Organic compound for luminescent device, application of organic compound and organic electroluminescent device

Abstract

The invention provides a boron-containing fused ring compound which is characterized in that the boron-containing fused ring compound is of a structure shown in a formula (1), a group A represents an aromatic group containing a dibenzo five-membered heterocycle, and the compound can be used as an organic electroluminescent dye and can effectively improve the voltage and efficiency of an organic electroluminescent device when applied to the organic electroluminescent device. The invention further provides an organic light-emitting device and a display device.

Description

Technical Field

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

[0002] In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them very suitable for manufacturing on flexible substrates. Beautiful and cool optoelectronic products can be designed and produced according to demand, gaining unparalleled advantages over inorganic materials. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field-effect transistors, organic photovoltaic cells, organic sensors, etc. Among them, OLED has developed particularly rapidly and has achieved commercial success in the field of information display. OLED can provide highly saturated red, green, and blue colors. Full-color display devices made of OLEDs do not require additional backlight sources and have the advantages of brilliant colors, lightness, thinness, and softness.

[0003] The core of OLED devices is a thin film structure containing a variety of organic functional materials. Common functionalized organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, luminescent host materials and luminescent guest (dyes), etc. When power is turned on, electrons and holes are injected and transported to the luminescent area respectively and recombine there, thereby generating excitons and emitting light.

[0004] People have developed a variety of organic materials, combined with various unique device structures, which can improve carrier mobility, regulate carrier balance, break through electroluminescence efficiency, and delay device attenuation. For quantum mechanical reasons, common fluorescent luminescent bodies mainly use singlet excitons generated when electrons and voids combine to emit light, and are still widely used in various OLED products. Some metal complexes, such as iridium complexes, can simultaneously use triplet excitons and singlet excitons to emit light, and are called phosphorescent luminescent bodies. Their energy conversion efficiency can be increased by up to four times that of traditional fluorescent luminescent bodies. Thermally excited delayed fluorescence (TADF) technology promotes the transformation of triplet excitons to singlet excitons. Without the use of metal complexes, triplet excitons can still be effectively utilized to achieve higher luminescence efficiency. Thermally excited sensitized fluorescence (TASF) technology uses materials with TADF properties to sensitize luminescent bodies by energy transfer, which can also achieve higher luminescence efficiency. Especially in the field of blue luminescence, which has always been difficult to effectively improve luminescence efficiency, it has a very broad application prospect.

[0005] Under the condition of electrical excitation, organic electroluminescent devices will produce 25% singlet and 75% triplet excitons. Traditional fluorescent materials can only use 25% of singlet excitons due to spin prohibition, so the external quantum efficiency is limited to less than 5%. Almost all triplet excitons can only be lost in the form of heat. In order to improve the efficiency of organic electroluminescent devices, triplet excitons must be fully utilized.

[0006] To this end, researchers have proposed many methods, the most notable of which is the use of phosphorescent materials. Phosphorescent materials introduce heavy atoms and have a spin-orbit coupling effect, which can fully utilize 75% of triplet excitons and achieve 100% internal quantum efficiency. However, phosphorescent materials use rare heavy metals, which makes the materials expensive and not conducive to cost control. If fluorescent devices can make good use of triplet excitons, this problem can be solved well. Researchers have proposed a method to improve the efficiency of fluorescent devices by quenching triplet excitons to produce singlet excitons in fluorescent devices, but the maximum external quantum efficiency that this method can theoretically achieve is only 62.5%, which is much lower than that of phosphorescent materials. Therefore, it is very necessary to find new technologies to make full use of the triplet energy levels of fluorescent materials to improve the luminescence efficiency. Summary of the invention

[0007] In view of the shortcomings of the prior art, the inventors have conducted in-depth research and found that a luminescent dye compound with more balanced luminous efficiency and life characteristics can be obtained through an ingenious molecular design scheme. One of the purposes of the present invention is to provide a boron-containing fused ring compound, which has good photoelectric properties when applied to OLED devices. Specifically, the first aspect of the present invention provides a compound, specifically a boron-containing fused ring compound, characterized in that it is a structure shown in formula (1):

[0008]

[0009] L 1 , L 2 Each independently represents absence, single bond, O, S, CR 4 R 5 、SiR 6 R 7 or NR 8 , L 1 or L 2 When it does not exist, the chemical bonds on both sides do not exist, and L 1 and L 2 Not existing at the same time;

[0010] R 4 , R 5 , R 6 , R 7Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; R 8 One selected from substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0011] Z 1 -Z 14 Each is independently denoted as CR 11 or N; R 11 is selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; each R 11 Same or different, adjacent R 11 Not connected or connected into rings by chemical bonds;

[0012] R 1 , R 2 , R 3 Each is independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 chain alkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 aryloxy, substituted or unsubstituted C1-C10 alkylthio, substituted or unsubstituted C1-C10 arylthio, substituted or unsubstituted C2-C10 alkenylthio, substituted or unsubstituted C1-C10 silyl, substituted or unsubstituted C1-C10 silylaryl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, C1-C10 alkyl substituted amino, C1-C10 aryl substituted amino; m is an integer of 0-4, and n is an integer of 0-3;

[0013] The above-mentioned “substituted or unsubstituted” substituents are each independently selected from any one or a combination of at least two of halogen, cyano, nitro, hydroxyl, amino, aldehyde, ester, C1-C20 straight or branched alkyl, C1-C20 alkoxy, C2-C10 alkenyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl;

[0014] The substituted substituents are each independently not connected to the adjacent ring structure or are connected to form a ring through a chemical bond; the expression of "—" crossing the ring structure indicates that the connection site is at any position on the ring structure that can form a bond.

