved. Therefore, it is necessary to continue to develop new materials to further improve the performance of organic electroluminescent devices. Summary of the Invention

[0004] In view of the above problems existing in the prior art, the purpose of the present application is to provide a nitrogen-containing compound and an electronic component and an electronic device containing the same. The nitrogen-containing compound is used in an organic electroluminescent device to improve the performance of the device.

[0005] According to a first aspect of the present application, a nitrogen-containing compound is provided, wherein the nitrogen-containing compound has a structure formed by the following formula 1 and formula 2 fused to each other, wherein formula 2 is fused to the * position on ring B in formula 1:

[0006]

[0007] Ring A is benzocyclohexane;

[0008] Ring C is selected from aromatic rings having 6 to 14 carbon atoms;

[0009] Groups A1 and A2 are independently selected from the structure represented by formula a-1 or the structure represented by formula a-2, and at least one of A1 and A2 is selected from the structure represented by formula a-1;

[0010]

[0011] L, L1, L2 and L3 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms;

[0012] Ar3 is selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms;

[0013] Het is a nitrogen-containing heteroarylene group having 3 to 20 carbon atoms;

[0014] Ar1 and Ar2 are the same or different and are each independently selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms;

[0015] Each R1, R2 and R3 is the same or different and is independently selected from deuterium, cyano, a halogen group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a deuterated alkyl group having 1 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, a triphenylsilyl group, an aryl group having 6 to 20 carbon atoms, a deuterated aryl group having 6 to 20 carbon atoms, a haloaryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms; optionally, any two adjacent R2 groups form a 6-14 membered aromatic ring, and the 6-14 membered aromatic ring is optionally substituted with 0, 1, 2, 3, 4, 5 or 6 R4 groups;

[0016] Each R4 is independently selected from deuterium, cyano, halogen, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, deuterated alkyl having 1 to 10 carbon atoms, or trialkylsilyl having 3 to 12 carbon atoms;

[0017] n1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0018] n2 is selected from 0, 1 or 2;

[0019] n3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0020] The substituents in L, L1, L2, L3, Ar1, Ar2 and Ar3 are the same or different and are independently selected from deuterium, cyano, halogen group, alkyl group with 1 to 10 carbon atoms, haloalkyl group with 1 to 10 carbon atoms, deuterated alkyl group with 1 to 10 carbon atoms, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, aryl group with 6 to 20 carbon atoms, deuterated aryl group with 6 to 20 carbon atoms, haloaryl group with 6 to 20 carbon atoms, heteroaryl group with 3 to 20 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms; optionally, any two adjacent substituents may form a saturated or unsaturated 3 to 15-membered ring.

[0021] According to a second aspect of the present application, an organic electroluminescent device is provided, comprising an anode and a cathode arranged opposite to each other, and a functional layer arranged between the anode and the cathode; the functional layer comprises the nitrogen-containing compound described above.

[0022] According to a third aspect of the present application, an electronic device is provided, comprising the organic electroluminescent device according to the second aspect.

[0023] The present invention's compounds use an indolecarbazole-type group fused to a cyclohexane as the core structure of the compound, and further connect an aryl or heteroaryl group via two nitrogen atoms in the indolecarbazole. The indolecarbazole group has excellent hole transport ability, and the group fused to a cyclohexane can further enhance the hole transport ability of the carbazole group through the hyperconjugation effect, giving the present invention's compounds even better hole transport ability. In addition, substituents are added to the cyclohexane of the parent core. These substituents are located outside the conjugated plane of the indolecarbazole group in terms of spatial configuration, forming a certain steric hindrance and finely regulating the stacking between the compound molecules, allowing the compound to form a better amorphous film. When the present invention's compounds are used as the main material of the light-emitting layer, the carrier balance in the light-emitting layer can be improved, the carrier recombination area can be widened, the exciton generation and utilization efficiency can be increased, and the device luminous efficiency and lifespan can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The accompanying drawings are used to provide further understanding of the present application and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present application, but do not constitute a limitation to the present application.

[0025] Figure 1 It is a schematic structural diagram of an organic electroluminescent device according to one embodiment of the present application.

[0026] Figure 2 It is a schematic structural diagram of an electronic device according to one embodiment of the present application.

[0027] Reference numerals

[0028] 100, anode 200, cathode 300, functional layer 310, hole injection layer

[0029] 321, first hole transport layer 322, second hole transport layer 330, organic light emitting layer 340, electron transport layer

[0030] 350, electron injection layer 400, electronic device DETAILED DESCRIPTION

[0031] The exemplary embodiments will now be described more fully with reference to the accompanying drawings. However, the exemplary embodiments can be implemented in a variety of forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this application will be more comprehensive and complete and will fully convey the concepts of the exemplary embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to provide a full understanding of the embodiments of the present application.

[0032] In a first aspect, the present application provides a nitrogen-containing compound having a structure formed by the following formula 1 and formula 2 fused together, wherein formula 2 is fused to the * position on ring B in formula 1:

[0033]

[0034] Ring A is benzocyclohexane;

[0035] Ring C is selected from aromatic rings having 6 to 14 carbon atoms;

[0036] Groups A1 and A2 are independently selected from the structure represented by formula a-1 or the structure represented by formula a-2, and at least one of A1 and A2 is selected from the structure represented by formula a-1;

[0037]

[0038] L, L1, L2 and L3 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms;

[0039] Ar3 is selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms;

[0040] Het is a nitrogen-containing heteroarylene group having 3 to 20 carbon atoms;

[0041] Ar1 and Ar2 are the same or different and are each independently selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms;

[0042] Each R1, R2 and R3 is the same or different and is independently selected from deuterium, cyano, a halogen group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a deuterated alkyl group having 1 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, a triphenylsilyl group, an aryl group having 6 to 20 carbon atoms, a deuterated aryl group having 6 to 20 carbon atoms, a haloaryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms; optionally, any two adjacent R2 groups form a 6-14 membered aromatic ring, and the 6-14 membered aromatic ring is optionally substituted with 0, 1, 2, 3, 4, 5 or 6 R4 groups;

[0043] Each R4 is independently selected from deuterium, cyano, halogen, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, deuterated alkyl having 1 to 10 carbon atoms, or trialkylsilyl having 3 to 12 carbon atoms;

[0044] n1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0045] n2 is selected from 0, 1 or 2;

[0046] n3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0047] The substituents in L, L1, L2, L3, Ar1, Ar2 and Ar3 are the same or different and are independently selected from deuterium, cyano, halogen group, alkyl group with 1 to 10 carbon atoms, haloalkyl group with 1 to 10 carbon atoms, deuterated alkyl group with 1 to 10 carbon atoms, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, aryl group with 6 to 20 carbon atoms, deuterated aryl group with 6 to 20 carbon atoms, haloaryl group with 6 to 20 carbon atoms, heteroaryl group with 3 to 20 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms; optionally, any two adjacent substituents may form a saturated or unsaturated 3 to 15-membered ring.

