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 represented by the following formula, wherein preferably at least one of RC is selected from a group represented by formula (1-2). The OLED device prepared from the compound provided by the invention has high luminous efficiency and longer service life. # 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] OLED (Organic Light-Emitting Diode) refers to an organic semiconductor that is made of an extremely thin organic material coating and a glass substrate and emits light when current passes through it. As a new generation of display technology, OLED has better display performance than LCD, with the advantages of self-luminescence, good display effect, low power consumption, high flexibility and ultra-thinness. It is widely used in the screens of smart phones, automotive electronics, smart wearable devices, VR devices and other products.

[0003] There are three main OLED light-emitting materials: blue, red, and green. Together, they determine the performance and lifespan of OLED self-luminescence. Among them, although blue light-emitting materials can emit brighter light, their luminous efficiency is lower and their lifespan is shorter than that of red and green light-emitting materials. Today, red and green OLED phosphorescent materials have been mass-produced and applied on OLED screens. However, blue OLED phosphorescent materials have always had defects in terms of color purity and service life, so blue fluorescent materials are still commonly used in commercial OLED products.

[0004] As OLED products gradually enter the market, people have higher and higher requirements for the performance of such products. In 2016, Professor Takuji Hatakeyama of Japan proposed a TADF (Thermally Activated Delayed Fluorescence) material design strategy based on BN resonance (Adv. Mater. 2016, 28, 2777-2781). This type of material is composed of boron atoms, nitrogen atoms and multiple benzene rings, presenting a rigid polycyclic aromatic hydrocarbon structure with a high fluorescence quantum yield. In particular, compared with traditional blue fluorescent dyes, it has a narrower spectrum and higher color purity, which has obvious advantages. However, due to its particularly planar rigid structure, it is easy to cause molecular accumulation and exciton annihilation, resulting in serious efficiency roll-off. Therefore, this type of organic electroluminescent material still has 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. Although this series of materials has broad application prospects, due to the serious intramolecular rotation, this type of material will lose energy due to vibrational-rotational energy levels, resulting in low external quantum efficiency; even as disclosed in the prior art, some compound structures use dimethylfluorene structures to suppress intramolecular rotational energy levels, but due to the unbalanced charge transfer, the device life is poor.

[0005] Therefore, the 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 blue light emitting material systems to meet commercial needs. The researchers of the present invention have discovered an ingenious molecular design scheme through careful thinking and continuous experiments, and will explain it in detail below, achieving a better blue light emitting effect. Surprisingly, the compounds disclosed by the present invention are very suitable for application in OLEDs and improve the device life. Summary of the invention

[0006] In order to solve the above technical problems, the object of the present invention is to provide a compound having a structure shown in formula (1):

[0007]

[0008] In formula (1), ring A, ring B, and ring C are each independently a C6-C50 aromatic ring or a C3-C50 heteroaromatic ring;

[0009] R a , R b , R c represents single substitution to maximum substitution, R a , R b , R cEach is independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C2-C10 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 a , R b , R c They are independently connected to each other by chemical bonds to form a ring or are not connected; The condition is that R b , R c At least one of the groups is a group represented by formula (1-2), preferably Select a site, R c At least one of them is a group represented by formula (1-2),

[0010]

[0011] In formula (1-2), Z 12 -Z 19 are independently selected from C, CR d or N, the R d 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-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 or substituted or unsubstituted C3-C60 heteroaryl; d The aromatic rings or heteroaromatic rings connected to each other are independently connected to form a ring by chemical bonds or are not connected; condition yes, Z 12 -Z 19 At least one of them is CR d And R d Any one selected from a substituted or unsubstituted C6-C60 aryl group or a substituted or unsubstituted C3-C60 heteroaryl group;

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

[0013] M is O, S, NR1 , CR 2 R 3 One of the following; Q is O, S, NR 4 , CR 5 R 6 One of;

[0014] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 Each 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;

[0015] The substituents mentioned above are each independently selected from any one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl. The expression of the ring structure crossed by “—” indicates that the connection site is at any bonding position on the ring structure, and the * indicates the connection site.

[0016] It is 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, Z 12 -Z 13 , Z 18 -Z 19 The C atoms in the molecule are the chemically possible attachment sites.

[0017] The parent nucleus of the compound provided by the present invention is very important, and other structural features are special substituents on the B ring or C ring, especially the presence of the substituent of formula (1-2) on the C ring can achieve better photoelectric efficiency, and when the aromatic ring is substituted at the ortho position in formula (1-2), the steric hindrance may restrict the rotation of the molecule, reducing the energy loss caused by non-radiative transitions, which is confirmed in theoretical calculations. In actual device applications, the photoelectric efficiency is high, and surprisingly, the material life also shows a significant increase, especially several material molecules with S atoms have achieved better results. The reason is not very clear, and there may be two reasons: 1. The self-selective coupling effect of the S atom enhances the reverse intersystem crossing rate of the material, reduces the triplet exciton lifetime of the material, and reduces the exciton quenching phenomenon in the device; 2. The ortho-substituted aromatic group enhances the CN bond energy in the material molecule and inhibits the degradation of the material molecule in the device.