[0015] There is a carbazole group in the group fused with the parent nucleus containing a boron atom, and an indole carbazole structure of the N atom opposite to B. The inventors speculate that it is precisely because of its stronger structural rigidity and larger twist angle that is conducive to lowering the sublimation temperature, so it can suppress the vibration of molecular bonds in the excited state relative to aromatic amines, reduce energy loss, and can reduce the operating voltage or keep the voltage relatively unchanged, thereby improving the life and EQE of the device, and is conducive to narrowing the spectrum and improving efficiency and life.

[0016] 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.

[0017] In this specification, the expression of Ca to Cb represents 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 30, 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.

[0018] 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.

[0019] 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.

[0020] The heteroatom in the present invention is generally selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0021] 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.

[0022] 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.

[0023] As used herein, the term "halo" or "halogen" group is defined to include F, Cl, Br, or I.

[0024] 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.

[0025] 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.

[0026] As used herein, the term "one or more" means 1 or more than 1, such as 2, 3, 4, 5 or 10, where reasonable.

[0027] Unless otherwise indicated, as used herein, the point of attachment of a substituent may be from any suitable position of the substituent.

[0028] 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.

[0029] The term "about" means within ±10% of the stated numerical value, preferably within ±5%, more preferably within ±2%.

[0030] In the structural formula disclosed in this specification, the expression of “—” crossing over a ring structure indicates that the connection site is at any position on the ring structure that can form a bond.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] In the present invention, the aryl ether group and heteroaryl ether group include groups formed by the above-mentioned aryl group and heteroaryl group and oxygen. In the present invention, the aryl amino group and heteroaryl amino group include groups formed by replacing one or two H in the -NH2 group with the above-mentioned aryl group and heteroaryl group.

[0037] In this specification, the chain alkyl group includes both straight-chain and branched alkyl groups. Examples of the C1-C20 alkyl group 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, trifluoromethyl, pentafluoroethyl, and 2,2,2-trifluoroethyl.

[0038] 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.

[0039] Specific examples of C2-C10 straight-chain or cyclic alkenyl groups 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.

[0040] The number of carbon atoms in the C2-C20 straight-chain or cyclic 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.

[0041] In the present specification, an alkoxy group refers to a group consisting of the above-mentioned chain alkyl group and oxygen, or a group consisting of the above-mentioned cycloalkyl group and oxygen.

[0042] 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.

[0043] 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-mentioned chain alkyl or cycloalkyl groups. Specifically, groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl and the like.

[0044] As a preferred embodiment of the present invention, the structure represented by formula (1) is a structure represented by the following formula (2) to formula (10),

[0045]

[0046] Z 1 -Z 14 , L 1 , L 2 , R 1 , R 2 , m, and n have the same meanings as those in formula (1), and the expression of “—” crossing the ring structure indicates that the connection site is at any position on the ring structure that can form a bond.

[0047] Preferably, formula (1) is a structure shown in formula (2), formula (3), formula (5), formula (8), formula (9), or formula (10). More preferably, formula (1) is a structure shown in formula (2), formula (3), or formula (10).

[0048] As a preferred embodiment of the present invention, R 3 is selected from H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, phenyl, tert-butylphenyl, dibenzocarbazolyl, phenyl-substituted dibenzocarbazolyl, and cyano, more preferably, selected from H, phenyl, and cyano,

[0049] m and n are preferably 0, 1 or 2,

[0050] Each R 1 is independently selected from H, methyl, ethyl, isopropyl, tert-butyl, tert-amyl, isobutyl, cyclopentyl, cyclohexyl, phenyl, tert-butylphenyl, dibenzocarbazolyl, phenyl-substituted dibenzocarbazolyl, cyano, more preferably, selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, cyano,

[0051] R 2 Independently selected from H, methyl, ethyl, isopropyl, tert-butyl, tert-amyl, isobutyl, cyclopentyl, cyclohexyl, phenyl, tert-butylphenyl, dibenzocarbazolyl, phenyl-substituted dibenzocarbazolyl, cyano, more preferably, selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, cyano.

[0052] As a preferred embodiment of the present invention, m is 2, or two R 1 For adjacent substitution, and two adjacent R 1 Connected to form the following ring structure,

[0053]

[0054] * indicates the attachment site.

[0055] n is 2, and two R2 are adjacently substituted, and two adjacent R 2 Connected to form the following ring structure,

[0056]

[0057] * indicates the attachment site.

[0058] As a preferred embodiment of the present invention, Z 1 -Z 14 All are CR 11 , R 11 is selected from H or one of the following substituted or unsubstituted groups,

[0059]

[0060]

[0061]

[0062] The substitution in the above “substituted or unsubstituted” refers to substitution by at least one selected from halogen, phenyl, cyano, methyl, ethyl, isopropyl, tert-butyl, and cyclohexane, and the wavy line indicates the linking site.

[0063] As a preferred embodiment of the present invention, Z 1 -Z 14 All are CR 11 , Z 1 -Z 14 R 11 1 to 4 of them are groups selected from the following groups, and the rest are H,

[0064] ,

[0065] Wavy lines indicate linkage sites.

[0066] As a preferred embodiment of the present invention, Z 1 -Z 14 All are CR 11 , Z 1 -Z 14 R 11 The two adjacent ones form the following ring structure,

[0067]

[0068]

[0069] * represents a bonding site, and the "substituted or unsubstituted" mentioned above means substituted by at least one selected from halogen, phenyl, cyano, methyl, ethyl, isopropyl, cyclohexyl, and cyclopentyl.