[0048] In this application, the terms "optionally" and "optionally" mean that the event or environment described subsequently may or may not occur. For example, "optionally, any two adjacent substituents form a ring" means that the two substituents may or may not form a ring, that is, including: the scenario where two adjacent substituents form a ring and the scenario where two adjacent substituents do not form a ring. For another example, "optionally, any two adjacent substituents among L, L1, L2, L3, Ar1, Ar2 and Ar3 form a ring" means that any two adjacent substituents among L, L1, L2, L3, Ar1, Ar2 and Ar3 are connected to each other to form a ring, or any two adjacent substituents among Ar1, Ar2 and Ar3 can also exist independently of each other. "Any two adjacent" can include two substituents on the same atom, and can also include one substituent on each of two adjacent atoms; wherein, when there are two substituents on the same atom, the two substituents can form a saturated or unsaturated spirocycle with the atom to which they are commonly connected; when there is one substituent on each of two adjacent atoms, the two substituents can be fused into a ring.

[0049] In this application, the descriptions used in this application are interchangeable with "each ... independently is" and "... independently is" and "... independently is" and should be understood in a broad sense. They can mean that in different groups, the specific options expressed by the same symbols do not affect each other, or in the same group, the specific options expressed by the same symbols do not affect each other. For example, Wherein, each q is independently 0, 1, 2 or 3, and each R" is independently selected from hydrogen, deuterium, fluorine, and chlorine. The meaning is: Formula Q-1 represents that there are q substituents R" on the benzene ring, and each R" can be the same or different, and the options of each R" do not affect each other; Formula Q-2 represents that there are q substituents R" on each benzene ring of biphenyl, and the number q of R" substituents on the two benzene rings can be the same or different, and each R" can be the same or different, and the options of each R" do not affect each other.

[0050] In this application, the term "substituted or unsubstituted" means that the functional group described after the term may or may not have a substituent (hereinafter, for ease of description, the 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 above-mentioned substituent Rc can be, for example, deuterium, a halogen group, a cyano group, a heteroaryl group, an aryl group, a trialkylsilyl group, an alkyl group, a haloalkyl group, a deuterated alkyl group, a deuterated aryl group, a haloaryl group, a cycloalkyl group, etc. The number of substitutions can be one or more.

[0051] In this application, "plurality" refers to more than two, for example, 2, 3, 4, 5, 6, etc.

[0052] The hydrogen atoms in the structures of the compounds of the present application include various isotope atoms of the hydrogen element, such as hydrogen (H), deuterium (D) or tritium (T).

[0053] In this application, the number of carbon atoms in a substituted or unsubstituted functional group refers to the total number of carbon atoms. For example, if L is a substituted arylene group with 12 carbon atoms, the total number of carbon atoms in the arylene group and its substituents is 12.

[0054] In the present application, aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. Aryl can be a monocyclic aryl (such as phenyl) or a polycyclic aryl. In other words, aryl can be a monocyclic aryl, a condensed ring aryl, two or more monocyclic aryl groups connected by carbon-carbon single bond conjugation, a monocyclic aryl and a condensed ring aryl connected by carbon-carbon single bond conjugation, two or more condensed ring aryl groups connected by carbon-carbon single bond conjugation. That is, unless otherwise indicated, two or more aromatic groups connected by carbon-carbon single bond conjugation can also be considered as aryl of the present application. Wherein, condensed ring aryl, for example, can include bicyclic condensed aryl (such as naphthyl), tricyclic condensed aryl (such as phenanthrenyl, fluorenyl, anthryl) etc. Aryl does not contain heteroatoms such as B, N, O, S, P, Se and Si. Examples of aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, phenyl-naphthyl, spirobifluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, triphenylene, perylene, benzo[9,10]phenanthrenyl, pyrenyl, benzofluoranthenyl, Ji et al.

[0055] In the present application, the arylene group refers to a divalent or multivalent group formed by further losing one or more hydrogen atoms from an aryl group.

[0056] In this application, terphenyl includes

[0057] In the present application, the number of carbon atoms of a substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group. For example, a substituted aryl group with 18 carbon atoms refers to the total number of carbon atoms of the aryl group and the substituents being 18.

[0058] In the present application, the number of carbon atoms of the substituted or unsubstituted aryl (arylene) group can be 6, 8, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 28, 30, 31, 33, 34, 35, 36, 38 or 40, etc. In some embodiments, the substituted or unsubstituted aryl group is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, in other embodiments, the substituted or unsubstituted aryl group is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, in other embodiments, the substituted or unsubstituted aryl group is a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, and in other embodiments, the substituted or unsubstituted aryl group is a substituted or unsubstituted aryl group having 6 to 15 carbon atoms.

[0059] In the present application, the fluorenyl group may be substituted by one or more substituents. In the case where the fluorenyl group is substituted, the substituted fluorenyl group may be: etc., but not limited thereto.

[0060] In the present application, the aryl group as a substituent of L, L1, L2, L3, Ar1, Ar2 and Ar3 includes, but is not limited to, phenyl, naphthyl, phenanthrenyl, biphenyl, fluorenyl, dimethylfluorenyl and the like.

[0061] In the present application, a 6- to 14-membered aromatic ring refers to an aromatic ring having 6 to 14 ring atoms, such as but not limited to a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring.

[0062] In the present application, a heteroaryl group refers to a monovalent aromatic ring or a derivative thereof containing 1, 2, 3, 4, 5 or 6 heteroatoms in the ring, and the heteroatoms can be one or more of B, O, N, P, Si, Se and S. A heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. In other words, a heteroaryl group can be a single aromatic ring system or a plurality of aromatic ring systems connected by conjugated carbon-carbon single bonds, and any aromatic ring system can be an aromatic monocyclic ring or an aromatic condensed ring. For example, the heteroaryl group may include a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a triazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, an acridinyl group, a pyridazinyl group, a pyrazinyl group, a quinolyl group, a quinazolinyl group, a quinoxalinyl group, a phenoxazinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinolyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothienyl group, a dibenzothienyl group, a thienothiphenyl group, a benzofuranyl group, a phenanthrolinyl group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a silafluorenyl group, a dibenzofuranyl group, and an N-phenylcarbazolyl group, an N-pyridylcarbazolyl group, an N-methylcarbazolyl group, and the like, without being limited thereto.

[0063] In the present application, the heteroarylene group refers to a divalent or multivalent group formed by further losing one or more hydrogen atoms from a heteroaryl group.

[0064] In the present application, the number of carbon atoms of the substituted or unsubstituted heteroaryl (heteroarylene) can be selected from 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 or 40, etc. In some embodiments, the substituted or unsubstituted heteroaryl is a substituted or unsubstituted heteroaryl having a total carbon number of 3 to 40, in other embodiments, the substituted or unsubstituted heteroaryl is a substituted or unsubstituted heteroaryl having a total carbon number of 3 to 30, and in other embodiments, the substituted or unsubstituted heteroaryl is a substituted or unsubstituted heteroaryl having a total carbon number of 5 to 12.

[0065] In the present application, the heteroaryl groups as substituents of L, L1, L2, L3, Ar1, Ar2 and Ar3 are exemplified by, but not limited to, pyridyl, carbazolyl, quinolyl, isoquinolyl, phenanthroline, benzoxazolyl, benzothiazolyl, benzimidazolyl, dibenzothiophenyl and dibenzofuranyl.

[0066] In the present application, a substituted heteroaryl group may be a heteroaryl group in which one or more hydrogen atoms are replaced by groups such as a deuterium atom, a halogen group, -CN, an aryl group, a heteroaryl group, a trialkylsilyl group, an alkyl group, a cycloalkyl group, a haloalkyl group, etc. It should be understood that the number of carbon atoms in the substituted heteroaryl group refers to the total number of carbon atoms in the heteroaryl group and the substituents on the heteroaryl group.