[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 (C6-C50 aromatic ring) and C3-C60 heteroaromatic ring (C3-C50 heteroaromatic ring) in the present invention, unless otherwise specified, are aromatic groups that satisfy 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 or C6-C50 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 or C3-C50 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 , 1,2,4-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, indolizinyl, 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-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-C20 alkynyl group includes the concepts of 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 alkylsilyl 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, the boron-nitrogen-containing organic compound has a structure as shown in formula (2-1) or formula (2-2):

[0047]

[0048] In formula (2-1) and formula (2-2), Ar 1 ,Ar 2 , Ring A, Ring C, M, R a , R c Having the same limited range as in formula (1);

[0049] Y 1 , Y 2 , Y 3 , Y 4 Each independently is CR 11 or N;

[0050] R 11 are each independently selected from any one of hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, 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 or substituted or unsubstituted C3-C60 heteroaryl, R 11 Each independently is not connected to the adjacent ring structure or is connected to form a ring through a chemical bond,

[0051] The substituents of the above substitutions are each independently selected from any one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl.

[0052] 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.

[0053] Preferably, the Y 1 , Y 2 , Y 3 and Y 4 At most one of them is N;

[0054] More preferably, the Y 1 , Y 2 , Y 3 and Y 4 Each independently is CR 11 ,

[0055] More preferably, Y 1 , Y 2 and Y 4 are independently CH, Y 3 CR 11 , R 11 is one or a combination of two of H, fluorine, chlorine, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, phenyl and naphthyl;

[0056] More preferably, Y 2 , Y 3 Each independently is CR 11 , and Y 2 , Y 3 Each R 11 Connect to form a methyl substituted cyclohexane ring.

[0057] In one embodiment of the present invention, ring A is a structure represented by formula (1-3);

[0058]

[0059] wherein the double bond is the position fused with formula (1), M is the same as defined in formula (1), and ring F is one of a substituted or unsubstituted C6-C50 aromatic ring and a substituted or unsubstituted C3-C50 heteroaromatic ring,

[0060] The substituents mentioned above are each independently selected from any one of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl, or a combination of at least two thereof.

[0061] In a preferred embodiment of the present invention, the ring C has a structure as shown in formula (f):

[0062]

[0063] Among them, the dotted lines represent the fused bonds of the groups;

[0064] Z1 , Z 2 , Z 3 Each independently is CR 31 or N;

[0065] R 31 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-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 or substituted or unsubstituted C3-C60 heteroaryl; 31 Not connected to adjacent ring structures or connected to form a ring through chemical bonds;

[0066] The substituents substituted above are each independently selected from any one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl, provided that at least one R 31 One selected from formula (1-2a) to formula (1-2d):

[0067]

[0068] Among them, Z 12 -Z 18 Each independently selected from CR d or N; said R d 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-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 or substituted or unsubstituted C3-C60 heteroaryl; Q is the same as the above range,

[0069] R 0 One selected from the following groups,

[0070]

[0071] In a preferred embodiment of the present invention, the boron-nitrogen-containing organic compound has a structure as shown in any one of the following formulas (3-1) to (3-5):

[0072]

[0073] Among them, Z 1 ~Z 3 , Y 1 ~Y 4 , Z 4’ ~Z 7’ , Z 8 ~Z 11 Each independently selected from CR 21 or N, where R 21 One selected from hydrogen, halogen, unsubstituted or R'substituted C1-C20 straight or branched alkyl, unsubstituted or R'substituted C3-C20 cycloalkyl, unsubstituted or R'substituted C2-C10 alkenyl, unsubstituted or R'substituted C1-C20 alkoxy, unsubstituted or R'substituted C1-C20 alkylsilyl, unsubstituted or R'substituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, unsubstituted or R'substituted C6-C30 arylamino, unsubstituted or R'substituted C3-C30 heteroarylamino, unsubstituted or R'substituted C6-C30 aryloxy, unsubstituted or R'substituted C3-C30 heteroaryloxy, unsubstituted or R'substituted C6-C60 aryl, unsubstituted or R'substituted C3-C60 heteroaryl, wherein the R's are not connected or connected to form a ring by chemical bonds;

[0074] M and M' are respectively the same as the definitions of M in formula (1), preferably M and M' are respectively independently selected from O or S, more preferably selected from S;

[0075] R' is independently selected from any one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl, and more preferably at least one of the following groups:

[0076]

[0077] Preferably, Z 1 ~Z 3Each independently is CR 21 , where at least one R 21 A group selected from the group represented by formula (1-2).

[0078] In a preferred embodiment of the present invention, the above Ar 1 ,Ar 2 Each is independently a group of formula (g),

[0079]

[0080] U 6 ~U 10 Each independently is CR 51 or N; R 51 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-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 or substituted or unsubstituted C3-C60 heteroaryl; 51 Each independently is not connected to the adjacent ring structure or is connected to form a ring through a chemical bond;

[0081] The substituents of the above substitutions are each independently selected from any one or a combination of two of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl;

[0082] It is further preferred that formula (g) is selected from any one of substituted phenyl, substituted benzocyclohexyl, substituted naphthyl, and substituted biphenyl, wherein the substituent is selected from one or a combination of two of halogen, amino, alkyl substituted amino, C1-C6 straight or branched alkyl, phenyl, biphenyl, and benzocyclohexyl;

[0083] It is further preferred that formula (g) is one of the following groups,

[0084]

[0085]

[0086]

[0087] Preferably, in the above formulas (3-1) to (3-5), Z 1 ~Z 3 , Y 1 ~Y 4 , Z 4’ ~Z 7’ , Z 8 ~Z 11 At most one of them is N;

[0088] Preferably, the Z 1 ~Z 3 , Y 1 ~Y 4 , Z 4’ ~Z 7’ , Z 8 ~Z 11 Each independently is CR 21 , and at least one of them is R 21 is any one of C1-C6 straight chain or branched chain alkyl substituted or unsubstituted C1-C20 straight chain or branched chain alkyl, C1-C6 straight chain or branched chain alkyl substituted or unsubstituted C3-C20 cycloalkyl, preferably R 21 It is one or a combination of two of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl and cyclohexyl.