[0070] As a preferred embodiment of the present invention, Z 1 -Z 14 Among them, Z 5 , Z 6 , Z 2 , Z 9 , Z 13 , Z 12 CR 21 , the rest are CH, Z 5 , Z 6 , Z 2 , Z 9 , Z 13 , Z 12 R 21 Medium, 1 to 4 Rs 21 is selected from the following groups, the rest are H,

[0071]

[0072] Wavy lines indicate linkage sites.

[0073] As a preferred embodiment of the present invention, Z 2 and Z 3 The two R's 11 connected to form a ring structure, and / or Z 4 and Z 5 The two R's 11 connected to form a ring structure, and / or Z 11 and Z 12 The two R's 11 Connected to form a ring structure, Z 9 and Z 10 The two R's 11 Connected to form a ring structure, the ring structure is one selected from the following structures:

[0074]

[0075] * indicates the attachment site.

[0076] As the boron-containing fused ring compound of the present invention, the following compounds can be specifically mentioned, but the present invention is not limited to the following compounds:

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] It should be noted that, for the sake of convenience, the possible effects of each group / feature are described separately in this application, but this does not mean that these groups / features act in isolation. In fact, the reason for obtaining good performance is essentially the optimized combination of the entire molecule, which is the result of the synergistic effect between the various groups, rather than the effect of a single group.

[0085] The above-mentioned compound of the present invention has excellent luminescent properties, can provide triplet excitons to achieve higher luminescent efficiency, and is suitable for use as a luminescent dye, especially as a green luminescent dye, based on its excellent carrier transfer efficiency. Of course, since the compound of the present invention can also be used as a sensitizer together with the host material and the dye to achieve a good luminescent layer. The devices used include but are not limited to organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information tags, electronic artificial skin sheets, sheet-type scanners or electronic paper, preferably organic electroluminescent devices.

[0086] In a second aspect, the present invention provides a use of the compound as described in the first aspect, wherein the compound is used in an organic electronic device.

[0087] 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.

[0088] Preferably, the compound is used in organic electroluminescent devices. The OLED device prepared by using the compound of the present invention has high luminous efficiency and better service life, especially can adjust the light color of red dye to achieve the light color required for mass production, and can meet the requirements of current panel and display manufacturers for high-performance materials.

[0089] Preferably, the compound is used as a light-emitting layer material in an organic electroluminescent device. Preferably, the compound is used as a light-emitting layer host material in an organic electroluminescent device.

[0090] 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 disposed between the first electrode and the second electrode; the organic layer comprises at least one compound as described in the first aspect. Preferably, the compound of the first aspect of the present invention is used as a luminescent dye in the luminescent layer.

[0091] The present invention also protects an electronic device having a display screen or a display panel, wherein the display screen or the display panel adopts the above-mentioned organic electroluminescent device. DETAILED DESCRIPTION

[0092] The technical solution of the present invention is further described in more detail below. It should be understood by those skilled in the art that the specific implementation methods and examples are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0093] The process of obtaining the compound of the present invention is as follows:

[0094] The following examples describe the general synthesis methods of the compounds of the present invention, and then the substituents are replaced by various coupling reactions.

[0095] For details, please refer to the specific synthesis examples below.

[0096] Description of organic EL elements

[0097] The OLED device structure of the present invention may be an existing device structure, generally comprising a first electrode, a second electrode, and an organic material layer between the electrodes. The organic material may be divided into multiple regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.

[0098] 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.

[0099] 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), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0100] 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.

[0101] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a hole transport layer (HTL) of a single-layer structure, 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 multi-layer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0102] 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-34 below; or any combination thereof.

[0103]

[0104]

[0105] 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-34 mentioned above, or one or more compounds of HI1-HI3 described below; or one or more compounds of HT-1 to HT-34 can be doped with one or more compounds of HI1-HI3 described below.

[0106]

[0107] The light-emitting layer includes a light-emitting dye (i.e., a dopant) that can emit different wavelength spectra, and can also include a host material (Host). 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-13 listed below.

[0108]

[0109] 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).

[0110] 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-57 listed below.

[0111]

[0112]

[0113]

[0114]

[0115] The device may also include an electron injection layer located between the electron transport layer and the cathode, and 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.

[0116] Example

[0117] 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.

[0118] Synthesis Example

[0119] 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 may 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 from commercial channels, or are made by themselves according to known methods through these raw materials. 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 purchased 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).

[0120] Synthesis Example 1: Synthesis of S3

[0121]

[0122] Synthesis of intermediate M3-1

[0123] At room temperature, raw material 1 (100 g, 320.81 mmol), raw material 2 (80.68 g, 288.72 mmol), potassium carbonate (48.77 g, 352.89 mmol), DMF (500 ml) as solvent were added to a 1L single-mouth bottle, nitrogen was replaced three times, and the reaction was carried out at 80°C overnight. After the reaction solution was cooled, water (500 ml) was added to precipitate a white solid, and stirred for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 165.5 g of white solid M3-1, with a yield of 90.3%. The molecular ion mass determined by mass spectrometry is: 570.25 (theoretical value: 570.22).

[0124] Synthesis of intermediate M3-2

[0125] At room temperature, add raw material M3-1 (15g, 26.26mmol), raw material 3 (7.02g, 26.26mmol), cesium carbonate (12.84g, 39.4mmol), DMF (200ml) as solvent to a 1L single-mouth bottle, replace nitrogen three times, and react at 110℃ overnight. After the reaction solution is cooled, add water (500ml) to precipitate a white solid, and stir for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 14.5g of white solid M3-2, with a yield of 67.46%. The molecular ion mass determined by mass spectrometry is: 817.34 (theoretical value: 817.32).

