Boron-nitrogen-containing organic compound, application thereof and organic electroluminescent device

Abstract

The invention provides an organic compound and application thereof, and an organic electroluminescent device containing the organic compound, particularly relates to a boron-nitrogen-containing organic compound, belongs to the technical field of organic luminescent materials, and also relates to application of the compound in the organic electroluminescent device. The organic compound has a structure as shown in the following formula. The organic compound provided by the invention is beneficial to prolonging the service life of a device. # imgabs0 #

Description

Technical Field

[0001] The invention relates to a boron-nitrogen-containing organic compound, belonging to the technical field of organic luminescent materials. The invention also relates to the application of the compound in an organic electroluminescent device and the organic electroluminescent device. Background Art

[0002] With the continuous progress and development of social sciences, display technology has become crucial in people's lives. Organic light-emitting diodes (OLEDs) have become one of the mainstream display devices due to their many advantages such as flexibility, bendability, self-luminescence, high contrast, large size, and low power consumption.

[0003] The luminescence mechanism of OLEDs is that electrons and holes recombine to form excitons under electrical excitation. Excitons obey probability statistical distribution, with singlet excitons accounting for about 25% and triplet excitons accounting for about 75%. The first generation of luminescence technology is collectively referred to as fluorescence technology, which uses singlet excitons to emit light; the second generation of luminescence technology is collectively referred to as phosphorescence technology, which uses triplet excitons to emit light. In theory, it can achieve 100% internal quantum efficiency, but the heavy metals required to construct phosphorescent dyes are not only expensive but also pollute the environment. Therefore, the third generation of thermally excited delayed fluorescence technology constructed using organic small molecules is currently widely used. When the single-triplet energy level difference is very small, triplet excitons can reverse intersystem crossing to the singlet state, and then return to the ground state to emit light. Among them, red and green dyes as the three primary colors have become the mainstream of current commercial display devices due to their high electroluminescence efficiency and low power consumption. However, the chromaticity and life of blue light materials do not meet the current commercial display requirements. Blue light devices still use traditional fluorescent materials to achieve high color purity and long device life.

[0004] In recent years, the research groups of Takuji Hatakeyama and Junji Kido in Japan have reported a series of organic small molecule materials DABNA-1 (Adv. Mater. 2016, 28, 2777–2781 J. Mater. Chem. C, 2019, 7, 3082-3089) based on the thermally excited delayed fluorescence of boron nitrogen resonance. The boron atoms, nitrogen atoms and phenyl groups in this type of compound constitute a rigid polycyclic aromatic resonance skeleton, thus having a higher fluorescence quantum yield. Compared with traditional blue fluorescent dyes, this type of compound has a narrower emission spectrum band gap and higher color purity. However, the rigid planar structure also leads to a large difference in energy levels between the singlet and triplet states, and the reverse intersystem crossing from the triplet state to the singlet state is slow. After the excitons recombine on the dye, they will cause severe efficiency roll-off and the device life is short. In addition, an overly planar rigid structure often leads to adverse effects such as widening of the emission spectrum and red shift due to excessive doping concentration.

[0005]

[0006] Existing organic electroluminescent materials still have a lot of room for improvement in terms of luminescent performance, and the industry urgently needs to develop new luminescent material systems to meet commercial needs. Boron nitrogen resonance materials have the advantages of high color purity and high luminescent efficiency, which has attracted widespread attention from the scientific research and industry. However, since the peripheral substituents have little effect on their energy levels, it is difficult to regulate the luminescent color of the material, and its light color has always been limited to the sky blue light region, which greatly limits the further application of such materials in high-resolution display, full-color display and white light illumination.

[0007] As OLED products gradually enter the market, people have higher and higher requirements for the performance of such products. Although this series of materials has broad application prospects, due to the serious intramolecular rotation, this type of material will lose energy due to the vibrational-rotational energy level, resulting in low external quantum efficiency; even as disclosed in the prior art, some compound structures use dimethylfluorene structures to suppress the intramolecular rotational energy level, but due to the imbalance of charge transfer, the device life is poor. Therefore, the existing organic electroluminescent materials still have a lot of room for improvement in luminescent performance, and the industry urgently needs to develop new luminescent material systems to meet commercial needs. Through careful thinking and continuous experiments, the researchers of the present invention have discovered an ingenious molecular design scheme, which is described in detail below. Surprisingly, the compounds disclosed in the present invention are very suitable for application in OLEDs and improve device life. Summary of the invention

[0008] In order to solve the above technical problems, the purpose of the present invention is to provide a boron-nitrogen-containing organic compound and its application, and an organic electroluminescent device containing the same. Through the design of the molecular structure, the organic compound has higher carrier mobility and stability, and can emit deep blue light. The resonance-type fluorescent dye containing boron and nitrogen structure can effectively adjust the light color of the material to deep blue light, and at the same time can improve the efficiency and life of the device. Specifically, the present invention provides a boron-nitrogen-containing organic compound having a structure shown in formula (1):

[0009]

[0010] In formula (1), ring A, B, and C are each independently a C6-C50 aromatic ring or a C3-C50 heteroaromatic ring;

[0011] R 1 , R 2 , R 3 represents single substitution to maximum substitution, R 1 , R 2 , R 3are each independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; said R 1 , R 2 , R 3 They are independently connected to each other by chemical bonds to form a ring or are not connected;

[0012] Ar 1 ,Ar 2 Each is independently selected from a substituted or unsubstituted C6-C50 aromatic ring, a substituted or unsubstituted C3-C50 heteroaromatic ring;