[0089] Furthermore, the organic compound of the present invention can preferably include the specific structural compounds shown below, which are only representative and do not limit the scope of the present invention:

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] 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.

[0102] 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.

[0103] Preferably, the organic compound is used as a light-emitting layer material in an organic electroluminescent device.

[0104] Preferably, the organic compound is used as a luminescent dye of a light-emitting layer in an organic electroluminescent device.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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, and can effectively improve the performance of the device. Its good carrier transport performance and high luminous efficiency have potential applications in solving the efficiency roll-off of OLED devices at high current density and extending the life of the device.

[0110] 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.

[0111] In a fourth aspect, the present invention provides a display device, the display device comprising the organic electroluminescent device as described in the third aspect. The OLED device prepared using the compound of the present invention has a low starting voltage, high luminous efficiency and a better service life, and can meet the requirements of current panel and display manufacturers for high-performance materials. DETAILED DESCRIPTION

[0112] The technical solution of the present invention is further described in more detail below.

[0113] Synthesis method of the compound of the present invention

[0114] The compound represented by formula (1) of the present invention can be obtained by a known method, for example, by a known organic synthesis method. In the following examples, exemplary synthesis routes are provided, but those skilled in the art can also obtain the compound by other known methods.

[0115] In order to facilitate understanding of the synthesis ideas, representative synthesis routes of the compounds shown in the general formula are provided as follows. These routes are not the only synthesis methods. It should be noted that the atom numbering in this part and the molecules used are exemplary numbers, which are different from the numbering system of the technical solution part of the present invention.

[0116]

[0117]

[0118]

[0119] 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.

[0120] Organic EL devices

[0121] 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. The compound of the present invention can be contained in the organic material layer, and is particularly suitable for being contained in the light emitting layer.

[0122] 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.

[0123] 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.

[0124] The organic layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic layer can be an organic small molecule, an organic macromolecule or a polymer, and a combination thereof.

[0125] 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.

[0126] 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, wherein the aromatic amine derivatives include the compounds shown in HT-1 to HT-51 below; or any combination thereof.

[0127]

[0128]

[0129]

[0130] 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.

[0131]

[0132] 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.

[0133] 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.

[0134] 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.

[0135]

[0136] In one aspect of the present invention, the barrier layer around the light-emitting layer can be selected from, but not limited to, one or more combinations of PH-1 to PH-85.

[0137]

[0138]

[0139]

[0140]

[0141] 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.

[0142] The OLED organic 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 multi-layer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0143] 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.

[0144]

[0145]

[0146]

[0147] 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.

[0148] 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.

[0149] 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.

[0150] Example

[0151] Theoretical calculations related to photoelectric properties

[0152] The calculations described in the patent were performed using the Gaussian16 program.

[0153] Optimize the ground state structure of the molecule at the B3LYP / 6-31G* calculation level.

[0154] The energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the molecule in the ground state were calculated using the B3LYP / 6-31G* method, and the UV-visible absorption spectrum of the molecule was obtained using the B3LYP / 6-31G* method in the SMD solvent model (toluene).

[0155] The structure of the lowest singlet excited state of the molecule was optimized using the B3LYP / 6-31G* method. The energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the molecule in the excited state were calculated using the B3LYP / 6-31G* method. The maximum fluorescence emission wavelength of the molecule was obtained using the B3LYP / 6-31G* method in the SMD solvent model (toluene).

[0156]

[0157]

[0158] From the table above, it can be seen that the comparative example structure (1) and the example structures (2) and (3) are not much different in theoretical calculation data, indicating that the phenyl occluding structure does not expand the conjugation range of the material, thereby causing red shift. It can be inferred that: structures (2) and (3) are connected to the ring C of the BN mother core, which may cause the spectrum to be red shifted because the conjugated structure of the material molecule is expanded. However, due to the presence of ortho-substituted phenyl occluding sites on the benzofuran and benzothiophene structures, the connected benzofuran and benzothiophene structures are vertical to the BN mother core in space, so the emission spectrum does not undergo red shift.

[0159] Synthesis of compounds

[0160] 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).

[0161] Synthesis of the compounds of the present invention

[0162] Synthesis Example (1): Synthesis of Intermediate A1

[0163]

[0164] Experimental steps: 3,5-di-tert-butylphenylboronic acid (30 g, 128.13 mmol), 2-bromo-4-tert-butylaniline (128.13 mmol, 29.23 g), tetrakistriphenylphosphine palladium (1.28 mmol, 1.48 g), potassium carbonate (166.56 mmol, 23.02 g) were added into a 1L three-necked flask, and 300 mL of a mixed solvent of 1,4-dioxane + water (5:1) was added. The mixture was heated to reflux under nitrogen protection for 3 h, and then a sample was taken for GC-MS testing. The raw material reaction was complete, the reaction was stopped, the washed liquid was concentrated, and pressure distillation was performed for purification to obtain the target intermediate (34.56 g, 79.9%).