[0126] Synthesis of final product S3

[0127] At room temperature, add M3-2 (14.5g, 17.72mmol) and xylene (100ml) to a 500ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (22.15ml, 35.43mmol, 1.6M) to the system at -70℃, stir at room temperature for 5min, heat to 60℃ and react for 2h, the system changes from anhydrous clear to dark red. Add boron tribromide (3.41ml, 35.43mmol, 2.60g / ml) to the system at -40℃, stir at low temperature for 10min, the system changes from dark red transparent to red turbid. Then add N,N-diisopropylethylamine (9.28ml, 53.15mmol, 0.74g / ml) at -40℃, heat to 120℃ and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, and the mixture was concentrated by silica gel chromatography (PE: DCM = 20:1). The crude product was recrystallized twice from toluene / ethanol to obtain 3.3 g of a red solid with a yield of 23.52%. The molecular ion mass determined by mass spectrometry was 791.37 (theoretical value: 791.35).

[0128] Synthesis Example 2: Synthesis of S5

[0129]

[0130] Synthesis of intermediate M5-1

[0131] At room temperature, add raw material M3-1 (10 g, 17.51 ​​mmol), raw material 4 (4.79 g, 17.51 ​​mmol), cesium carbonate (8.56 g, 26.26 mmol), DMF (200 ml) as solvent to a 1L single-mouth bottle, replace nitrogen three times, and react at 110°C overnight. After the reaction solution is cooled, add water (500 ml) to precipitate a white solid, and stir for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 11.2 g of white solid M5-1, with a yield of 77.58%. The molecular ion mass determined by mass spectrometry is: 823.31 (theoretical value: 823.28).

[0132] Synthesis of final product S5

[0133] At room temperature, add M5-1 (14.5g, 17.5mmol) and xylene (100ml) to a 500ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (16.98ml, 27.17mmol, 1.6M) to the system at -70℃, stir at room temperature for 5min, heat to 60℃ and react for 2h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.62ml, 27.17mmol, 2.60g / ml) to the system at -40℃, stir at low temperature for 10min, the system changes from dark red transparent to red turbid. Then add N,N-diisopropylethylamine (7.12ml, 40.75mmol, 0.74g / ml) at -40℃, heat to 120℃ and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, silica gel was added to concentrate, column chromatography (PE: DCM = 20: 1), and the crude product was recrystallized twice from toluene / ethanol to obtain 2.7 g of red solid, with a yield of 24.91%. The molecular ion mass determined by mass spectrometry was 791.33 (theoretical value: 797.30).

[0134] Synthesis Example 3: Synthesis of S11

[0135]

[0136] Synthesis of intermediate M11-1

[0137] At room temperature, raw material 1 (50 g, 160.40 mmol), raw material 5 (40.34 g, 144.36 mmol), potassium carbonate (24.39 g, 176.44 mmol), DMF (300 ml) as solvent were added to a 1L single-mouth bottle, nitrogen was replaced three times, and the reaction was carried out at 80°C overnight. After the reaction solution was cooled, water (500 ml) was added to precipitate a white solid, and stirred for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 82.3 g of white solid M11-1, with a yield of 89.84%. The molecular ion mass determined by mass spectrometry is: 570.24 (theoretical value: 570.22).

[0138] Synthesis of intermediate M11-2

[0139] At room temperature, add raw material M11-1 (10 g, 17.51 ​​mmol), raw material 6 (5.59 g, 17.51 ​​mmol), cesium carbonate (8.56 g, 26.26 mmol), DMF (200 ml) as solvent to a 1L single-mouth bottle, replace nitrogen three times, and react at 110°C overnight. After the reaction solution is cooled, add water (200 ml) to precipitate a white solid, and stir for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 11.3 g of white solid M11-2, with a yield of 74.14%. The molecular ion mass determined by mass spectrometry is: 869.41 (theoretical value: 869.35).

[0140] Synthesis of final product S11

[0141] At room temperature, add M11-2 (11.3 g, 12.98 mmol) and xylene (100 ml) to a 500 ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (16.23 ml, 25.96 mmol, 1.6 M) to the system at -70 ° C, stir at room temperature for 5 min, heat to 60 ° C and react for 2 h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.5 ml, 25.96 mmol, 2.60 g / ml) to the system at -40 ° C, stir at low temperature for 10 min, the system changes from dark red transparent to red turbid. Then add N, N-diisopropylethylamine (6.8 ml, 38.94 mmol, 0.74 g / ml) at -40 ° C, heat to 120 ° C and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, silica gel was added to concentrate, column chromatography (PE: DCM = 20: 1), and the crude product was recrystallized twice from toluene / ethanol to obtain 2.5 g of red solid, with a yield of 22.82%. The molecular ion mass determined by mass spectrometry was 843.41 (theoretical value: 843.38).

[0142] Synthesis Example 4: Synthesis of S15

[0143]

[0144] Synthesis of intermediate M15-1

[0145] At room temperature, add raw material M11-1 (10 g, 17.51 ​​mmol), raw material 7 (5.82 g, 17.51 ​​mmol), cesium carbonate (8.56 g, 26.26 mmol), DMF (200 ml) as solvent to a 1L single-mouth bottle, replace nitrogen three times, and react at 110°C overnight. After the reaction solution is cooled, add water (200 ml) to precipitate a white solid, and stir for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 12.2 g of white solid M15-1, with a yield of 78.86%. The molecular ion mass determined by mass spectrometry is: 882.41 (theoretical value: 882.35).