[0013] Among them, R 1 , R 2 , R 3 ,Ar 1 ,Ar 2 At least one of them is a structure represented by formula (2),

[0014] In formula (2), X 1 -X 10 are each independently selected from C, CR' or N, R' is independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, wherein X 1 , X 2 , X 3 , X 4 , X 5 At least one of them is CR', and R' is a substituted or unsubstituted C1-C20 straight or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, X 1 -X 5 R' and X in6 -X 10 R' is not connected, X 6 -X 10 R' in is not connected to ring A or B;

[0015] Y 1 -Y 4 are independently selected from CR" or N, and the R" is independently selected from any one of hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl or C3-C60 heteroaryl; the R" and the connected aromatic ring or heteroaromatic ring are independently connected to each other by chemical bonds to form a ring or are not connected,

[0016] The substituents of the above substitutions are each independently selected from any one of C1-C20 straight or branched alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6-C30 aryl, C3-C30 heteroaryl, or a combination of at least two thereof. The * sign indicates the connection site, and the expression of the ring structure crossed by “—” indicates that the connection site is at any position on the ring structure that can form a bond. It can be understood by those skilled in the art that the so-called connection site is an example of any position on the ring structure that can form a bond, for example, X 1 -X 5 The C atoms in the molecule are the chemically possible attachment sites.

[0017] The most significant feature of the compound of the present invention is that by introducing an alkyl-substituted biphenyl group at the ortho position of the N atom, the steric hindrance of the compound is increased, aggregation quenching and molecular vibration are suppressed, and the efficiency and life of the device are improved and the spectrum is narrowed.

[0018] It should be noted that, unless otherwise defined below, the meanings of all technical terms and scientific terms used herein are intended to be the same as those generally understood by those skilled in the art. Reference to the technology used herein is intended to refer to the technology generally understood in the art, including those changes in technology or replacement of equivalent technology that are obvious to those skilled in the art. Although it is believed that the following terms are well understood by those skilled in the art, the following definitions are still set forth to better explain the present invention.

[0019] In this specification, the expression of Ca to Cb indicates that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms in the substituent. When describing C1 to C30, it includes but is not limited to C1, C2, C3, C4, C3, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C22, C24, C26, C28, etc., and other numerical ranges are not repeated.

[0020] The terms "comprises," "comprising," "having," "containing," or "involving" and other variations thereof herein are inclusive or open-ended and do not exclude additional unrecited elements or method steps.

[0021] In the present invention, the expression of chemical elements, unless otherwise specified, generally includes the concept of isotopes with the same chemical properties. For example, the expression "hydrogen" also includes the concepts of "deuterium" and "tritium" with the same chemical properties, and carbon (C) includes 12 C. 13 C, etc., no further details.

[0022] The heteroatom in the present invention is generally selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0023] As used herein, the terms "heterocyclyl" and "heterocycle" refer to a saturated (i.e., heterocycloalkyl) or partially unsaturated (i.e., having one or more double and / or triple bonds within the ring) cyclic group having at least one ring atom that is a heteroatom selected from N, O and S and the remaining ring atoms being C.

[0024] As used herein, the terms "(ylidene)aryl" and "aromatic ring" refer to an all-carbon monocyclic or fused-ring polycyclic aromatic group having a conjugated π electron system. As used herein, the terms "(ylidene)heteroaryl" and "heteroaromatic ring" refer to a monocyclic, bicyclic or tricyclic aromatic ring system. As used herein, the term "aralkyl" preferably refers to an alkyl substituted with an aryl or heteroaryl group, wherein the aryl, heteroaryl and alkyl groups are as defined herein.

[0025] As used herein, the term "halo" or "halogen" group is defined to include F, Cl, Br, or I.

[0026] The term "substituted" means that one or more (e.g., one, two, three, or four) hydrogens on the designated atom are replaced by a selection from the indicated group, provided that the normal valence of the designated atom in the present context is not exceeded and the substitution forms a stable compound. Combinations of substituents and / or variables are permitted only if such combinations form stable compounds.

[0027] If substituents are described as being "independently selected" from a group, each substituent is selected independently of the other. Thus, each substituent may be the same as or different from another (other) substituent.

[0028] As used herein, the term "one or more" means 1 or more than 1, such as 2, 3, 4, 5 or 10, where reasonable.

[0029] Unless otherwise indicated, as used herein, the point of attachment of a substituent may be from any suitable position of the substituent.

[0030] When a bond to a substituent is shown to pass through a bond connecting two atoms in a ring, then such substituent may be bonded to any ring atom in the substitutable ring.

[0031] The term "about" means within ±10% of the stated numerical value, preferably within ±5%, more preferably within ±2%.

[0032] In the structural formula disclosed in this specification, the expression of the ring structure crossed by “—” indicates that the connection site is any position on the ring structure that can form a bond.

[0033] The above-mentioned C6-C60 aromatic ring and C3-C60 heteroaromatic ring in the present invention, unless otherwise specified, are aromatic groups satisfying the π conjugated system, including both monocyclic residues and condensed ring residues. The so-called monocyclic residue refers to a molecule containing at least one phenyl group. When the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by a single bond, such as phenyl, biphenyl, terphenyl, etc.; a fused ring residue refers to a molecule containing at least two benzene rings, but the benzene rings are not independent of each other, but are fused to each other by sharing the ring edge, such as naphthyl, anthracenyl, phenanthryl, etc.; a monocyclic heteroaryl refers to a molecule containing at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and the other groups are independent of each other and connected by a single bond, such as pyridine, furan, thiophene, etc.; a fused heteroaryl refers to a molecule composed of at least one phenyl group and at least one heteroaryl group fused together, or composed of at least two heteroaryl rings fused together, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, etc.