[0165] MS: 337.28 / 337.55 (calculated / found).

[0166] Synthesis Example (2): Synthesis of Intermediate A2

[0167]

[0168] Experimental steps: Referring to the method for synthesizing intermediate A1, intermediate A2 (37.84 g, 87.5%) was synthesized.

[0169] MS: 335.26 / 335.54 (calculated / found).

[0170] Synthesis Example (3): Synthesis of Intermediate B1

[0171]

[0172] Experimental steps: Add intermediate A1 (33 g, 97.76 mmol), 4-tert-butyl bromobenzene (20.84 g, 97.76 mmol), Pd(dppf)Cl2 (1.42 g, 1.96 mmol), sodium tert-butoxide (12.21 g, 127.09 mmol) into a 1L three-necked flask, add 300 mL of toluene, react at 100 degrees Celsius under nitrogen protection for 10 hours, then take a sample for GC-MS testing. The raw materials are completely reacted, the reaction system is washed with water, the separated liquid is filtered and dried, and concentrated to dryness under reduced pressure. Purify by column chromatography to obtain the target intermediate (38.81 g, 84.5%).

[0173] MS: 469.37 / 469.76 (calculated / found).

[0174] Synthesis Example (4): Synthesis of Intermediate B2

[0175]

[0176] Experimental steps: Intermediate B2 (34.26 g, 74.5%) was synthesized by referring to the method for synthesizing intermediate B1.

[0177] MS: 467.36 / 467.74 (calculated / found).

[0178] Synthesis Example (5): Synthesis of Intermediate B3

[0179]

[0180] Experimental steps: Intermediate B3 (31.46 g, 83.64%) was synthesized by referring to the method for synthesizing intermediate B1.

[0181] MS: 337.19 / 337.53 (calculated / found).

[0182] Synthesis Example (6): Synthesis of Intermediate B4

[0183]

[0184] Experimental steps: Intermediate B4 (35.58 g, 81.53%) was synthesized by referring to the method for synthesizing intermediate B1.

[0185] MS: 391.23 / 391.62 (calculated / found).

[0186] Synthesis Example (7): Synthesis of Intermediate B5

[0187]

[0188] Experimental steps: Intermediate B5 (29.16 g, 80.24%) was synthesized by referring to the method for synthesizing intermediate B1.

[0189] MS: 391.23 / 391.62 (calculated / found).

[0190] Synthesis Example (8): Synthesis of Intermediate C1

[0191]

[0192] Experimental steps: Add phenylboric acid (30 g, 246.04 mmol) into a 1L single-necked flask, add o-bromophenol (51.08 g, 295.25 mmol), tetrakistriphenylphosphine palladium (5.7 g, 4.92 mmol), potassium carbonate (44.21 g, 319.86 mmol), and then add 300 mL of a mixed solvent of 1,4-dioxane: water = 5:1 (v:v), react at 100 ° C under nitrogen protection for 5 h, then take a sample for TLC detection, the raw material reaction is complete, and it is purified by reduced pressure distillation to obtain the target intermediate C1 (30.33 g, 72.42%).

[0193] MS: 170.07 / 170.21 (calculated / found).

[0194] Synthesis Example (9): Synthesis of Intermediate C2

[0195]

[0196] Experimental steps: Intermediate C2 (27.96 g, 77.25%) was synthesized by referring to the method for synthesizing intermediate C1.

[0197] MS: 282.20 / 282.43 (calculated / found).

[0198] Synthesis Example (10): Synthesis of Intermediate C3

[0199]

[0200] Experimental steps: Intermediate C3 (29.56 g, 81.56%) was synthesized by referring to the method for synthesizing intermediate C1.

[0201] MS: 280.18 / 280.41 (calculated / found).

[0202] Synthesis Example (11): Synthesis of Intermediate C4

[0203]

[0204] Experimental steps: Intermediate C4 (35.74 g, 85.54%) was synthesized by referring to the method for synthesizing intermediate C1.

[0205] MS: 171.07 / 171.20 (calculated / found).

[0206] Synthesis Example (12): Synthesis of Intermediate C5

[0207]

[0208] Experimental procedure: Intermediate C5 (26.76 g, 69.65%) was synthesized by referring to the method for synthesizing intermediate C1. MS: 220.09 / 220.27 (calculated value / measured value).

[0209] Synthesis Example (13): Synthesis of Intermediate C6

[0210]

[0211] Experimental procedure: Referring to the synthesis procedure of intermediate C1, intermediate C6 (54.31 g, 85.67%) was synthesized. MS: 357.98 / 359.65 (calculated value / measured value).

[0212] Synthesis Example (14): Synthesis of Material C7

[0213]

[0214] Experimental procedure: Referring to the synthesis procedure of intermediate C1, intermediate C7 (38.84 g, 77.49%) was synthesized. MS: 470.10 / 471.86 (calculated value / measured value).

[0215] Synthesis Example (15): Synthesis of Material C8

[0216]

[0217] Experimental procedure: Referring to the synthesis procedure of intermediate C1, intermediate C8 (41.27 g, 82.09%) was synthesized. MS: 468.09 / 469.85 (calculated value / measured value).