[0146] Synthesis of final product S15

[0147] At room temperature, add M15-1 (12.2g, 13.81mmol) and xylene (100ml) to a 500ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (17.26ml, 27.62mmol, 1.6M) to the system at -70℃, stir at room temperature for 5min, heat to 60℃ and react for 2h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.66ml, 27.62mmol, 2.60g / ml) to the system at -40℃, stir at low temperature for 10min, the system changes from dark red transparent to red turbid. Then add N,N-diisopropylethylamine (7.24ml, 41.42mmol, 0.74g / ml) at -40℃, heat to 120℃ and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, the mixture was concentrated by silica gel, column chromatography (PE: DCM = 20: 1), and the crude product was recrystallized twice from toluene / ethanol to obtain 2.8 g of a red solid with a yield of 23.66%. The molecular ion mass determined by mass spectrometry was 856.41 (theoretical value: 856.37).

[0148] Synthesis Example 5: Synthesis of S55

[0149]

[0150] Synthesis of intermediate M55-1

[0151] At room temperature, add raw material M3-1 (10 g, 17.51 ​​mmol), raw material 8 (4.5 g, 17.51 ​​mmol), cesium carbonate (8.56 g, 26.26 mmol), DMF (200 ml) as solvent to a 1L single-mouth bottle, replace nitrogen three times, and react at 110°C overnight. After the reaction solution is cooled, add water (500 ml) to precipitate a white solid, and stir for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 11.7 g of white solid M55-1, with a yield of 82.66%. The molecular ion mass determined by mass spectrometry is: 807.33 (theoretical value: 807.30).

[0152] Synthesis of final product S55

[0153] At room temperature, add M55-1 (11.7 g, 14.47 mmol) and xylene (100 ml) to a 500 ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (18.09 ml, 28.95 mmol, 1.6 M) to the system at -70 ° C, stir at room temperature for 5 min, heat to 60 ° C and react for 2 h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.79 ml, 28.95 mmol, 2.60 g / ml) to the system at -40 ° C, stir at low temperature for 10 min, the system changes from dark red transparent to red turbid. Then add N, N-diisopropylethylamine (7.58 ml, 43.42 mmol, 0.74 g / ml) at -40 ° C, heat to 120 ° C and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, silica gel was added to concentrate, column chromatography (PE: DCM = 20: 1), and the crude product was recrystallized twice from toluene / ethanol to obtain 2.9 g of red solid, with a yield of 25.63%. The molecular ion mass determined by mass spectrometry was 781.35 (theoretical value: 781.33).

[0154] Synthesis Example 6: Synthesis of S57

[0155]

[0156] Synthesis of intermediate M57-1

[0157] At room temperature, add raw material M3-1 (10 g, 17.51 ​​mmol), raw material 9 (5.84 g, 17.51 ​​mmol), cesium carbonate (8.56 g, 26.26 mmol), DMF (200 ml) as solvent to a 1L single-mouth bottle, replace nitrogen three times, and react at 110°C overnight. After the reaction solution is cooled, add water (500 ml) to precipitate a white solid, and stir for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 11.5 g of white solid M57-1, with a yield of 74.26%. The molecular ion mass determined by mass spectrometry is: 883.34 (theoretical value: 883.33).

[0158] Synthesis of final product S57

[0159] At room temperature, add M57-1 (11.5 g, 13.00 mmol) and xylene (100 ml) to a 500 ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (16.26 ml, 26.00 mmol, 1.6 M) to the system at -70 ° C, stir at room temperature for 5 min, heat to 60 ° C and react for 2 h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.51 ml, 26.00 mmol, 2.60 g / ml) to the system at -40 ° C, stir at low temperature for 10 min, the system changes from dark red transparent to red turbid. Then add N, N-diisopropylethylamine (6.81 ml, 39.00 mmol, 0.74 g / ml) at -40 ° C, heat to 120 ° C and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, silica gel was added to concentrate, column chromatography (PE: DCM = 20: 1), and the crude product was recrystallized twice from toluene / ethanol to obtain 2.4 g of a red solid with a yield of 21.52%. The molecular ion mass determined by mass spectrometry was 857.41 (theoretical value: 857.36).

[0160] Synthesis Example 7: Synthesis of S63

[0161]

[0162] Synthesis of intermediate M63-1

[0163] At room temperature, raw material 1 (50 g, 160.40 mmol), raw material 6 (46.11 g, 144.36 mmol), potassium carbonate (24.39 g, 176.44 mmol), DMF (300 ml) as solvent were added to a 1L single-mouth bottle, nitrogen was replaced three times, and the reaction was carried out at 80°C overnight. After the reaction solution was cooled, water (500 ml) was added to precipitate a white solid, and stirred for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 75.7 g of white solid M63-1, with a yield of 77.23%. The molecular ion mass determined by mass spectrometry is: 610.18 (theoretical value: 610.16).

[0164] Synthesis of intermediate M63-2

[0165] At room temperature, add raw material M63-1 (10 g, 16.36 mmol), raw material 10 (4.47 g, 16.36 mmol), cesium carbonate (8.00 g, 24.55 mmol), DMF (200 ml) as solvent to a 1L single-mouth bottle, replace nitrogen three times, and react at 110°C overnight. After the reaction solution is cooled, add water (200 ml) to precipitate a white solid, and stir for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 10.2 g of white solid M63-2, with a yield of 72.11%. The molecular ion mass determined by mass spectrometry is: 863.24 (theoretical value: 863.22).