[0034] In the present specification, the substituted or unsubstituted C6-C60 aromatic ring is preferably a C6-C30 aromatic ring, and more preferably an aromatic ring in the group consisting of phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, triphenylenyl, pyrene, chrysene, peryl, fluoranthene, naphthyl, pentacene, benzopyrene, biphenyl, isophenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, and spiroisotrimerized indenyl. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl. Preferred examples of the aromatic ring in the present invention include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, pyrenyl, peryl, The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl. The fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9-dimethylfluorene, 9,9-spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the naphthyl group is selected from the group consisting of 1-naphthyl, 2-naphthyl and 9-naphthyl.

[0035] In the present specification, the substituted or unsubstituted C6-C60 aromatic group is preferably a C6-C30 aromatic group, and more preferably a group selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, triphenylenyl, pyrene, chrysene, peryl, fluoranthene, naphthyl, pentacene, benzopyrene, biphenyl, isophenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, and spiroisotrimerized indenyl. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl. Preferred examples of the aryl group in the present invention include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, pyrenyl, peryl, The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl. The fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9-dimethylfluorene, 9,9-spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the naphthyl group is selected from the group consisting of 1-naphthyl, 2-naphthyl and 9-naphthyl. The C6-C60 aryl group of the present invention can also be a group formed by combining the above groups by single bond connection or / and fusion.

[0036] In the present specification, the substituted or unsubstituted C3-C60 heteroaromatic ring is preferably a C3-C30 heteroaromatic ring, which can be a nitrogen-containing heteroaromatic group, an oxygen-containing heteroaromatic group, a sulfur-containing heteroaromatic group, etc. Specific examples include: furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and its derivatives, quinolyl, isoquinolyl, acridinyl, phenanthridinyl , benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, phenothiazinyl, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1, 1,2,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolyl, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purinyl, pteridinyl, indolizine, benzothiadiazole and the like. Preferred examples of heteroaromatic rings in the present invention include heteroaromatic rings of furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazolebenzocarbazole, dibenzocarbazole or indolecarbazole.

[0037] In the present specification, the substituted or unsubstituted C3-C60 heteroaryl group is preferably a C3-C30 heteroaryl group, more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, etc. Specific examples include: furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and its derivatives, quinolyl, isoquinolyl, acridinyl, phenanthridine yl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, phenothiazinyl, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidazinyl, pyridinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolyl, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purinyl, pteridinyl, indolizine, benzothiadiazole and the like. Preferred examples of heteroaryl groups in the present invention include furanyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazolebenzocarbazole, dibenzocarbazole or indolecarbazole. The C3-C60 heteroaryl group of the present invention may also be a group formed by combining the above groups by single bond connection or / and fusion.

[0038] In the present invention, the aryloxy group and heteroaryloxy group include groups formed by the above-mentioned aryl group and heteroaryl group and oxygen. In the present invention, the arylamino group and heteroarylamino group include groups formed by replacing one or two H in the -NH2 group with the above-mentioned aryl group and heteroaryl group.

[0039] In the present specification, examples of C1-C20 straight-chain or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2-ethylhexyl, etc. Examples of C1-C20 chain halogenated alkyl groups include trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, etc.

[0040] In the present specification, the C3-C20 cycloalkyl group includes a monocyclic alkyl group and a polycyclic alkyl group, and specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl and the like.

[0041] The C2 to C20 alkenyl group includes both straight-chain and branched alkenyl groups, and the number of carbon atoms of the alkenyl group is preferably 2 to 10. Specific examples include vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, 7-octenyl, and groups in which these groups have substituents such as alkyl and alkoxy groups.

[0042] The C2 to C20 alkynyl group includes both straight-chain and branched alkenyl groups, and the number of carbon atoms of the alkynyl group is preferably 2 to 10. Specific examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 5-hexynyl, and groups in which these groups have substituents such as alkyl and alkoxy groups.

[0043] In the present specification, the alkoxy group refers to a group consisting of the above-mentioned straight-chain or branched alkyl group and oxygen, or a group consisting of the above-mentioned cycloalkyl group and oxygen.

[0044] Examples of C1-C20 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like, among which methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy and isopentyloxy are preferred, and methoxy is more preferred.

[0045] In the present specification, examples of C1-C20 silyl groups include silyl groups substituted with the groups listed above for the C1-C20 alkyl groups, i.e., groups formed by replacing one, two or three hydrogen atoms on the silyl group with the above straight or branched alkyl or cycloalkyl groups. Specifically, groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl and the like.

[0046] In a preferred embodiment of the present invention, the boron-nitrogen-containing organic compound has a structure as shown in formula (1-1):

[0047]

[0048] Ar 1 ,Ar 2 , Ring A, Ring B, R 1 , R 2 Having the same limited range as in formula (1);

[0049] Z 1 , Z 2 , Z 3 Each independently is CR 4 or N;

[0050] R 4 are each independently selected from any one of hydrogen, halogen, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, R 4 Each independently is not connected to the adjacent ring structure or is connected to form a ring through a chemical bond;

[0051] Preferably, the Z 1 , Z 2 , Z 3 At most one of them is N,

[0052] Preferably, the Z 1 , Z 2 , Z 3 Each independently is CR 4 ,

[0053] The substituents mentioned above are each independently selected from any one or a combination of at least two of C1~C20 straight or branched alkyl, C1~C20 chain halogenated alkyl, C2~C20 alkenyl, C3~C20 cycloalkyl, C1~C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6~C30 aryl, and C3~C30 heteroaryl. The expression of the ring structure crossed by "—" indicates that the connection site is at any position on the ring structure that can form a bond.