[0218] Synthesis Example (16): Synthesis of Material C9

[0219]

[0220] Experimental procedure: Referring to the synthetic procedure of the synthetic intermediate C1, the intermediate C9 (44.23 g, 79.26%) was synthesized. MS: 407.99 / 409.71 (calculated value / measured value).

[0221] Synthesis Example (17): Synthesis of Material C10

[0222]

[0223] Experimental steps: Referring to the synthesis steps of intermediate C1, intermediate C10 (47.84 g, 75.69%) was synthesized.

[0224] MS: 358.97 / 360.64 (calculated / found).

[0225] Synthesis Example (18): Synthesis of Material C11

[0226]

[0227] Experimental steps: Add phenylboric acid (12.29 g, 100.81 mmol), 4-bromo-6-chlorodibenzothiophene (30 g, 100.81 mmol), tetrakistriphenylphosphine palladium (2.33 g, 2.02 mmol) and potassium carbonate (21 g, 151.21 mmol) into a 1L single-necked flask, add 300 mL of a mixed solvent of 1,4-dioxane + water = 5:1, react at 100 °C under nitrogen protection for 3 hours, then stop heating, wash with water, separate, dry, concentrate, and purify by column chromatography to obtain the target intermediate C11 (20.91 g, 70.35%).

[0228] MS: 294.03 / 294.80 (calculated / found).

[0229] Synthesis Example (19): Synthesis of Material C12

[0230]

[0231] Experimental steps: Referring to the synthesis steps of intermediate C11, intermediate C12 (19.16 g, 79.94%) was synthesized.

[0232] MS: 351.11 / 351.47 (calculated / found).

[0233] Synthesis Example (20): Synthesis of Intermediate D1

[0234]

[0235] Experimental steps: Add 4-aminophenylboronic acid (15.23 g, 111.22 mmol) into a 1L single-necked flask, add intermediate C6 (40 g, 111.23 mmol), tetrakistriphenylphosphine palladium (2.57 g, 2.22 mmol), potassium carbonate (20 g, 144.59 mmol), and then add 300 mL of a mixed solvent of 1,4-dioxane: water = 5:1, react at 100 °C under nitrogen protection for 5 h, then take a sample for TLC detection, the raw material reaction is complete, and purified by reduced pressure distillation to obtain the target intermediate D1 (32.98 g, 79.73%).

[0236] MS: 371.11 / 371.86 (calculated / found).

[0237] Synthesis Example (21): Synthesis of Intermediate D2

[0238]

[0239] Experimental steps: Referring to the synthesis steps of intermediate D1, intermediate D2 (24.19 g, 73.7%) was synthesized.

[0240] MS: 483.23 / 484.08 (calculated / found).

[0241] Synthesis Example (22): Synthesis of Intermediate D3

[0242]

[0243] Experimental steps: Referring to the synthesis steps of intermediate D1, intermediate D3 (25.53 g, 82.94%) was synthesized.

[0244] MS: 481.22 / 482.06 (calculated / found).

[0245] Synthesis Example (23): Synthesis of Intermediate D4

[0246]

[0247] Experimental steps: Referring to the synthesis steps of intermediate D1, intermediate D4 (24.97 g, 80.94%) was synthesized.

[0248] MS: 372.10 / 372.85 (calculated / found).

[0249] Synthesis Example (24): Synthesis of Intermediate D5

[0250]

[0251] Experimental steps: Referring to the synthesis steps of intermediate D1, intermediate D5 (25.13 g, 81.35%) was synthesized.

[0252] MS: 421.12 / 421.92 (calculated / found).

[0253] Synthesis Example (25): Synthesis of Intermediate D6

[0254]

[0255] Experimental steps: Add intermediate D1 (25 g, 67.23 mmol), palladium acetate (0.8 g, 3.36 mmol), tricyclohexylphosphine (2.83 g, 10.08 mmol), and potassium carbonate (11.15 g, 80.67 mmol) into a 1L single-necked flask, add 300 mL of toluene, react at 100 °C under nitrogen protection for 3 hours, then stop the reaction, wash the separated liquid with water, dry and concentrate, and purify by column chromatography to obtain 18.64 g (82.66%) of the target intermediate.

[0256] MS: 335.13 / 335.41 (calculated / found).

[0257] Synthesis Example (26): Synthesis of Intermediate D7

[0258]

[0259] Experimental procedure: Intermediate D7 (19.90 g, 86.07%) was synthesized by referring to the synthesis procedure of intermediate D6. MS: 447.26 / 447.62 (calculated value / measured value).

[0260] Synthesis Example (27): Synthesis of Intermediate D8

[0261]

[0262] Experimental procedure: Referring to the synthetic procedure of the synthetic intermediate D6, the intermediate D8 (18.84 g, 81.52%) was synthesized. MS: 445.24 / 445.61 (calculated value / measured value).

[0263] Synthesis Example (28): Synthesis of Intermediate D9

[0264]

[0265] Experimental procedure: Referring to the synthetic procedure of intermediate D6, intermediate D9 (19.06 g, 84.48%) was synthesized. MS: 336.13 / 336.39 (calculated value / measured value).

[0266] Synthesis Example (29): Synthesis of Intermediate D10

[0267]

[0268] Experimental procedure: Referring to the synthetic procedure of the synthetic intermediate D6, the intermediate D10 (20.08 g, 87.91%) was synthesized. MS: 385.15 / 385.47 (calculated value / measured value).