[0166] Synthesis of final product S63

[0167] At room temperature, add M63-2 (10.2g, 11.80mmol) and xylene (100ml) to a 500ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (14.75ml, 23.6mmol, 1.6M) to the system at -70℃, stir at room temperature for 5min, heat to 60℃ and react for 2h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.27ml, 23.6mmol, 2.60g / ml) to the system at -40℃, stir at low temperature for 10min, the system changes from dark red transparent to red turbid. Then add N,N-diisopropylethylamine (6.18ml, 35.4mmol, 0.74g / ml) at -40℃, heat to 120℃ and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, silica gel was added to concentrate, column chromatography (PE: DCM = 20: 1), and the crude product was recrystallized twice from toluene / ethanol to obtain 2.6 g of red solid, with a yield of 26.3%. The molecular ion mass determined by mass spectrometry was 837.25 (theoretical value: 837.24).

[0168] Synthesis Example 8: Synthesis of S99

[0169]

[0170] Synthesis of intermediate M99-1

[0171] At room temperature, add raw material M63-1 (10 g, 16.36 mmol), raw material 11 (5.13 g, 16.36 mmol), cesium carbonate (8.00 g, 24.55 mmol), DMF (100 ml) as solvent to a 1L single-mouth bottle, replace nitrogen three times, and react at 110°C overnight. After the reaction solution is cooled, add water (200 ml) to precipitate a white solid, and stir for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 12.3 g of white solid M99-1, with a yield of 83.1%. The molecular ion mass determined by mass spectrometry is: 903.32 (theoretical value: 903.3).

[0172] Synthesis of final product S99

[0173] At room temperature, add M99-1 (12.3g, 13.6mmol) and xylene (100ml) to a 500ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (17ml, 27.2mmol, 1.6M) to the system at -70℃, stir at room temperature for 5min, heat to 60℃ and react for 2h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.62ml, 27.2mmol, 2.60g / ml) to the system at -40℃, stir at low temperature for 10min, the system changes from dark red transparent to red turbid. Then add N,N-diisopropylethylamine (7.13ml, 40.8mmol, 0.74g / ml) at -40℃, heat to 120℃ and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, silica gel was added to concentrate, column chromatography (PE: DCM = 20: 1), and the crude product was recrystallized twice from toluene / ethanol to obtain 2.8 g of red solid, with a yield of 23.46%. The molecular ion mass determined by mass spectrometry was 877.35 (theoretical value: 877.33).

[0174] Synthesis Example 9: Synthesis of S101

[0175]

[0176] Synthesis of intermediate M101-1

[0177] At room temperature, add raw material M3-1 (10 g, 17.51 ​​mmol), raw material 12 (5.17 g, 17.51 ​​mmol), cesium carbonate (8.56 g, 26.26 mmol), DMF (200 ml) as solvent to a 1L single-mouth bottle, replace nitrogen three times, and react at 110°C overnight. After the reaction solution is cooled, add water (500 ml) to precipitate a white solid, and stir for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 12.3 g of white solid M101-1, with a yield of 82.98%. The molecular ion mass determined by mass spectrometry is: 845.43 (theoretical value: 845.41).

[0178] Synthesis of final product S101

[0179] At room temperature, add M101-1 (12.3 g, 14.53 mmol) and xylene (100 ml) to a 500 ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (18.16 ml, 29.06 mmol, 1.6 M) to the system at -70 ° C, stir at room temperature for 5 min, heat to 60 ° C and react for 2 h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.80 ml, 29.06 mmol, 2.60 g / ml) to the system at -40 ° C, stir at low temperature for 10 min, the system changes from dark red transparent to red turbid. Then add N, N-diisopropylethylamine (7.61 ml, 43.59 mmol, 0.74 g / ml) at -40 ° C, heat to 120 ° C and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, and the mixture was concentrated by silica gel chromatography (PE: DCM = 20:1). The crude product was recrystallized twice from toluene / ethanol to obtain 2.3 g of a red solid with a yield of 19.31%. The molecular ion mass determined by mass spectrometry was 819.43 (theoretical value: 819.44).

[0180] Synthesis Example 10: Synthesis of S102

[0181]

[0182] Synthesis of intermediate M102-1

[0183] At room temperature, raw material M3-1 (10 g, 17.51 ​​mmol), raw material 13 (3.49 g, 17.51 ​​mmol), cesium carbonate (8.56 g, 26.26 mmol), DMF (200 ml) as solvent were added to a 1L single-mouth bottle, nitrogen was replaced three times, and the reaction was carried out at 110°C overnight. After the reaction solution was cooled, water (500 ml) was added to precipitate a white solid, and stirred for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 11.5 g of white solid M102-1, with a yield of 87.53%. The molecular ion mass determined by mass spectrometry is: 749.31 (theoretical value: 749.26).

[0184] Synthesis of final product S102

[0185] At room temperature, add M102-1 (11.5 g, 15.33 mmol) and xylene (100 ml) to a 500 ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (19.16 ml, 30.65 mmol, 1.6 M) to the system at -70 ° C, stir at room temperature for 5 min, heat to 60 ° C and react for 2 h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.95 ml, 30.65 mmol, 2.60 g / ml) to the system at -40 ° C, stir at low temperature for 10 min, the system changes from dark red transparent to red turbid. Then add N, N-diisopropylethylamine (8.03 ml, 45.98 mmol, 0.74 g / ml) at -40 ° C, heat to 120 ° C and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, and the mixture was concentrated by silica gel chromatography (PE: DCM = 20:1). The crude product was recrystallized twice from toluene / ethanol to obtain 2.5 g of a red solid with a yield of 22.54%. The molecular ion mass determined by mass spectrometry was 723.31 (theoretical value: 723.29).