[0054] In a preferred embodiment of the present invention, the boron-nitrogen-containing organic compound has a structure as shown in any one of formulas (3-1) to (3-7):

[0055]

[0056] X, X ’ Selected from O or S, Ar 1 ,Ar 2 Has the same limited range as in formula (1); Z 1 , Z 2 , Z 3 Having the same limited range as in formula (1-1);

[0057] U 1 , U 2 , U 3 , U 4 , U 5 , U 6 , U 7 , U 8 , U 1’ , U 2’ , U 3’ , U 4’ , U 5’ , U 6’ , U 7’ , U 8’ Each independently is CR 5 or N;

[0058] R 5 are each independently selected from any one of hydrogen, halogen, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, R 5 Each independently is not connected to the adjacent ring structure or is connected to form a ring through a chemical bond;

[0059] Preferably, the U 1 , U 2 , U 3 and U 4 At most one of them is N; U 5 , U 6 , U7 , U 8 At most one of them is N; 1’ , U 2’ , U 3’ , U 4’ At most one of them is N; U 5’ , U 6’ , U 7’ , U 8’ At most one of them is N;

[0060] Preferably, the U 1 , U 2 , U 3 and U 4 Each independently is CR 5 ; U 5 , U 6 , U 7 and U 8 Each independently is CR 5 ; The U 1’ , U 2’ , U 3’ and U 4’ Each independently is CR 5 ; U 5’ , U 6’ , U 7’ , U 8’ Each independently is CR 5 ;

[0061] More preferably, R 5 Each is independently any one of hydrogen, substituted or unsubstituted C1-C10 straight or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0062] More preferably, R 5 Each is independently any one or a combination of two of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, and phenyl,

[0063] The substituents mentioned above are each independently selected from any one of C1-C20 straight or branched alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6-C30 aromatic, and C3-C30 heteroaromatic groups, or a combination of at least two thereof.

[0064] In a preferred embodiment of the present invention, Ar 1 ,Ar 2 At least one is a structure represented by formula (2),

[0065] Preferably, the Ar 1 ,Ar 2 One of them is a structure represented by formula (2).

[0066] In a preferred embodiment of the present invention, the Ar 1 ,Ar 2 One of the structures is selected from any one of formulas (2-1) to (2-3):

[0067]

[0068] Among them, X 1 -X 10 and Y 1 -Y 4 Having the same limited range as in formula (2);

[0069] Preferably, in formula (2-1), X 1 -X 10 Not for N, X 4 is CR' and R' is selected from any one of substituted or unsubstituted C1-C20 straight chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl; in formula (2-2), X 1 -X 10 Not for N, X 3 or X 4 is CR' and R' is selected from any one of substituted or unsubstituted C1-C20 straight chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl; in formula (2-3), X 1 -X 10 Not for N, X 2 or X 4 CR' and R' is selected from any one of substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl;

[0070] More preferably, R' is any one of methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl and cyclohexyl;

[0071] The above-mentioned substituents are each independently selected from any one of C1-C20 straight or branched alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6-C30 aryl, C3-C30 heteroaryl, or a combination of at least two thereof, and the * indicates the connection site.

[0072] In a preferred embodiment of the present invention, the Ar 1 ,Ar 2At least one of them is selected from formula (2-1).

[0073] In a preferred embodiment of the present invention, the boron-nitrogen-containing organic compound has a structure as shown in formula (3-2):

[0074]

[0075] Ar 1 is a structure selected from any one of formulas (2-1) to (2-3), Ar 2 Independently selected from substituted or unsubstituted C6-C50 aromatic rings;

[0076] More preferably, Ar 1 is one selected from the following groups,

[0077]

[0078]

[0079] More preferably, Ar 2 is one selected from the following groups,

[0080]

[0081] More preferably, Z 1 and Z 3 CH, Z 2 CR 4 ; R 4 One selected from hydrogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, preferably R 4 It is one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl and cyclohexyl.

[0082] Furthermore, the organic compound of the present invention can preferably include the specific structural compounds M1 to M98 shown below, which are only representative and do not limit the scope of the present invention:

[0083]

[0084]

[0085]

[0086]

[0087] The preparation process of the compound of the present invention is simple and easy, the raw materials are easily available, it is suitable for mass production and amplification, and it is very suitable for industrial application.

[0088] In a second aspect, the present invention provides a use of the organic compound as described in the first aspect, wherein the organic compound is applied to an organic electronic device.

[0089] Preferably, the organic electronic device includes an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet-type scanner or electronic paper, and an organic electroluminescent device is further preferred.

[0090] Preferably, the organic compound is used as a light-emitting layer material in an organic electroluminescent device.

[0091] Preferably, the organic compound is used as a luminescent dye of a light-emitting layer in an organic electroluminescent device.

[0092] In a third aspect, the present invention provides an organic electroluminescent device, comprising a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode; the organic layer comprises at least one organic compound as described in the first aspect, preferably comprises at least one organic compound with the structure shown in the above-mentioned present invention.

[0093] Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises at least one organic compound as described in the first aspect, and preferably comprises at least one organic compound having the structure shown in the above-mentioned present invention.

[0094] Preferably, the light-emitting layer comprises a host material and a dye, and the dye comprises at least one organic compound as described in the first aspect, and further preferably comprises at least one organic compound having the structure shown in the present invention.