[0269] Synthesis Example (30): Synthesis of Intermediate D11

[0270]

[0271] Experimental steps: Add intermediate D6 (20 g, 59.63 mmol) into a 500 mL single-necked flask, add 200 mL of DMF, slowly add NBS (26.53 g, 149.07 mmol) at 0°C, return to room temperature for reaction for 1 hour, then add 500 mL of water, a large amount of solid precipitated, filter and wash three times with 200 mL of water, then recrystallize once with toluene + ethanol, filter and dry to obtain 22.17 g (75.38%) of the target intermediate.

[0272] MS: 490.95 / 493.20 (calculated / found).

[0273] Synthesis Example (31): Synthesis of Intermediate D12

[0274]

[0275] Experimental steps: Referring to the synthesis steps of the synthetic intermediate D11, the intermediate D12 (20.69 g, 76.48%) was synthesized.

[0276] MS: 603.08 / 605.41 (calculated / found).

[0277] Synthesis Example (32): Synthesis of Intermediate D13

[0278]

[0279] Experimental steps: Referring to the synthesis steps of intermediate D11, intermediate D13 (21.03 g, 77.65%) was synthesized.

[0280] MS: 601.06 / 603.40 (calculated / found).

[0281] Synthesis Example (33): Synthesis of Intermediate D14

[0282]

[0283] Experimental steps: add isobutyl nitrite (6.3g, 60.83mmol) and cupric chloride (11g, 81.10mmol) into a 500mL three-necked flask, add 200mL of acetonitrile, activate at 60°C for 1 hour under nitrogen protection, then slowly add intermediate D11 (20g, 40.55mmol), react at 60°C for 5 hours after the addition is complete, then stop the reaction, wash the separated liquid with water, dry and concentrate, purify by column chromatography to obtain the target intermediate D14 (16.92g, 81.38%).

[0284] MS: 509.90 / 512.63 (calculated / found).

[0285] Synthesis Example (34): Synthesis of Intermediate D15

[0286]

[0287] Experimental steps: Referring to the synthesis steps of intermediate D14, intermediate D15 (15.58 g, 75.48%) was synthesized.

[0288] MS: 622.03 / 624.84 (calculated / found).

[0289] Synthesis Example (35): Synthesis of Intermediate D16

[0290]

[0291] Experimental steps: Referring to the synthesis steps of intermediate D14, intermediate D16 (15.88 g, 76.93%) was synthesized.

[0292] MS: 620.01 / 622.83 (calculated / found).

[0293] Synthesis Example (36): Synthesis of Intermediate D17

[0294]

[0295] Experimental steps: Referring to the synthesis steps of intermediate D11, intermediate D17 (21.47 g, 74.08%) was synthesized.

[0296] MS: 506.93 / 509.26 (calculated / found).

[0297] Synthesis Example (37): Synthesis of Intermediate D18

[0298]

[0299] Experimental steps: Referring to the synthesis steps of intermediate D14, intermediate D18 (15.47 g, 74.52%) was synthesized.

[0300] MS: 525.88 / 528.69 (calculated / found).

[0301] Synthesis Example (38): Synthesis of Intermediate E1

[0302]

[0303] Experimental steps: Add intermediate B1 (20 g, 42.48 mmol), intermediate D14 (21.83 g, 42.58 mmol), sodium tert-butoxide (6.2 g, 63.86 mmol), Pd2(dba)3 (1.95 g, 2.13 mmol) and tri-tert-butylphosphine tetrafluoroborate (1.85 g, 6.39 mmol) into a 1L single-necked flask, react at 100 °C under nitrogen protection for 2 hours, then stop heating, wash the separated liquid with water, dry and concentrate, and purify by column chromatography to obtain the target intermediate E1 (31.12 g, 81.08%).

[0304] MS: 899.35 / 901.47 (calculated / found).

[0305] Synthesis Example (39): Synthesis of Intermediate E2

[0306]

[0307] Experimental steps: referring to the synthetic steps of synthetic product E1, synthetic product E2 (33.54 g, 77.71%),

[0308] MS: 1011.47 / 1013.69 (calculated / found).

[0309] Synthesis Example (40): Synthesis of Intermediate E3

[0310]

[0311] Experimental steps: referring to the synthetic steps of synthetic product E1, synthetic product E3 (32.94 g, 76.48%) was synthesized.

[0312] MS: 1009.46 / 1011.67 (calculated / found).

[0313] Synthesis Example (41): Synthesis of Intermediate E4

[0314]

[0315] Experimental procedure: referring to the synthetic procedure of the synthetic product E1, the synthetic product E4 (31.71 g, 73.30%) was synthesized. MS: 1009.46 / 1011.67 (calculated value / measured value).

[0316] Synthesis Example (42): Synthesis of Product E5

[0317]

[0318] Experimental procedure: Referring to the synthetic procedure of the synthetic product E1, the synthetic product E5 (30.04 g, 76.91%) was synthesized. MS: 915.32 / 917.53 (calculated value / measured value).

[0319] Synthesis Example (43): Synthesis of Product E6

[0320]

[0321] Experimental procedure: Referring to the synthetic procedure of the synthetic product E1, the synthetic product E6 (38.76 g, 66.08%) was synthesized. MS: 823.32 / 825.37 (calculated value / measured value).

[0322] Synthesis Example (44): Synthesis of Product E7

[0323]

[0324] Experimental procedure: Referring to the synthetic procedure of the synthetic product E1, the synthetic product E7 (38.76 g, 66.08%) was synthesized. MS: 821.30 / 823.36 (calculated value / measured value).