[0186] Synthesis Example 11: Synthesis of S117

[0187]

[0188] Synthesis of intermediate M117-1

[0189] At room temperature, raw material M3-1 (10 g, 17.51 ​​mmol), raw material 14 (4.52 g, 17.51 ​​mmol), cesium carbonate (8.56 g, 26.26 mmol), DMF (200 ml) as solvent were added to a 1L single-mouth bottle, nitrogen was replaced three times, and the reaction was carried out at 110°C overnight. After the reaction solution was cooled, water (500 ml) was added to precipitate a white solid, and stirred for 30 minutes. Filter, dissolve the filter cake in dichloromethane, perform rapid column chromatography, concentrate, and wash with ethanol to obtain 10.6 g of white solid M117-1, with a yield of 74.79%. The molecular ion mass determined by mass spectrometry is: 808.34 (theoretical value: 808.33).

[0190] Synthesis of final product S117

[0191] At room temperature, add M117-1 (10.6 g, 13.1 mmol) and xylene (100 ml) to a 500 ml three-necked flask, replace nitrogen 3 times, add tert-butyl lithium n-hexane solution (16.37 ml, 26.19 mmol, 1.6 M) to the system at -70 ° C, stir at room temperature for 5 min, heat to 60 ° C and react for 2 h, the system changes from anhydrous clear to dark red. Add boron tribromide (2.52 ml, 26.19 mmol, 2.60 g / ml) to the system at -40 ° C, stir at low temperature for 10 min, the system changes from dark red transparent to red turbid. Then add N, N-diisopropylethylamine (6.86 ml, 39.29 mmol, 0.74 g / ml) at -40 ° C, heat to 120 ° C and react overnight. The system was cooled to room temperature, dichloromethane (200 ml) was added to dissolve, and the mixture was concentrated by silica gel chromatography (PE: DCM = 20:1). The crude product was recrystallized twice from toluene / ethanol to obtain 2.4 g of a red solid with a yield of 23.41%. The molecular ion mass determined by mass spectrometry was 782.39 (theoretical value: 782.36).

[0192] Device Embodiment

[0193] The preparation process of the organic electroluminescent device in this embodiment is as follows:

[0194] Example 1

[0195] The device structure of Example 1 is as follows:

[0196] ITO(150nm) / HI-2(10nm) / HT-2(40nm) / BFH-3:S3(30nm, 5%wt) / ET-59(25nm) / LiF(0.5nm) / Al(150nm).

[0197] The preparation process is as follows: a glass plate coated with a transparent conductive layer of ITO (thickness 150 nm) was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0198] The glass substrate with the anode is placed in a vacuum chamber, and the vacuum is evacuated to 1×10-5~1×10-4Pa. HI-2 and HT-2 are vacuum-deposited on the anode layer as a hole injection layer and a hole transport layer, respectively, at a deposition rate of 0.1nm / s, and the deposition film thicknesses are 10nm and 40nm, respectively.

[0199] "BFH-3: S3 (30nm, 5%wt)" is vacuum evaporated on the hole transport layer as the light-emitting layer of the organic electroluminescent device. The evaporation rate is 0.1nm / s and the total film thickness of the evaporation is 30nm; "5%wt" refers to the doping ratio of the green light dye, that is, the weight ratio of the main material to S3 is 95:5.

[0200] ET-59 was vacuum-deposited on the light-emitting layer as the electron transport layer of the organic electroluminescent device, with a deposition rate of 0.1 nm / s and a total deposition film thickness of 20 nm;

[0201] 0.5 nm of LiF as an electron injection layer and 150 nm of Al as a cathode were vacuum-deposited on the electron transport layer.

[0202] Examples 2-13, Comparative Examples 1-3

[0203] The manufacturing process of Examples 2-13 and Comparative Examples 1-3 is the same as that of Device Example 1, except that the dye of the light-emitting layer is replaced with the substances listed in the following table, namely R-1, R-2, and R-3.

[0204]

[0205] Performance test of organic electroluminescent devices:

[0206] At the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 1-13 and Comparative Examples 1-3 were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 1000 cd / m 2 The voltage at this time is the driving voltage, and the current density at this time is measured at the same time; the external quantum efficiency is measured using an integrating sphere; the life test of LT95 is as follows: use a brightness meter at 10000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 9500cd / m 2The LT95 life test value of Comparative Example 2 is recorded as 1, and the LT95 life of each device embodiment and other comparative examples are the ratios of their respective LT95 life test values ​​to the test value of Comparative Example 2 (relative life).

[0207]

[0208]

[0209] The novel compound of the present invention is used for an organic electroluminescent device. In contrast to R-2 and R-3, in Examples 1-13, the carbazole with at least one side connected to a boron atom is an indole carbazole structure with a N atom in the position opposite to B. Since the structure is more rigid and has a larger twist angle, it is beneficial to reduce the sublimation temperature. Therefore, it can suppress the vibration of molecular bonds in an excited state relative to aromatic amine, reduce energy loss, reduce the operating voltage or keep the voltage relatively unchanged, and improve the life and EQE of the device. Compared with R-1, the carbazole structure is more rigid, which is beneficial to narrowing the spectrum and improving efficiency and life.