[0095] As a preferred technical solution of the present invention, the organic compound, when used as a dye of the light-emitting layer, especially as a luminescent dye, has good luminescent properties, can improve the life and external quantum efficiency of the device, and make the device have high luminescent efficiency and better color purity, which can meet the current requirements of panel and display manufacturers for high-performance materials.

[0096] The organic compound provided by the present invention can be used as a TADF material, as a dye (guest material) of the light-emitting layer, and is suitable for organic electroluminescent devices with a TADF mechanism or an organic electroluminescent device with a TASF (thermally activated sensitized fluorescence) mechanism. It can effectively improve the performance of the device, has good carrier transport performance and high luminous efficiency, and has potential applications in solving the efficiency roll-off of OLED devices at high current density and extending the life of the device.

[0097] Preferably, the organic layer further comprises any one of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, or a combination of at least two thereof.

[0098] In a fourth aspect, the present invention provides a display device, comprising the organic electroluminescent device as described in the third aspect.

[0099] The OLED device prepared by using the compound of the present invention has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel and display manufacturers for high-performance materials. DETAILED DESCRIPTION

[0100] The technical solution of the present invention is further described in more detail below.

[0101] Synthesis methods of compounds

[0102] The compound represented by formula (I) of the present invention can be obtained by known methods, for example, by known organic synthesis methods. An exemplary synthesis route is given below, but those skilled in the art can also obtain it by other known methods. A representative synthesis route of the compound represented by the general formula of the present invention is as follows:

[0103]

[0104] The organic compounds of the present invention were synthesized representatively, and applied together with corresponding comparative compounds in organic electroluminescent devices to test the device performance under the same conditions.

[0105] The following synthesis examples of the present invention illustratively provide specific synthesis methods for representative compounds. The solvents and reagents, intermediates, ethyl acetate, methanol, ethanol and other chemical reagents used in the following synthesis examples can all be purchased or customized from the domestic chemical product market.

[0106] The specific preparation method of the organic compound of the present invention will be described in detail in the specification by taking multiple preparation examples and synthesis examples as examples, but the preparation method of the present invention is not limited to these synthesis examples. It should be noted that obtaining the organic compound is not limited to the synthesis method and raw materials used in the present invention, and those skilled in the art can also select other methods or routes to obtain the organic compound proposed in the present invention.

[0107] In addition, although representative exemplary synthetic routes of the compounds of the present invention are described in the examples, those skilled in the art can also obtain the compounds by other methods known in the art.

[0108] Organic EL devices

[0109] The OLED structure of the present invention can refer to the known technology. For example, the organic electroluminescent device OLED includes a first electrode and a second electrode, and an organic material layer between the electrodes. The organic material can be divided into multiple regions. For example, the organic material layer can include a hole transport region, a light emitting layer, and an electron transport region.

[0110] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) may also be provided on the substrate used as a display.

[0111] The first electrode can be formed by sputtering or depositing the material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as a cathode, a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0112] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic material layer can be organic small molecules, organic macromolecules and polymers, and combinations thereof.

[0113] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL is located between the HTL and the light-emitting layer.

[0114] The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives such as the compounds shown in HT-1 to HT-51 below; or any combination thereof.

[0115]

[0116]

[0117]

[0118]

[0119] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of HT-1 to HT-51 above, or one or more compounds of HI-1 to HI-3 below; or one or more compounds of HT-1 to HT-51 can be doped with one or more compounds of HI-1 to HI-3 below.

[0120]

[0121] The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit light of different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochrome light-emitting layer that emits a single color such as red, green, and blue. A plurality of monochrome light-emitting layers of different colors may be arranged in a plane according to a pixel pattern, or may be stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they may be separated from each other or may be connected to each other. The light-emitting layer may also be a single color light-emitting layer that can simultaneously emit different colors such as red, green, and blue.

[0122] According to different technologies, the light-emitting layer material can be made of different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent materials. In an OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different light-emitting materials classified by technology can emit light of the same color or different colors.

[0123] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0124]

[0125]

[0126] In one aspect of the present invention, the barrier layer surrounding the light-emitting layer may be selected from, but not limited to, a combination of one or more of PH-1 to PH-85.

[0127]

[0128]

[0129]

[0130]

[0131] The fluorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of TDE1-TDE49 listed below.

[0132]

[0133]

[0134]

[0135] In one aspect of the present invention, an electron blocking layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may be, but not limited to, one or more of the compounds HT-1 to HT-51 described above, or one or more of the compounds PH-47 to PH-77 described above; or a mixture of, but not limited to, one or more of the compounds HT-1 to HT-51 and one or more of the compounds PH-47 to PH-77.

[0136] The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0137] In one aspect of the present invention, the electron transport layer material can be selected from, but not limited to, one or more combinations of ET-1 to ET-73 listed below.

[0138]

[0139]

[0140]

[0141] In one aspect of the present invention, a hole blocking layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer may be, but not limited to, one or more compounds of ET-1 to ET-73, or one or more compounds of PH-1 to PH-46; or a mixture of one or more compounds of ET-1 to ET-73 and one or more compounds of PH-1 to PH-46.

[0142] The device may also include an electron injection layer located between the electron transport layer and the cathode. The electron injection layer material includes but is not limited to one or more combinations of the following: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, and Yb.