[0067] In the present application, the alkyl group having 1 to 10 carbon atoms may include a straight-chain alkyl group having 1 to 10 carbon atoms and a branched-chain alkyl group having 3 to 10 carbon atoms. The number of carbon atoms of the alkyl group is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and n-hexyl.

[0068] In the present application, the halogen group is, for example, fluorine, chlorine, bromine, or iodine.

[0069] In the present application, specific examples of trialkylsilyl include, but are not limited to, trimethylsilyl, triethylsilyl, and the like.

[0070] In the present application, specific examples of the haloalkyl group include, but are not limited to, trifluoromethyl.

[0071] In the present application, specific examples of deuterated alkyl groups include, but are not limited to, trideuterated methyl groups.

[0072] In the present application, a deuterated aryl group refers to an aryl group containing deuterium, such as, but not limited to, deuterated phenyl, deuterated naphthyl, deuterated biphenyl, and the like.

[0073] In the present application, a halogenated aryl group refers to an aryl group with a halogen substituent, such as but not limited to fluorophenyl, fluoronaphthyl, fluorobiphenyl, and the like.

[0074] In the present application, the number of carbon atoms in the cycloalkyl group having 3 to 10 is, for example, 3, 4, 5, 6, 7, 8 or 10. Specific examples of the cycloalkyl group include, but are not limited to, cyclopentyl, cyclohexyl, and adamantyl.

[0075] In this application, no single bond extending from the ring system is involved in the positioning of the connecting bond. This means that one end of the link can be connected to any position in the ring system that the link passes through, and the other end is connected to the rest of the compound molecule. For example, as shown in the following formula (f), the naphthyl represented by formula (f) is connected to other positions of the molecule via two non-positional linkers that pass through the bicyclic ring. The meaning of this includes any possible connection method shown in formulas (f-1) to (f-10):

[0076]

[0077] For example, as shown in the following formula (X'), the dibenzofuranyl group represented by formula (X') is connected to other positions of the molecule through a non-positional connecting bond extending from the middle of one benzene ring. The meaning represented by it includes any possible connection method shown in formulas (X'-1) to (X'-4):

[0078]

[0079] A non-positional substituent herein refers to a substituent connected via a single bond extending from the center of the ring system, indicating that the substituent can be attached at any possible position within the ring system. For example, as shown in the following formula (Y), the substituent R' represented by formula (Y) is connected to the quinoline ring via a non-positional bond, and its meaning includes any possible connection method shown in formulas (Y-1) to (Y-7):

[0080]

[0081] In some embodiments, the structure of Formula 1 is represented by the following formulas (i-1) to (i-3):

[0082]

[0083] In some embodiments, Ring C is selected from a benzene ring, a naphthalene ring, or a phenanthrene ring.

[0084] Optionally, ring C is selected from the following structures:

[0085] * Position indicates the fusion site.

[0086] In some embodiments, each of R1, R2, and R3 is the same or different and is independently selected from deuterium, cyano, fluorine, trideuteromethyl, trimethylsilyl, trifluoromethyl, cyclopentyl, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, or naphthyl;

[0087] Optionally, any two adjacent R2 form a benzene ring, which is optionally substituted by 0, 1, 2, 3, 4, 5 or 6 R4; each R4 is independently selected from deuterium, cyano, fluorine, trideuteromethyl or trifluoromethyl.

[0088] In some embodiments, the nitrogen-containing compound has the following structural formulas (S-1) to (S-21):

[0089]

[0090]

[0091] wherein each of R1, R2, and R3 is the same or different and is independently selected from deuterium, cyano, fluorine, trideuteromethyl, trimethylsilyl, trifluoromethyl, cyclopentyl, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, or naphthyl;

[0092] Each R4 is independently selected from deuterium, cyano, fluorine, trideuterated methyl or trifluoromethyl;

[0093] n2 is selected from 0, 1 or 2;

[0094] n3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0095] n4 is selected from 0, 1 or 2;

[0096] n5 is selected from 0, 1, 2, 3 or 4.

[0097] In some embodiments, A1 and A2 are both represented by formula a-1; or, one of A1 and A2 has the structure represented by formula a-1, and the other has the structure represented by formula a-2. When the two L3 are the same or different, the two Ar3 are the same or different.

[0098] In the compounds of the present application, when tetramethylcyclohexane indole carbazole is connected to an aryl group or a heteroaryl group, it can constitute a material with excellent hole transport properties; when tetramethylcyclohexane indole carbazole is connected to an electron-deficient heteroaryl group (Het) containing at least two nitrogen atoms, it can constitute an electronic light-emitting layer host material or a light-emitting layer host material with bipolarity.

[0099] In some embodiments, Het is selected from the following groups:

[0100]

[0101] represents the bond connected to L, represents the bond connected to L1, Represents the bond connected to L2; the formula does not contain , which means the location is connected to In the formula (a), L2 is a single bond and Ar2 is hydrogen.

[0102] Optionally, Het is selected from the following groups:

[0103]

[0104] represents the bond connected to L, represents the bond connected to L1, Represents the bond connected to L2; the formula does not contain , which means the location is connected to In the formula (a), L2 is a single bond and Ar2 is hydrogen.

[0105] In some embodiments, L, L1, L2 and L3 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 18 carbon atoms.

[0106] In some embodiments, L, L1, L2 and L3 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 carbon atoms, or a substituted or unsubstituted heteroarylene group having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 carbon atoms.

[0107] Optionally, the substituents in L, L1, L2 and L3 are each independently selected from deuterium, fluorine, cyano, an alkyl group having 1 to 5 carbon atoms, a trialkylsilyl group having 3 to 8 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, a phenyl group or a naphthyl group.

[0108] In some embodiments, L, L1, L2 and L3 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted carbazolylene group.

[0109] Optionally, the substituents in L, L1, L2 and L3 are the same or different and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trifluoromethyl, trideuteromethyl, trimethylsilyl or phenyl.

[0110] In some embodiments, L is selected from a single bond or the following groups:

[0111]

[0112] In some embodiments, L1, L2, and L3 are each independently selected from a single bond or the following groups:

[0113]

[0114] In some embodiments, Ar1 and Ar2 are the same or different and are each independently selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms.

[0115] In some embodiments, Ar1 is selected from a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, or a substituted or unsubstituted heteroaryl group having 7 to 20 carbon atoms; Ar2 is selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, or a substituted or unsubstituted heteroaryl group having 7 to 20 carbon atoms.

[0116] In some embodiments, Ar3 is selected from a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, and a substituted or unsubstituted heteroaryl group having 7 to 20 carbon atoms.

[0117] In some embodiments, Ar1 and Ar2 are each independently selected from hydrogen, 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, or 25 carbon atoms, or a substituted or unsubstituted heteroaryl group having 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.

[0118] In some embodiments, Ar3 is selected from substituted or unsubstituted aryl having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 carbon atoms, and substituted or unsubstituted heteroaryl having 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.

[0119] In some embodiments, the substituents in Ar1 and Ar2 are each independently selected from deuterium, a halogen group, a cyano group, a haloalkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 5 to 12 carbon atoms, or a trialkylsilyl group having 3 to 8 carbon atoms. Optionally, any two adjacent substituents form a benzene ring or a fluorene ring.