[0325] Synthesis Example (45): Synthesis of Product E8

[0326]

[0327] Experimental procedure: Referring to the synthetic procedure of the synthetic product E1, the synthetic product E8 (39.47 g, 72.77%) was synthesized. MS: 761.21 / 763.22 (calculated value / measured value).

[0328] Synthesis Example (46): Synthesis of Product E9

[0329]

[0330] Experimental procedure: Referring to the synthetic procedure of the synthetic product E1, the synthetic product E9 (30.22 g, 78.57%) was synthesized. MS: 897.33 / 899.45 (calculated value / measured value).

[0331] Synthesis Example (47): Synthesis of Product F1

[0332]

[0333] Experimental procedure: Referring to the synthetic procedure of the synthetic product E1, the synthetic product F1 (17.64 g, 65.60%) was synthesized. MS: 1210.65 / 1212.18 (calculated value / measured value).

[0334] Synthesis Example (48): Synthesis of Product F2

[0335]

[0336] Experimental procedure: Product F2 (18.46 g, 69.92%) was synthesized by referring to the synthetic procedure of product F1. MS: 1320.76 / 1322.38 (calculated value / measured value).

[0337] Synthesis Example (49): Synthesis of Product F3

[0338]

[0339] Experimental procedure: Product F3 (18.27 g, 68.24%) was synthesized by referring to the synthetic procedure of product F1. MS: 1226.63 / 1228.24 (calculated value / measured value).

[0340] Synthesis Example (50): Synthesis of Product F4

[0341]

[0342] Experimental procedure: Referring to the synthetic procedure of the synthetic product F1, the synthetic product F4 (19.25 g, 71.53%) was synthesized. MS: 1208.64 / 1210.16 (calculated value / measured value).

[0343] Synthesis Example (51): Synthesis of Product F5

[0344]

[0345] Experimental procedure: Referring to the synthetic procedure of synthetic product F1, synthetic product F5 (18.86 g, 72.17%) was synthesized. MS: 1322.78 / 1324.39 (calculated value / measured value).

[0346] Synthesis Example (52): Synthesis of Product F6

[0347]

[0348] Experimental procedure: Referring to the synthetic procedure of synthetic product F1, synthetic product F6 (19.04 g, 69.16%) was synthesized. MS: 1134.62 / 1136.08 (calculated value / measured value).

[0349] Synthesis Example (53): Synthesis of Product F7

[0350]

[0351] Experimental procedure: Referring to the synthetic procedure of the synthetic product F1, the synthetic product F7 (18.79 g, 68.20%) was synthesized. MS: 1132.61 / 1134.06 (calculated value / measured value).

[0352] Synthesis Example (54): Synthesis of Product F8

[0353]

[0354] Experimental procedure: Referring to the synthetic procedure of synthetic product F1, synthetic product F8 (16.72 g, 59.41%) was synthesized. MS: 1072.51 / 1073.92 (calculated value / measured value).

[0355] Synthesis Example (55): Synthesis of Product F9

[0356]

[0357] Experimental steps: Referring to the synthetic steps of synthetic product F1, synthetic product F9 (18.76 g, 69.76%) was obtained.

[0358] MS: 1210.65 / 1212.18 (calculated / found).

[0359] Synthesis Example (56): Synthesis of Product F10

[0360]

[0361] Experimental steps: Referring to the synthetic steps of synthetic product F1, synthetic product F10 (17.98 g, 67.16%) was obtained.

[0362] MS: 1226.63 / 1228.24 (calculated / found).

[0363] Synthesis Example (57): Synthesis of Product F11

[0364]

[0365] Experimental steps: referring to the synthetic steps of synthetic product F1, synthetic product F11 (18.12 g, 67.63%).

[0366] MS: 1224.62 / 1226.22 (calculated / found).

[0367] Synthesis Example (58): Synthesis of Product M-1

[0368]

[0369] Experimental steps: Add intermediate F1 (20 g, 16.50 mmol) into a 500 mL three-necked flask, add 100 mL of ultra-dry xylene, slowly add tert-butyl lithium (28 mL, 41.25 mmol) at -60 ° C under nitrogen protection, then return to room temperature, heat at 60 ° C for 2 hours, cool to -60 ° C, add boron tribromide (12.40 g, 49.50 mmol), DMAP (8.53 g, 66.00 mmol) successively, return to room temperature, heat at 100 ° C for 10 hours, stop heating, wash the separated liquid with water, dry and concentrate, purify by column chromatography to obtain the target product M-1 (5.35 g, 27.35%).

[0370] MS: 1184.68 / 1185.52 (calculated / measured).

[0371] Synthesis Example (59): Synthesis of Product M-6

[0372]

[0373] Experimental steps: referring to the synthetic steps of the synthetic product M-1, the synthetic product M-6 (5.71 g, 29.13%) was synthesized. MS: 1294.79 / 1295.72 (calculated value / measured value).

[0374] Synthesis Example (60): Synthesis of Product M-8

[0375]

[0376] Experimental steps: referring to the synthetic steps of the synthetic product M-1, the synthetic product M-8 (5.13 g, 28.26%) was synthesized. MS: 1296.80 / 1297.74 (calculated value / measured value).