[0143] Specific embodiments are described below. Those skilled in the art should understand that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0144] Example

[0145] Synthesis of compounds

[0146] The specific preparation method of the above-mentioned new compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the preparation method of the present invention is not limited to these synthesis examples. It should be noted that obtaining the compound is not limited to the synthesis method and raw materials used in the present invention, and those skilled in the art can also select other methods or routes to obtain the compound proposed by the present invention. The compounds of the synthesis method not mentioned in the present invention are raw materials obtained through commercial channels, or are made by these raw materials according to known methods. The solvents and reagents used in the present invention, such as dichloromethane, petroleum ether, ethanol, tert-butylbenzene, boron tribromide, carbazole, diphenylamine, and other chemical reagents, can all be purchased from the domestic chemical product market, such as from Sinopharm Group Reagent Company, TCI Company, Shanghai Bid Pharmaceutical Company, Bailingwei Reagent Company, etc. The analysis and detection of the intermediates and compounds in the present invention uses an ABSCIEX mass spectrometer (4000QTRAP). The structural analysis and detection of the intermediates and compounds in the present invention uses a gas chromatography-mass spectrometer (GC-MS, Shimadzu QP2010 SE).

[0147] Synthesis of the compounds of the present invention

[0148] Synthesis Example 1

[0149] Synthesis of compound M10

[0150]

[0151] Synthesis of intermediate M10-1

[0152] To a 1000mL flask, 3-bromo-5,4'-di-tert-butyl-biphenyl (60g), 2-(4-tert-butylanilino)-5-tert-butylphenylboronic acid pinacol ester (77.86g), tetrakistriphenylphosphine palladium (10.04g), potassium carbonate (48.02g), 1000mL of 1,4-dioxane, and 200mL of water were added. Under nitrogen protection, the mixture was heated to 110°C for reaction for 5 hours. After stopping the heating, dichloromethane and water were added for extraction. The organic phase was spin-dried and column chromatography was performed to obtain 65.3g of a white solid.

[0153] Synthesis of intermediate M10-2

[0154] To a 1000 mL flask, add 2-bromo-4-tert-butyl-iodobenzene (20 g), M10-1 (64.4 g), cuprous iodide (1.12 g), 1,10-phenanthroline (1.06 g), potassium carbonate (16.31 g), and DMF 400 mL. Under nitrogen protection, heat to 140 ° C and react for 24 hours. After stopping the heating, add dichloromethane and water for extraction. The organic phase is spin-dried and column chromatography is performed to obtain 32.15 g of a white solid.

[0155] Synthesis of intermediate M10-3

[0156] To a 1000 mL flask, add intermediate M10-2 (20 g), raw material A (10.66 g), Pd2(dba)3 (1.25 g), tri-tert-butylphosphine tetrafluoroborate (1.18 g), sodium tert-butoxide (5.23 g), and 400 mL of toluene. Heat to reflux under nitrogen protection, react for 5 hours, filter on silica gel, dry the solvent, and recrystallize from toluene and ethanol to obtain 25.47 g of a white solid.

[0157] Synthesis of compound M10

[0158] Add intermediate M10-3 (10 g) and boron tribromide (24.1 g) to a 1000 mL flask, dissolve in 100 mL o-dichlorobenzene, heat to 180 ° C under nitrogen protection, and react for 24 hours. After silica gel column chromatography, recrystallize with ethyl acetate to obtain 3.4 g of yellow solid. Mass spectrometry detected molecular weight: 1074.70 (theoretical value: 1074.70).

[0159] Synthesis Example 2

[0160] Synthesis of compound M34:

[0161]

[0162] The synthesis of compound M34 is exactly the same as that of M10, except that 3-bromo-5,4'-di-tert-butyl-biphenyl is replaced by 2-bromo-5,4'-di-tert-butyl-biphenyl, and raw material A is replaced by raw material B. The molecular weight of the obtained product is 1074.71 (actual value 1074.70).

[0163] Synthesis Example 3

[0164] Synthesis of compound M83:

[0165]

[0166] The synthesis of compound M83 is exactly the same as that of M10, except that 3-bromo-5,4'-di-tert-butyl-biphenyl is replaced by 4-bromo-6-methyl-4'-tert-butylbiphenyl, and raw material A is replaced by raw material C. The molecular weight of the obtained product is 978.61 (actual value 978.61).

[0167] The present invention exemplifies the specific synthesis methods of the above compounds. For other compounds for which no specific synthesis methods are given, they can be prepared by similar methods, and they can be obtained by simply replacing the raw materials. They will not be described in detail here, or those skilled in the art can also prepare them by other methods in the prior art.

[0168] Device Example:

[0169] The preparation process of the organic electroluminescent device in this embodiment is as follows:

[0170] Device Example 1 Fabrication method: A glass plate coated with an ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent, baked in a clean environment until the water is completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0171] Place the glass substrate with the anode in a vacuum chamber and evacuate to a vacuum of <1×10 -5Pa, vacuum thermally evaporate 10nm of HT-4:HI-3 (97 / 3, w / w) mixture as hole injection layer, 60nm of compound HT-4 as hole transport layer, 5nm of compound HT-14 as electron blocking layer, 20nm of compound BFH-4:M1 (100:3, w / w) binary mixture as light emitting layer, 5nm of ET-23 as hole blocking layer, 25nm of compound ET-69:ET-57 (50 / 50, w / w) mixture as electron transport layer, 1nm of LiF as electron injection layer, and 150nm of metal aluminum as cathode on the above anode layer film in order. The total evaporation rate of all organic layers and LiF is controlled at 0.1nm / sec, and the evaporation rate of metal electrode is controlled at 1nm / sec.

[0172] Device Examples 2 to 12 are manufactured in the same manner as Device Example 1, except that the dopants in the light-emitting layer are different. The specific dopant material scheme is detailed in Table 2 below.