[0120] In some embodiments, the substituents in Ar3 are each independently selected from deuterium, a halogen group, a cyano group, a haloalkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 5 to 12 carbon atoms, or a trialkylsilyl group having 3 to 8 carbon atoms. Optionally, any two adjacent substituents form a benzene ring or a fluorene ring.

[0121] In some embodiments, Ar1 and Ar3 are each independently selected from a substituted or unsubstituted group V; Ar2 is selected from hydrogen, a substituted or unsubstituted group V; wherein the unsubstituted group V is selected from the following groups:

[0122]

[0123] The substituted group V has one or more substituents, each of which is independently selected from deuterium, fluorine, cyano, trideuteromethyl, trimethylsilyl, trifluoromethyl, cyclopentyl, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzoxazolyl or benzothiazolyl, and when the number of substituents on the group V is greater than 1, the substituents are the same or different.

[0124] In some embodiments, Ar1 and Ar3 are each independently selected from the following groups; Ar2 is selected from hydrogen or the following groups:

[0125]

[0126]

[0127] In some embodiments, at least one of A1 and A2 is a structure shown in formula a-1, and the structure shown in formula a-1 Selected from the following groups:

[0128]

[0129]

[0130] In some embodiments, the structure shown in formula a-1 Selected from the group consisting of:

[0131]

[0132]

[0133] In some embodiments, Selected from the group consisting of the following groups, is selected from hydrogen or the following groups:

[0134]

[0135] In some embodiments, the structure shown in formula a-2 Selected from the group consisting of:

[0136]

[0137]

[0138] Optionally, the nitrogen-containing compound is selected from the group consisting of the following compounds:

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160] In a second aspect of the present application, an organic electroluminescent device is provided, comprising an anode, a cathode, and a functional layer disposed between the anode and the cathode; wherein the functional layer comprises the nitrogen-containing compound described in the first aspect of the present application.

[0161] The nitrogen-containing compound provided in the present application can be used to form at least one organic film layer in the functional layer to improve the luminous efficiency, lifespan and other characteristics of the organic electroluminescent device.

[0162] Optionally, the functional layer includes an organic light-emitting layer, and the organic light-emitting layer includes the nitrogen-containing compound. The organic light-emitting layer can be composed of the nitrogen-containing compound provided in this application, or can be composed of the nitrogen-containing compound provided in this application and other materials.

[0163] According to a specific embodiment, the organic electroluminescent device is as follows Figure 1 As shown, the organic electroluminescent device may include an anode 100, a hole injection layer 310, a first hole transport layer 321, a second hole transport layer (hole auxiliary layer) 322, an organic light-emitting layer 330, an electron transport layer 340, an electron injection layer 350 and a cathode 200, which are stacked in sequence.

[0164] In the present application, the anode 100 includes an anode material, which is preferably a material with a large work function that facilitates hole injection into the functional layer. Specific examples of anode materials include: metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combined 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 are not limited thereto. Preferably, a transparent electrode comprising indium tin oxide (ITO) as an anode is included.

[0165] In the present application, the hole transport layer may include one or more hole transport materials. The hole transport layer material may be selected from carbazole polymers, carbazole-linked triarylamine compounds or other types of compounds, and may specifically be selected from the following compounds or any combination thereof:

[0166]

[0167] In one embodiment, the first hole transport layer 321 may be composed of HT-1 or NPB.

[0168] In one embodiment, the second hole transport layer 322 is composed of HT-2 or HT-15.

[0169] Optionally, a hole injection layer 310 is provided between the anode 100 and the first hole transport layer 321 to enhance the ability to inject holes into the first hole transport layer 321. The hole injection layer 310 may be made of a benzidine derivative, a starburst arylamine compound, a phthalocyanine derivative, or other materials, and this application does not impose any particular limitation thereto. The material of the hole injection layer 310 is, for example, selected from the following compounds or any combination thereof:

[0170]

[0171]

[0172] In one embodiment, the hole injection layer 310 is composed of PD.

[0173] In the present application, the organic light-emitting layer 330 may be composed of a single light-emitting material or may include a host material and a guest material. Optionally, the organic light-emitting layer 330 is composed of a host material and a guest material. Holes and electrons injected into the organic light-emitting layer 330 may recombine in the organic light-emitting layer 330 to form excitons. The excitons transfer energy to the host material, and the host material transfers energy to the guest material, thereby enabling the guest material to emit light.

[0174] The host material of the organic light-emitting layer 330 may include metal chelate compounds, bisphenylethylene derivatives, aromatic amine derivatives, dibenzofuran derivatives, or other types of materials. Optionally, the host material includes the nitrogen-containing compound of the present application.

[0175] The guest material of the organic light-emitting layer 330 can be a compound having a condensed aromatic ring or its derivative, a compound having a heteroaromatic ring or its derivative, an aromatic amine derivative or other materials, and this application does not impose any special restrictions on this. The guest material is also called a doping material or dopant. According to the type of luminescence, it can be divided into fluorescent dopants and phosphorescent dopants. Specific examples of the phosphorescent dopant include, but are not limited to,

[0176]

[0177] In one embodiment of the present application, the organic electroluminescent device is a red organic electroluminescent device. In a more specific embodiment, the host material of the organic light-emitting layer 330 comprises the nitrogen-containing compound of the present application. The guest material is, for example, RD-1 or GD.

[0178] In one embodiment of the present application, the organic electroluminescent device is a green organic electroluminescent device. In a more specific embodiment, the host material of the organic light-emitting layer 330 comprises the nitrogen-containing compound of the present application. The guest material is, for example, fac-Ir(ppy)3.

[0179] The electron transport layer 340 may be a single-layer structure or a multi-layer structure, and may include one or more electron transport materials. The electron transport materials may be selected from, but not limited to, BTB, LiQ, benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials, and are not specifically limited in this application. The materials of the electron transport layer 340 include, but are not limited to, the following compounds:

[0180]

[0181] In one embodiment of the present application, the electron transport layer 340 may be composed of ET-1 and LiQ, or ET-2 and LiQ, or ET-6 and LiQ.

[0182] In the present application, cathode 200 may include a cathode material having a small work function that facilitates electron injection 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 alloys thereof; or multilayer materials such as LiF / Al, Liq / Al, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca. Alternatively, a metal electrode containing magnesium and silver may be included as the cathode.

[0183] Optionally, an electron injection layer 350 is further provided between the cathode 200 and the electron transport layer 340 to enhance the ability to inject electrons into the electron transport layer 340. The electron injection layer 350 may include an inorganic material such as an alkali metal sulfide or an alkali metal halide, or may include a complex of an alkali metal and an organic matter. In one embodiment of the present application, the electron injection layer 350 may include ytterbium (Yb).

[0184] A third aspect of the present application provides an electronic device comprising the organic electroluminescent device described in the second aspect of the present application.

[0185] According to one embodiment, Figure 2 As shown, the provided electronic device is electronic device 400, which includes the above-mentioned organic electroluminescent device. Electronic device 400 can be, for example, a display device, a lighting device, an optical communication device, or other types of electronic devices, including but not limited to computer screens, mobile phone screens, televisions, electronic paper, emergency lighting, optical modules, etc.

[0186] The synthesis method of the nitrogen-containing compound of the present application is described in detail below with reference to synthesis examples, but the present disclosure is not limited thereby.