[0210] 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-containing fused ring compound, characterized in that: It is a structure shown in formula (1): L 1 , L 2 Each independently represents absence, single bond, O, S, CR 4 R 5 、SiR 6 R 7 or NR 8 , L 1 or L 2 When it does not exist, the chemical bonds on both sides do not exist, and L 1 and L 2 Not existing at the same time; R 4 , R 5 , R 6 , R 7 Each is independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 silyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; R 8 One selected from substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; Z 1 -Z 14 Each is independently denoted as CR 11 or N; R 11 is selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; each R 11 Same or different, adjacent R 11 Not connected or connected into rings by chemical bonds; R 1 , R 2 , R 3 Each is independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 chain alkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 aryloxy, substituted or unsubstituted C1-C10 alkylthio, substituted or unsubstituted C1-C10 arylthio, substituted or unsubstituted C2-C10 alkenylthio, substituted or unsubstituted C1-C10 silyl, substituted or unsubstituted C1-C10 silylaryl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, C1-C10 alkyl substituted amino, C1-C10 aryl substituted amino; m is an integer of 0-4, and n is an integer of 0-3; The above-mentioned "substituted or unsubstituted" substituents are each independently selected from any one or a combination of at least two of halogen, cyano, nitro, hydroxyl, amino, aldehyde, ester, C1-C20 straight or branched alkyl, C1-C20 alkoxy, C2-C10 alkenyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl; The substituted substituents are each independently not connected to the adjacent ring structure or are connected to form a ring through a chemical bond; the expression of "—" crossing the ring structure indicates that the connection site is at any position on the ring structure that can form a bond.

2. The boron-containing fused ring compound according to claim 1, characterized in that: The structure represented by formula (1) is represented by the following formulas (2) to (10), Z 1 -Z 14 , L 1 , L 2 , R 1 , R 2 , m, and n have the same meanings as those in formula (1). The expression of "—" crossing the ring structure indicates that the connection site is at any position on the ring structure that can form a bond. Preferably, formula (1) is the structure shown by formula (2), formula (3), formula (5), formula (8), formula (9), and formula (10); more preferably, formula (1) is the structure shown by formula (2), formula (3), and formula (10).

3. The boron-containing fused ring compound according to claim 1, characterized in that: R 3 is selected from H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, phenyl, tert-butylphenyl, dibenzocarbazolyl, phenyl-substituted dibenzocarbazolyl, and cyano, more preferably, selected from H, phenyl, and cyano, m and n are preferably 0, 1 or 2, Each R 1 is independently selected from H, methyl, ethyl, isopropyl, tert-butyl, tert-amyl, isobutyl, cyclopentyl, cyclohexyl, phenyl, tert-butylphenyl, dibenzocarbazolyl, phenyl-substituted dibenzocarbazolyl, cyano, more preferably, selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, cyano, R 2 Independently selected from H, methyl, ethyl, isopropyl, tert-butyl, tert-amyl, isobutyl, cyclopentyl, cyclohexyl, phenyl, tert-butylphenyl, dibenzocarbazolyl, phenyl-substituted dibenzocarbazolyl, cyano, more preferably, selected from H, methyl, ethyl, isopropyl, tert-butyl, phenyl, cyano.

4. The boron-containing fused ring compound according to claim 1, characterized in that: m is 2, and two R 1 For adjacent substitution, and two adjacent R 1 Connected to form the following ring structure, * indicates the attachment site.

5. The boron-containing fused ring compound according to claim 1, characterized in that: n is 2, and two R 2 For adjacent substitution, and two adjacent R 2 Connected to form the following ring structure, * indicates the attachment site.

6. The boron-containing fused ring compound according to claim 1, characterized in that: Z 1 -Z 14 All are CR 11 , R 11 is selected from H or one of the following substituted or unsubstituted groups, The substitution in the above "substituted or unsubstituted" refers to substitution by at least one selected from halogen, phenyl, cyano, methyl, ethyl, isopropyl, tert-butyl, and cyclohexane, and the wavy line indicates the linking site.

7. The boron-containing fused ring compound according to claim 1, characterized in that: Z 1 -Z 14 All are CR 11 , Z 1 -Z 14 R 11 1 to 4 of them are groups selected from the following groups, and the rest are H, ， Wavy lines indicate linkage sites.

8. The boron-containing fused ring compound according to claim 1, wherein Z 1 -Z 14 All are CR 11 , Z 1 -Z 14 R 11 The two adjacent ones form the following ring structure, * represents a bonding site, and the "substituted or unsubstituted" mentioned above means substituted by at least one selected from halogen, phenyl, cyano, methyl, ethyl, isopropyl, cyclohexyl, and cyclopentyl.

9. The boron-containing fused ring compound according to claim 7, wherein: Z 1 -Z 14 Among them, Z 5 , Z 6 , Z 2 , Z 9 , Z 13 , Z 12 CR 21 , the rest are CH, Z 5 , Z 6 , Z 2 , Z 9 , Z 13 , Z 12 R 21 Medium, 1 to 4 Rs 21 is selected from the following groups, the rest are H, Wavy lines indicate linkage sites.

10. The boron-containing fused ring compound according to claim 8, wherein Z 2 and Z 3 The two R's 11 connected to form a ring structure, and / or Z 4 and Z 5 The two R's 11 connected to form a ring structure, and / or Z 11 and Z 12 The two R's 11 Connected to form a ring structure, Z 9 and Z 10 The two R's 11 Connected to form a ring structure, the ring structure is one selected from the following structures: * indicates the attachment site.

11. The boron-containing fused ring compound according to claim 1, characterized in that: It is one of the following compounds:

12. Use of the organic compound according to any one of claims 1 to 11 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.

13. 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 11; 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 11. 14 . The organic electroluminescent device according to claim 13 , wherein the light-emitting layer comprises a host material and a dye, and the dye comprises at least one organic compound according to claim 1 .

15. A display device, characterized in that: The display device comprises the organic electroluminescent device as claimed in claim 13.

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