[0173] Device comparison examples 1 to 9 are prepared using the same method as device example 1, except that the dopants in the light-emitting layer are replaced by compounds C1, C2, C3, C4 and C5 in the prior art; and compounds C1, C2, C3, C4, C5, C-M1, C-M10, C-M85 and C-M86 prepared by a method similar to example 1.

[0174]

[0175] Device test method (including equipment and test conditions):

[0176] The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

[0177] The external quantum efficiency (EQE%) of the device was measured by the integrating sphere method; the luminescence peak and half-peak width of the device were tested by testing the fluorescence emission spectrum;

[0178] At the same brightness, the lifespan of the organic electroluminescent devices prepared in Examples 1 to 12 and Comparative Examples 1 to 9 was measured using a digital source meter and PR650. Specifically,

[0179] The LT97 life test is as follows: Use a brightness meter at 40mA / cm 2 The initial brightness value of the device under the current density is measured by maintaining a constant current and measuring the time for the device brightness to drop to 97% of the initial brightness, in hours; the LT97 life test value of device comparison example 1 is recorded as 1.0, and the ratio of the LT97 life test value of other devices to the LT97 life test value of device comparison example 1 is calculated;

[0180] The performance data of the organic electroluminescent devices prepared in the above device embodiments and comparative examples are shown in Table 1 below.

[0181] Table 1:

[0182]

[0183]

[0184] Compared with compound C1, the compound of the present invention exhibits higher efficiency and longer life, mainly because the compound of the present invention has a biphenyl substituent at the ortho position of the N atom, which can better inhibit exciton quenching compared to the di-tert-butylphenyl group in C1, thereby achieving improved life and efficiency.

[0185] Compared with the comparative compound C2, the compound of the present invention exhibits higher efficiency and longer lifespan, which may be due to the fact that there is no further alkyl substitution on the biphenyl substituent ortho to the N atom of C2, and the alkyl substitution on the biphenyl of the compound of the present invention can more effectively inhibit exciton quenching, thereby achieving improved lifespan and efficiency.

[0186] Compared with the comparative compound C3, the compounds of the present invention exhibit higher efficiency and longer lifespan, which may be due to the fact that the aromatic group adjacent to the N atom in the compounds of the present invention has an alkyl substitution, thereby being able to better protect the parent core and being beneficial to improving efficiency and lifespan.

[0187] Compared with the comparative compound C4, the compounds of the present invention exhibit higher efficiency and longer lifespan, which may be due to the fact that the aromatic group adjacent to the N atom in the compounds of the present invention has an alkyl substitution, which can better protect the parent nucleus and prevent exciton quenching, thereby facilitating the improvement of efficiency and lifespan.

[0188] Compared with the comparative compound C5, the compound of the present invention exhibits higher efficiency and longer life. This may be because the biphenyl structure of C5 is bonded to the adjacent position of the N atom through an oxygen atom, resulting in excessive distortion of the molecular structure, thereby reducing the luminous efficiency and stability of the compound. The compound of the present invention does not have oxygen atom bonding, so the efficiency and life are better.

[0189] Compared with the comparative compounds C-M1, C-M10, C-M85, and C-M86, the compounds of the present invention exhibit higher efficiency and longer lifespan, which may be due to the fact that the alkyl substitution on the side chain of the compounds of the present invention is beneficial to inhibiting exciton quenching, thereby improving efficiency and lifespan.

[0190] In addition, compared with the comparative compound, the compound of the present invention exhibits a narrower half-peak width, which may be due to the fact that the compound of the present invention is more rigid, suppressing the vibration of the molecule, thereby narrowing the spectrum.

[0191] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

[0192] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Although the present invention is described in conjunction with the embodiments, the present invention is not limited to the above-mentioned embodiments. It should be understood that under the guidance of the concept of the present invention, those skilled in the art can make various modifications and improvements. The attached claims summarize the scope of the present invention. The equivalent replacement of the raw materials of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A boron-nitrogen-containing organic compound having a structure shown in formula (1): In formula (1), ring A, B, and C are each independently a C6-C50 aromatic ring or a C3-C50 heteroaromatic ring; R 1 , R 2 , R 3 represents single substitution to maximum substitution, R 1 , R 2 , R 3 are each independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; said R 1 , R 2 , R 3 They are independently connected to each other by chemical bonds to form a ring or are not connected; Ar 1 ,Ar 2 Each is independently selected from a substituted or unsubstituted C6-C50 aromatic ring, a substituted or unsubstituted C3-C50 heteroaromatic ring; in, R 1 , R 2 , R 3 ,Ar 1 ,Ar 2 At least one of them is a structure represented by formula (2), In formula (2), X 1 -X 10 Each is independently selected from C, CR' or N, R' is independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, Where X 1 , X 2 , X 3 , X 4 , X 5 At least one of them is CR', and R' is a substituted or unsubstituted C1-C20 straight or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, X 1 -X 5 R' and X in 6 -X 10 R' is not connected, X 6 -X 10 R' in is not connected to ring A or B; Y 1 -Y 4 are independently selected from CR" or N, and the R" is independently selected from any one of hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl or C3-C60 heteroaryl; the R" and the connected aromatic ring or heteroaromatic ring are independently connected to each other by chemical bonds to form a ring or are not connected, The substituents mentioned above are each independently selected from any one of C1-C20 straight or branched alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6-C30 aryl, C3-C30 heteroaryl, or a combination of at least two thereof. The expression of a ring structure crossed by "—" indicates that the connection site is any position on the ring structure that can form a bond, and the * indicates the connection site.