[0187] Synthesis Example

[0188] Those skilled in the art will recognize that the chemical reactions described herein can be used to appropriately prepare many of the organic compounds described herein, and that other methods for preparing the compounds described herein are considered within the scope of this application. For example, the synthesis of compounds not exemplified herein can be successfully accomplished by one skilled in the art through modifications such as appropriate protection of interfering groups, the use of known reagents other than those described herein, or conventional modifications of reaction conditions. Compounds for which the syntheses are not described herein are obtained from commercially available raw materials.

[0189] Synthesis of Sub-a1:

[0190]

[0191] Under nitrogen, 10-bromo-7H-benzo[C]carbazole (29.62 g, 100 mmol), benzyl bromide (25.65 g, 150 mmol), potassium hydroxide (11.22 g, 200 mmol), and tetrahydrofuran (300 mL) were added sequentially to a 500 mL three-necked flask. Stirring and heating were initiated, and the temperature was raised to 60°C for 6 h. After cooling to room temperature, the mixture was extracted with tetrahydrofuran (100 mL x 3). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation to obtain the crude product. Purification by silica gel column chromatography using n-heptane / dichloromethane as the mobile phase afforded Sub-a1 (33.22 g, 86% yield) as a white solid.

[0192] Referring to the synthesis of Sub-a1, Sub-a2 to Sub a-10 were synthesized by using reactant A shown in Table 1 instead of 10-bromo-7H-benzo[C]carbazole.

[0193] Table 1: Synthesis of Sub-a2 to Sub-a10

[0194]

[0195] Synthesis of Sub-b1:

[0196]

[0197] Under nitrogen atmosphere, Sub-a1 (19.31 g, 50 mmol), diboronic acid pinacol ester (15.24 g, 60 mmol), potassium acetate (9.81 g, 100 mmol) and 1,4-dioxane (220 mL) were added in sequence to a 500 mL three-necked flask. Stirring and heating were started. When the system was heated to 40 ° C, tris(dibenzylideneacetone)dipalladium (0.46 g, 0.5 mmol) and 2-dicyclohexylphosphine-2',4',6'triisopropylbiphenyl (0.48 g, 1.0 mmol) were quickly added. The temperature was continued to rise to reflux and the reaction was stirred overnight. After the system was cooled to room temperature, 200 mL of water was added to the system, and the mixture was stirred thoroughly for 30 min. The mixture was filtered under reduced pressure, and the filter cake was washed with deionized water until neutral, and then rinsed with 100 mL of anhydrous ethanol to obtain a gray solid crude product. The crude product was slurried once with n-heptane, dissolved with 200 mL of toluene, and passed through a silica gel column to remove the catalyst. After concentration, a white solid Sub-b1 (16.46 g, 76% yield) was obtained.

[0198] Referring to the synthesis of Sub-b1, reactant B shown in Table 2 was used instead of Sub-a1 to synthesize Sub-b2 to Sub-b18.

[0199] Table 2: Synthesis of Sub-b2 to Sub-b18

[0200]

[0201]

[0202] Synthesis of Sub-c1:

[0203]

[0204] Under nitrogen, a 1000 mL three-necked flask was charged with Sub-b1 (23.83 g, 55 mmol), CAS: 116233-18-2 (15.61 g, 50 mmol), tetrakis(triphenylphosphine)palladium (0.58 g, 0.5 mmol), anhydrous potassium carbonate (13.82 g, 100 mmol), toluene (240 mL), anhydrous ethanol (60 mL), and deionized water (60 mL). Stirring and heating were initiated, and the temperature was raised to reflux for 16 h. After cooling to room temperature, the mixture was extracted with dichloromethane (100 mL x 3). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to obtain the crude product. Purification by silica gel column chromatography using n-heptane / dichloromethane as the mobile phase afforded Sub-c1 (21.0 g, 78% yield) as a white solid.

[0205] Sub-c2 to Sub-c18 were synthesized by referring to Sub-c1 and using reactant C shown in Table 3 instead of Sub-b1.

[0206] Table 3: Synthesis of Sub-c2 to Sub-c18

[0207]

[0208]

[0209] Synthesis of Sub-d1:

[0210]

[0211] Under a nitrogen atmosphere, Sub-c1 (26.93 g, 50 mmol), triphenylphosphine (32.78 g, 125 mmol), and o-dichlorobenzene (150 mL) were added to a 250 mL three-necked flask. Stirring and heating were initiated, and the temperature was raised to reflux for 16 hours. After the system was cooled to room temperature, the solvent was removed by distillation under reduced pressure to obtain the crude product. Purification by silica gel column chromatography using n-heptane as the mobile phase afforded Sub-d1 (14.18 g, 56% yield) as a gray-green solid.

[0212] Sub-d2 to Sub-d18 were synthesized by referring to Sub-d1 and using reactant D shown in Table 4 instead of Sub-c1.

[0213] Table 4: Synthesis of Sub-d2 to Sub-d18

[0214]

[0215]

[0216] Synthesis of Sub-e1:

[0217]

[0218] Under nitrogen, a 500 mL three-necked flask was charged with Sub-a8 (16.81 g, 50 mmol), CAS: 116233-20-6 (14.11 g, 50 mmol), tris(dibenzylideneacetone)dipalladium (0.916 g, 1 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.95 g, 2 mmol), sodium tert-butoxide (9.61 g, 100 mmol), and xylene (250 mL). The mixture was heated to reflux and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane (100 mL x 3). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to obtain the crude product. Purification by silica gel column chromatography using n-heptane / dichloromethane as the mobile phase afforded Sub-e1 (14.24 g, 53% yield) as a gray-green solid.

[0219] Sub-e2 to Sub-e7 were synthesized by referring to Sub-e1 and using reactant E shown in Table 5 instead of Sub-d1.

[0220] Table 5: Synthesis of Sub-e2 to Sub-e7

[0221]

[0222] Synthesis of Sub-f1:

[0223]

[0224] Under nitrogen, Sub-e1 (26.88 g, 50 mmol), palladium acetate (0.56 g, 2.5 mmol), tricyclohexylphosphine tetrafluoroborate (CAS: 58656-04-5, 1.84 g, 5 mmol), cesium carbonate (32.58 g, 100 mmol), and N,N-dimethylacetamide (260 mL) were added sequentially to a 500 mL three-necked flask. The mixture was heated to reflux and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane (100 mL x 3). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to obtain the crude product. Purification by silica gel column chromatography using n-heptane / dichloromethane as the mobile phase afforded Sub-f1 (10.27 g, 45% yield) as an off-white solid.

[0225] Referring to the synthesis of Sub-f1, reactant F shown in Table 6 was used instead of Sub-e1 to synthesize Sub-f2 to Sub-f7.

[0226] Table 6: Synthesis of Sub-f2 to Sub-f7

[0227]

[0228] Synthesis of Sub-g1:

[0229]

[0230] Under nitrogen, a 500 mL three-necked flask was charged with Sub-d1 (25.33 g, 50 mmol), bromobenzene (7.85 g, 55 mmol), tris(dibenzylideneacetone)dipalladium (0.916 g, 1 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos, 0.95 g, 2 mmol), sodium tert-butoxide (9.61 g, 100 mmol), and xylene (250 mL). The mixture was heated to reflux and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane (100 mL x 3). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to obtain the crude product. Purification by silica gel column chromatography using n-heptane / dichloromethane as the mobile phase afforded Sub-g1 as an off-white solid (15.05 g, 73% yield).

[0231] Referring to the synthesis of Sub-g1, reactant G shown in Table 7 was used instead of Sub-d1 to synthesize Sub-g2 to Sub-g13.

[0232] Table 7: Synthesis of Sub-g2 to Sub-g13

[0233]

[0234]

[0235] Synthesis of Sub-g14:

[0236]

[0237] Under a nitrogen atmosphere, Sub-e1 (14.57 g, 25 mmol) and 200 mL of benzene-D6 were added to a 100 mL three-necked flask. The temperature was raised to 60°C, and trifluoromethanesulfonic acid (22.51 g, 150 mmol) was added. The temperature was continued to rise to boiling and stirred for 24 hours. After the reaction system cooled to room temperature, 50 mL of heavy water was added, stirred for 10 minutes, and then a saturated aqueous solution of K3PO4 was added to neutralize the reaction solution. The organic layer was extracted with dichloromethane (50 mL × 3 times), the organic phases were combined and dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to obtain the crude product. Silica gel column chromatography using n-heptane / dichloromethane as the mobile phase gave Sub-g14 (9.48 g, 64% yield) as a white solid.

[0238] Referring to the synthesis of Sub-g14, Sub-g15 was synthesized by using reactant H shown in Table 8 instead of Sub-e1.

[0239] Table 8: Synthesis of Sub-g15

[0240]

[0241] Synthesis of Sub-h1:

[0242]

[0243] Under a nitrogen atmosphere, Sub-e1 (20.11 g, 50 mmol), potassium tert-butoxide (56.10 g, 500 mmol), and DMSO (300 mL) were added sequentially to a 500 mL three-necked flask. Stirring and heating were initiated, and the temperature was raised to 60°C for 4 hours. After the system cooled to room temperature, the reaction solution was poured into 500 mL of deionized water, resulting in precipitation. The filter cake was collected by suction and dissolved in dichloromethane (200 mL). After drying with anhydrous sodium sulfate, the filtrate was filtered and the solvent was removed by vacuum distillation to obtain the crude product. Purification by silica gel column chromatography using n-heptane / dichloromethane as the mobile phase afforded Sub-h1 (13.11 g, 84% yield) as an off-white solid.

[0244] Referring to the synthesis of Sub-h1, reactant J shown in Table 9 was used instead of Sub-e1 to synthesize Sub-h2 to Sub-h15.

[0245] Table 9: Synthesis of Sub-h2 to Sub-h15

[0246]

[0247]

[0248] Synthesis of compound A-3:

[0249]

[0250] Under nitrogen, Sub-h1 (12.32 g, 25 mmol), RA-1 (7.26 g, 30 mmol), tris(dibenzylideneacetone)dipalladium (0.46 g, 0.5 mmol), 2-dicyclohexylphosphine-2',4',6'triisopropylbiphenyl (SPhos, 0.41 g, 1 mmol), sodium tert-butoxide (4.80 g, 50 mmol), and xylene (120 mL) were added sequentially to a 250 mL three-necked flask. The mixture was heated to reflux and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane (100 mL × 3 times). The organic phases were combined and dried over anhydrous sodium sulfate. After filtration, the solvent was removed by distillation under reduced pressure to obtain the crude product. Purification by silica gel column chromatography using n-heptane / dichloromethane as the mobile phase gave A-3 as a white solid (10.29 g; yield 63%), m / z = 654.4 [M+H] + .

[0251] Referring to the synthesis of compound A-3, the following compounds of the present application were synthesized using reactant K shown in Table 10 instead of Sub-h1 and reactant L instead of RA-1.

[0252] Table 10: Synthesis of compounds of the present invention

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259] Synthesis of compound B-3:

[0260]

[0261] Under nitrogen atmosphere, Sub-h9 (11.06 g, 25 mmol), 2-chloro-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine (12.89 g, 37.5 mmol) and dry DMF (200 mL) were added to a 500 mL three-necked flask in sequence. The system was cooled to -10°C and sodium hydroxide (60% content, 1.1 g, 55 mmol) was quickly added. The reaction was stirred overnight. The reaction solution was poured into 200 mL of deionized water and stirred thoroughly for 30 min. The filtered solid was collected and washed with deionized water until neutral, and then rinsed with anhydrous ethanol (200 mL) to obtain a crude product. The crude product was purified by silica gel column chromatography using n-heptane / dichloromethane as the mobile phase to obtain a white solid B-3 (14.43 g, 77% yield), m / z = 750.4 [M+H] + .

[0262] Referring to the synthesis of compound B-3, the reactant M shown in Table 11 was used instead of Sub-h9, and the reactant N was used instead of 2-chloro-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine to synthesize the compounds of the present application in Table 12.

[0263] Table 12: Synthesis of compounds of the present application

[0264]

[0265]

[0266]

[0267]

[0268] Synthesis of compound B-172:

[0269]

[0270] Under a nitrogen atmosphere, Sub-h1 (14.78 g, 30 mmol), CAS: 1801233-15-7 (9.8 g, 33 mmol), anhydrous potassium carbonate (K2CO3, 4.15 g, 30 mmol), 4-dimethylaminopyridine (1.83 g, 15 mmol), and N,N-dimethylacetamide (100 mL) were added to a 500 mL three-necked flask in sequence and the mixture was heated to reflux for 16 h. After the system cooled to room temperature, it was extracted with dichloromethane (100 mL × 3 times). The organic phases were combined and dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation to obtain the crude product. The crude product was purified by silica gel column chromatography using n-heptane / dichloromethane as the mobile phase to obtain B-172 (13.10 g, 58% yield) as a white solid with m / z = 753.3 [M+H]. + .

[0271] Referring to the synthesis of compound B-172, reactant O shown in Table 13 was used to replace Sub-h1, and reactant P was used to replace CAS: 1801233-15-7 to synthesize the compounds of the present application in Table 13.

[0272] Table 13: Synthesis of compounds of the present invention

[0273]

[0274]

[0275] Compound A-8 NMR: 1 H-NMR(400MHz,CD2Cl2)δppm 8.91(d,1H),8.21(d,1H),7.99(d,1H),7.91(d,1H),7.87(d,1H),7.77(d,1H),7.74(d,1H),7.6 3(t,1H),7.59-7.35(m,15H),7.30(t,1H),7.27(s,1H),6.88(s,1H),1.77(s,4H),1.39(d,12H);

[0276] Compound A-129 NMR: 1 H-NMR(400MHz,CD2Cl2)δppm 8.22(d,1H),7.96(s,1H),7.89-7.77(m,4H),7.70-7.63(m,6H),7.58(t,2H), 7.52-7.40(m,5H),7.38-7.25(m,5H),7.15(d,2H),1.74(s,4H),1.34(d,12H);

[0277] Compound A-324 NMR: 1 H-NMR(400MHz,CD2Cl2)δppm 8.92(s,1H),8.60(d,1H),8.22(d,1H),8.12(d,1H),8.06(s,1H),7.68(d,2H),7.63(d,1H ),7.59-7.26(m,18H),7.19(t,1H),7 / 07(d,2H),6.97(s,1H),1.78(s,4H),1.40(d,12H);

[0278] Compound B-157 NMR: 1H-NMR(400MHz,CD2Cl2)δppm 10.02(s,1H),8.84(s,1H),8.61(d,1H),8.52(d,2H),8.21(d,1H),8.10(s,1H),8.04(d,1H),8.00(d,1 H),7.91(d,1H),7.84(s,1H),7.81(d,1H),7.68(s,1H),7.66-7.31(m,9H),1.75(s,4H),1.36(d,12H);

[0279] Compound B-182 NMR: 1 H-NMR(400MHz,CD2Cl2)δppm 8.54(d,1H),8.36(s,1H),8.21(s,1H),8.15(s,1H),8.12-7.98(m,6H),7.95(d,1H),7.91- 7.80(m,4H),7.66-7.46(m,8H),7.44-7.38(m,2H),7.27(s,1H),1.77(s,4H),1.38(d,12H);

[0280] Preparation and evaluation of organic electroluminescent devices:

[0281] Example 1: Red organic electroluminescent device

[0282] First, the anode pretreatment is carried out through the following process: On the ITO / Ag / ITO substrate, the surface treatment was performed using ultraviolet ozone and O2:N2 plasma to increase the work function of the anode, and the surface of the ITO substrate was cleaned with an organic solvent to remove impurities and oil stains on the surface of the ITO substrate.