2. The boron-nitrogen-containing organic compound according to claim 1, characterized in that: The boron-nitrogen-containing organic compound has a structure as shown in formula (1-1): Ar 1 ,Ar 2 , Ring A, Ring B, R 1 , R 2 Having the same limited range as in formula (1); Z 1 , Z 2 , Z 3 Each independently is CR 4 or N; R 4 are each independently selected from any one of hydrogen, halogen, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, R 4 Each independently is not connected to the adjacent ring structure or is connected to form a ring through a chemical bond; Preferably, the Z 1 , Z 2 , Z 3 At most one of them is N, Preferably, the Z 1 , Z 2 , Z 3 Each independently is CR 4 , The substituents mentioned above are each independently selected from any one of C1-C20 straight or branched alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6-C30 aryl, and C3-C30 heteroaryl, or a combination of at least two thereof. The expression of a ring structure crossed by "—" indicates that the connection site is at any position on the ring structure that can form a bond.

3. The boron-nitrogen-containing organic compound according to claim 2, characterized in that: The boron-nitrogen-containing organic compound has a structure as shown in any one of formulas (3-1) to (3-7): X, X ’ Selected from O or S, Ar 1 ,Ar 2 Has the same limited range as in formula (1); Z 1 , Z 2 , Z 3 Having the same limited range as in formula (1-1); U 1 , U 2 , U 3 , U 4 , U 5 , U 6 , U 7 , U 8 , U 1’ , U 2’ , U 3’ , U 4’ , U 5’ , U 6’ , U 7’ , U 8’ Each independent territory CR 5 Some N; R 5 are each independently selected from any one of hydrogen, halogen, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, R 5 Each independently is not connected to the adjacent ring structure or is connected to form a ring through a chemical bond; Preferably, the U 1 , U 2 , U 3 and U 4 At most one of them is N; U 5 , U 6 , U 7 , U 8 At most one of them is N; 1’ , U 2’ , U 3’ , U 4’ At most one of them is N; U 5’ , U 6’ , U 7’ , U 8’ At most one of them is N; Preferably, the U 1 , U 2 , U 3 and U 4 Each independently is CR 5 ; U 5 , U 6 , U 7 and U 8 Each independently is CR 5 ; The U 1’ , U 2’ , U 3’ and U 4’ Each independently is CR 5 ; U 5’ , U 6’ , U 7’ , U 8’ Each independently is CR 5 ; More preferably, R 5 Each is independently any one of hydrogen, substituted or unsubstituted C1-C10 straight or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; More preferably, R 5 Each is independently any one or a combination of two of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, and phenyl, The substituents mentioned above are each independently selected from any one of C1-C20 straight or branched alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6-C30 aromatic, and C3-C30 heteroaromatic groups, or a combination of at least two thereof.

4. The boron-nitrogen-containing organic compound according to any one of claims 1 to 3, characterized in that Ar 1 ,Ar 2 At least one is a structure represented by formula (2), Preferably, the Ar 1 ,Ar 2 One of them is a structure represented by formula (2).

5. The boron-nitrogen-containing organic compound according to claim 1, characterized in that: The Ar 1 ,Ar 2 One of the structures is any one of formula (2-1) to (2-3): Among them, X 1 -X 10 and Y 1 -Y 4 Having the same limited range as in formula (2); Preferably, in formula (2-1), X 1 -X 10 Not for N, X 4 is CR' and R' is selected from any one of substituted or unsubstituted C1-C20 straight chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl; in formula (2-2), X 1 -X 10 Not for N, X 3 or X 4 is CR' and R' is selected from any one of substituted or unsubstituted C1-C20 straight chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl; in formula (2-3), X 1 -X 10 Not for N, X 2 or X 4 CR' and R' is selected from any one of substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl; More preferably, R' is any one of methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl and cyclohexyl; The above-mentioned substituents are each independently selected from any one of C1-C20 straight or branched alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6-C30 aryl, C3-C30 heteroaryl, or a combination of at least two thereof, and the * indicates the connection site.

6. The boron-nitrogen-containing organic compound according to claim 5, characterized in that: The Ar 1 ,Ar 2 At least one of them is selected from formula (2-1).

7. The boron-nitrogen-containing organic compound according to claim 5, characterized in that: The boron-nitrogen-containing organic compound has a structure as shown in formula (3-2): Ar 1 is a structure selected from any one of formulas (2-1) to (2-3), Ar 2 Independently selected from substituted or unsubstituted C6-C50 aromatic rings; More preferably, Ar 1 is one selected from the following groups, More preferably, Ar 2 is one selected from the following groups, More preferably, Z 1 and Z 3 CH, Z 2 CR 4 ; R 4 One selected from hydrogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, preferably R 4 It is one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl and cyclohexyl.

8. The boron-nitrogen-containing organic compound according to claim 1, which is the following specific compound, 9. Use of the organic compound according to any one of claims 1 to 8 in an organic electronic device; Preferably, the organic electronic device comprises an organic electroluminescent device; Preferably, the application is application as a light-emitting layer material in an organic electroluminescent device.

10. An organic electroluminescent device comprising a first electrode, a second electrode and an organic layer inserted between the first electrode and the second electrode, characterized in that: The organic layer contains the organic compound according to any one of claims 1 to 8; Preferably, at least one of the organic layers is a light-emitting layer, and the light-emitting layer contains the organic compound according to any one of claims 1 to 8. Preferably, the light-emitting layer comprises a host material and a dye, and the dye comprises at least one organic compound according to any one of claims 1 to 8.

11. A display device, characterized in that: The display device comprises the organic electroluminescent device according to claim 10.

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