[0283] PD was vacuum-deposited on the experimental substrate (anode) to form a The hole injection layer (HIL) is then vacuum-deposited with HT-1 to a thickness of The first hole transport layer.

[0284] Compound HT-2 is vacuum evaporated on the first hole transport layer to form a layer with a thickness of The second hole transport layer

[0285] Next, compound A-3:RH-N:RD-1 was co-deposited on the second hole transport layer at a deposition rate ratio of 49%:49%:2% to form a layer with a thickness of red light emitting layer (EML).

[0286] On the light-emitting layer, compound ET-1 and LiQ were mixed in a weight ratio of 1:1 and evaporated to form Yb is evaporated on the electron transport layer to form a layer with a thickness of Then, magnesium (Mg) and silver (Ag) were mixed at a 1:9 evaporation rate and vacuum evaporated on the electron injection layer to form a layer with a thickness of cathode.

[0287] In addition, CPL-1 is vacuum-deposited on the cathode to form a layer with a thickness of The covering layer is formed, thereby completing the manufacture of the red organic electroluminescent device.

[0288] Examples 2 to 45

[0289] An organic electroluminescent device was prepared by the same method as in Example 1, except that the compounds listed in Table 14 below were used instead of Compound A-3 in Example 1 when preparing the light-emitting layer.

[0290] Comparative Examples 1 to 3

[0291] An organic electroluminescent device was prepared using the same method as in Example 1, except that Compound A, Compound B, and Compound C were used to replace Compound A-3 in Example 1 when preparing the light-emitting layer.

[0292] Among them, the compound structures used in each embodiment and comparative example are as follows:

[0293]

[0294] The performance of the red organic electroluminescent devices prepared in Examples 1 to 45 and Comparative Examples 1 to 3 was tested. Specifically, at 10 mA / cm 2 The IVL performance of the device was tested under the conditions of T95 device life at 20mA / cm 2 The test was carried out under the conditions of , and the test results are shown in Table 14.

[0295] Table 14

[0296]

[0297]

[0298]

[0299] As can be seen from Table 15 above, when the compound of the present invention is used as a hole transport host material in a mixed red light host material, the efficiency is increased by at least 11.3% and the lifetime is increased by at least 10.8%.

[0300] Example 46: Red organic electroluminescent device

[0301] First, the anode pretreatment is carried out through the following process: On the ITO / Ag / ITO substrate, the surface treatment was performed using ultraviolet ozone and O2:N2 plasma to increase the work function of the anode, and the surface of the ITO substrate was cleaned with an organic solvent to remove impurities and oil stains on the surface of the ITO substrate.

[0302] PD was vacuum-deposited on the experimental substrate (anode) to form a Then HT-1 was vacuum-deposited on the hole injection layer to form a hole injection layer with a thickness of The first hole transport layer.

[0303] Compound HT-2 is vacuum evaporated on the first hole transport layer to form a layer with a thickness of a second hole transport layer.

[0304] Next, compound B-49:RD-1 was co-evaporated on the second hole transport layer at an evaporation rate ratio of 98%:2% to form a film with a thickness of red light emitting layer (EML).

[0305] On the light-emitting layer, compound ET-1 and LiQ were mixed in a weight ratio of 1:1 and evaporated to form Yb is evaporated on the electron transport layer to form a layer with a thickness of Then, magnesium (Mg) and silver (Ag) were mixed at a 1:9 evaporation rate and vacuum evaporated on the electron injection layer to form a layer with a thickness of cathode.

[0306] In addition, CPL-1 is vacuum-deposited on the cathode to form a layer with a thickness of The covering layer is formed, thereby completing the manufacture of the red organic electroluminescent device.

[0307] Examples 47 to 69

[0308] An organic electroluminescent device was prepared by the same method as in Example 46, except that the compound shown in Table 15 below was used instead of Compound B-49 in Example 46 when preparing the light-emitting layer.

[0309] Comparative Examples 4-5

[0310] An organic electroluminescent device was prepared by the same method as in Example 46, except that Compound D and Compound E were used instead of Compound B-49 in Example 46 when preparing the light-emitting layer.

[0311] Among them, in Examples 46 to 69 and Comparative Examples 4 to 5, the structures of the compounds used are as follows:

[0312]

[0313] The performance of the red organic electroluminescent devices prepared in Examples 46 to 69 and Comparative Examples 4 to 5 was tested. Specifically, at 10 mA / cm 2 The IVL performance of the device was tested under the conditions of T95 device life at 20mA / cm 2 The test was carried out under the conditions of , and the test results are shown in Table 15.

[0314] Table 15

[0315]

[0316]

[0317] As can be seen from Table 15 above, when the compound of the present invention is used as a bipolar red light host material, the device efficiency is increased by at least 15.0%, and the life span is increased by at least 10.6%.

[0318] Example 70: Green organic electroluminescent device

[0319] First, the anode pretreatment is carried out through the following process: On the ITO / Ag / ITO substrate, the surface treatment was performed using ultraviolet ozone and O2:N2 plasma to increase the work function of the anode, and the surface of the ITO substrate was cleaned with an organic solvent to remove impurities and oil stains on the surface of the ITO substrate.

[0320] PD was vacuum-deposited on the experimental substrate (anode) to form a The hole injection layer (HIL) is formed by evaporating NPB on the hole injection layer to form a thickness of The first hole transport layer.

[0321] HT-15 is vacuum evaporated on the first hole transport layer to form a layer with a thickness of a second hole transport layer.

[0322] On the second hole transport layer, compound B-3:GH-P:GD were co-evaporated at an evaporation rate ratio of 40%:55%:5% to form a layer with a thickness of green emitting layer (EML).

[0323] ET-6 and LiQ were mixed in a weight ratio of 1:1 and evaporated to form Yb is evaporated on the electron transport layer to form a layer with a thickness of Then, magnesium (Mg) and silver (Ag) were mixed at a deposition rate of 1:9 and vacuum-deposited on the electron injection layer to form an electron injection layer with a thickness of cathode.

[0324] In addition, CPL-1 is evaporated on the cathode to form a layer with a thickness of A covering layer is formed, thereby completing the manufacture of the organic light-emitting device, and the prepared device is recorded as Example 70.

[0325] Example 71 to Example 80

[0326] An organic electroluminescent device was prepared by the same method as in Example 70, except that the compound shown in Table 16 was used instead of Compound B-3 in Example 70 when forming the light-emitting layer.

[0327] Comparative Examples 6 and 7

[0328] An organic electroluminescent device was prepared using the same method as in Example 70, except that Compound G and Compound H were used instead of Compound B-3 in Example 70 when preparing the light-emitting layer.

[0329] Among them, when preparing each embodiment and comparative example, the compound structure used is as follows:

[0330]

[0331] The green organic electroluminescent devices prepared in Examples 70 to 80 and Comparative Examples 6 to 7 were tested for their performance. Specifically, at 10 mA / cm 2 The IVL performance of the device was tested under the conditions of T95 device life at 20mA / cm 2 The test was carried out under the following conditions. The test results are shown in Table 16.

[0332] Table 16

[0333]

[0334]

[0335] As can be seen from Table 16 above, when the compound of the present invention is used as an electron transport host material in a hybrid green light host material, the device efficiency is increased by at least 16.1%, and the lifespan is increased by at least 14.1%.

[0336] The reason for this is that the structure of the compound of the present application contains a core structure of tetramethylcyclohexane-indole-carbazole, further connected to an aryl or heteroaryl group, as well as an electron-deficient heteroaryl group containing at least two nitrogen atoms, through the two nitrogen atoms in the indole-carbazole. The indole-carbazole group has excellent hole transport ability, and the structure of tetramethylcyclohexane can further enhance the hole transport ability of the carbazole group through the hyperconjugation effect, giving the compound of the present application excellent hole transport ability. When tetramethylcyclohexane-indole-carbazole is connected to an electron-rich aryl or heteroaryl group, it can form a material with excellent hole transport properties; when tetramethylcyclohexane-indole-carbazole is connected to an electron-deficient heteroaryl group containing at least two nitrogen atoms, it can form a material with electron transport properties or a bipolar material. In addition, the four methyl groups are spatially configured outside the conjugated plane of the carbazole group, forming a certain amount of steric hindrance, which can finely control the intermolecular stacking of the compound and enable the compound to form a good amorphous film. When the compound of the present application is used as a host material, the carrier balance in the light-emitting layer can be improved, the carrier recombination area can be widened, the exciton generation and utilization efficiency can be increased, and the luminous efficiency and life of the device can be improved.

[0337] The preferred embodiments of the present invention are described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the scope of protection of the present invention.

Claims

1. A nitrogen-containing compound, characterized in that It has a structure formed by the mutual fusion of the following formula i-1 and formula 2, wherein formula 2 is fused to the * position on ring B in formula i-1: Ring C is selected from aromatic rings having 6 to 14 carbon atoms; Groups A1 and A2 are independently selected from the structure represented by formula a-1 or the structure represented by formula a-2, and at least one of A1 and A2 is selected from the structure represented by formula a-1; L, L1, L2 and L3 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms; Ar3 is selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms; Het is a nitrogen-containing heteroarylene group having 3 to 20 carbon atoms; Ar1 and Ar2 are the same or different and are each independently selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms; Each R2 and R3 is the same or different and is independently selected from deuterium, cyano, a halogen group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a deuterated alkyl group having 1 to 10 carbon atoms, a phenyl group, or a deuterated phenyl group; optionally, any two adjacent R2 groups form a 6-membered aromatic ring, and the 6-membered aromatic ring is optionally substituted with 0, 1, 2, 3 or 4 R4 groups; Each R4 is independently selected from deuterium, cyano, halogen, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, and deuterated alkyl having 1 to 10 carbon atoms; n2 is selected from 0, 1 or 2; n3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; The substituents in L1, L2, L3, Ar1, Ar2 and Ar3 are the same or different and are independently selected from deuterium, cyano, halogen, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, deuterated alkyl having 1 to 10 carbon atoms, phenyl or deuterated phenyl; optionally, any two adjacent substituents in Ar3 form a benzene ring or a fluorene ring; The following compounds are excluded:

2. The nitrogen-containing compound according to claim 1, wherein Ring C is selected from a benzene ring, a naphthalene ring or a phenanthrene ring.

3. The nitrogen-containing compound according to claim 1, wherein each R2 and R3 are the same or different and are independently selected from deuterium, cyano, fluorine, trideuteromethyl, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, phenyl; Optionally, any two adjacent R2 form a benzene ring, which is substituted by 0, 1, 2, 3 or 4 R4; each R4 is independently selected from deuterium, cyano, fluorine, trideuterated methyl or trifluoromethyl.

4. The nitrogen-containing compound according to claim 1, wherein Het is selected from the following groups: -# indicates the bond connected to L, represents the bond connected to L1, Represents the bond connected to L2; the formula does not contain , which means the location is connected to In the formula (a), L2 is a single bond and Ar2 is hydrogen.

5. The nitrogen-containing compound according to claim 1, wherein Het is selected from the following groups: -# indicates the bond connected to L, represents the bond connected to L1, Represents the bond connected to L2; the formula does not contain , which means the location is connected to In the formula (a), L2 is a single bond and Ar2 is hydrogen.

6. The nitrogen-containing compound according to claim 1, wherein L, L1, L2 and L3 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted carbazolylene group.

7. The nitrogen-containing compound according to claim 6, wherein The substituents in L, L1, L2 and L3 are the same or different and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trideuterated methyl or phenyl.

8. The nitrogen-containing compound according to claim 1, wherein Ar1 and Ar3 are each independently selected from a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, or a substituted or unsubstituted heteroaryl group having 7 to 20 carbon atoms; Ar2 is selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, or a substituted or unsubstituted heteroaryl group having 7 to 20 carbon atoms.

9. The nitrogen-containing compound according to claim 8, wherein The substituents in Ar1, Ar2 and Ar3 are each independently selected from deuterium, a halogen group, a cyano group, a haloalkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms or a phenyl group. Optionally, any two adjacent substituents in Ar3 form a benzene ring or a fluorene ring.

10. The nitrogen-containing compound according to claim 1, wherein Ar3 are each independently selected from the following substituted or unsubstituted groups; The substituted groups have one or more substituents, and the substituents in each group are independently selected from deuterium, fluorine, cyano, trideuteromethyl, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, and phenyl; Ar1 is selected from a substituted or unsubstituted group V; Ar2 is selected from hydrogen, a substituted or unsubstituted group V; wherein the unsubstituted group V is selected from the following groups: The substituted group V has one or more substituents, and the substituents of the group V are each independently selected from deuterium, fluorine, cyano, trideuteromethyl, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, and phenyl. When the number of substituents on the group V is greater than 1, the substituents are the same or different.

11. The nitrogen-containing compound according to claim 1, wherein At least one of A1 and A2 is a structure represented by formula a-1, and the structure represented by formula a-1 Selected from the following groups:

12. The nitrogen-containing compound according to claim 1, wherein Selected from the group consisting of the following groups, is selected from hydrogen or the following groups:

13. Nitrogen-containing compounds, wherein The nitrogen-containing compound is selected from the group consisting of the following compounds:

14. Nitrogen-containing compounds having the following structure:

15. An organic electroluminescent device comprising an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode; characterized in that: The functional layer comprises the nitrogen-containing compound according to any one of claims 1 to 14.

16. The organic electroluminescent device according to claim 15, characterized in that: The functional layer includes an organic light-emitting layer, and the organic light-emitting layer contains the nitrogen-containing compound.

17. An electronic device, characterized in that The organic electroluminescent device according to claim 15 or 16.

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