[0377] Synthesis Example (61): Synthesis of Product M-10

[0378]

[0379] Experimental steps: referring to the synthetic steps of the synthetic product M-1, the synthetic product M-10 (4.94 g, 25.24%) was synthesized. MS: 1200.66 / 1201.58 (calculated value / measured value).

[0380] Synthesis Example (62): Synthesis of Product M-25

[0381]

[0382] Experimental steps: referring to the synthetic steps of the synthetic product M-1, the synthetic product M-25 (5.21 g, 26.62%) was synthesized. MS: 1182.66 / 1183.60 (calculated value / measured value).

[0383] Synthesis Example (63): Synthesis of Product M-20

[0384]

[0385] Experimental steps: Referring to the synthetic steps of the synthetic product M-1, the synthetic product M-20 (5.67 g, 29.03%) was synthesized. MS: 1108.65 / 1109.42 (calculated value / measured value)

[0386] Synthesis Example (64): Synthesis of Product M-18

[0387]

[0388] Experimental steps: referring to the synthetic steps of the synthetic product M-1, the synthetic product M-18 (4.82 g, 24.67%) was synthesized. MS: 1106.63 / 1107.41 (calculated value / measured value).

[0389] Synthesis Example (65): Synthesis of Product M-21

[0390]

[0391] Experimental steps: referring to the synthetic steps of the synthetic product M-1, the synthetic product M-21 (5.07 g, 26.00%) was synthesized. MS: 1046.54 / 1047.27 (calculated value / measured value).

[0392] Synthesis Example (66): Synthesis of Product M-97

[0393]

[0394] Experimental steps: referring to the synthetic steps of the synthetic product M-1, the synthetic product M-97 (4.79 g, 25.58%) was synthesized. MS: 1184.68 / 1185.52 (calculated value / measured value).

[0395] Synthesis Example (67): Synthesis of Product M-100

[0396]

[0397] Experimental steps: referring to the synthetic steps of the synthetic product M-1, the synthetic product M-100 (4.49 g, 22.94%) was synthesized. MS: 1200.66 / 1201.58 (calculated value / measured value).

[0398] Synthesis Example (68): Synthesis of Product M-106

[0399]

[0400] Experimental steps: Referring to the synthesis steps of the synthetic product M-1, the synthetic product M-106 (4.27 g, 21.82%) was synthesized.

[0401] MS: 1198.64 / 1199.56 (calculated / measured).

[0402] 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.

[0403] Device Embodiment

[0404] The preparation process of the organic electroluminescent device in this embodiment is as follows:

[0405] The glass plate coated with the ITO transparent conductive layer 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 to completely remove the water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0406] Place the glass substrate with the anode in a vacuum chamber and evacuate the chamber to a vacuum of less than 1*10 -5 Pa, vacuum evaporating a mixture of HT-4:HI-3 (97 / 3, w / w) on the above anode layer as a hole injection layer, the evaporation rate is 0.1 nm / s, and the evaporation film thickness is 10 nm;

[0407] HT-4 was vacuum-deposited on the hole injection layer as the hole transport layer of the device, with a deposition rate of 0.1 nm / s and a total deposition film thickness of 60 nm.

[0408] HT-14 was vacuum-deposited on the hole transport layer as the electron blocking layer of the device, with a deposition rate of 0.1 nm / s and a total deposition film thickness of 5 nm.

[0409] The light-emitting layer of the device is vacuum-evaporated on the electron blocking layer. The light-emitting layer includes a main material and a dye material. A 20 nm binary mixture of compound BFH4: fluorescent dye (100:3, w / w) is evaporated as the light-emitting layer by a multi-source co-evaporation method. The fluorescent dye is the compound M-1 of the present invention.

[0410] 5 nm of ET-23 was vacuum-deposited on the light-emitting layer as a hole blocking layer, and 25 nm of a mixture of compounds ET-69:ET-57 (50 / 50, w / w) was vacuum-deposited as an electron transport layer at a rate of 0.1 nm / s;

[0411] LiF with a thickness of 1 nm was vacuum-deposited on the electron transport layer (ETL) as an electron injection layer, and 150 nm of metal aluminum was used as a cathode. The total evaporation rate of LiF was controlled at 0.1 nm / sec, and the evaporation rate of the metal electrode was controlled at 1 nm / sec.

[0412] Device Example 2 to Device Example 11:

[0413] The same method as device Example 1 was used to prepare the device, except that the luminescent dye in the luminescent layer was replaced by the compounds of the present invention listed in Table 1 instead of the compound M-1 of the present invention.

[0414] Device Comparative Examples 1 to 7 were prepared in the same manner as in Device Example 1, except that the luminescent dye in the luminescent layer was replaced by the compound M1 of the present invention with the following prior art compounds N-1 to N-5, or N-1 to N-5, CM1, and CM25 were prepared by a similar preparation process to that of Example 1. The specific structures are shown below:

[0415]

[0416] Device test method (including equipment and test conditions):

[0417] The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

[0418] The external quantum efficiency (EQE%) of the organic electroluminescent device was measured using an integrating sphere; the external quantum efficiency of the device in comparative example 1 was set to 1.0, and the external quantum efficiencies of the other materials were all ratios thereof;

[0419] The life test of LT97 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;

[0420] The performance of the organic electroluminescent devices prepared in the above device embodiments and comparative examples is shown in Table 1 below.

[0421] Table 1:

[0422]

[0423]

[0424] As shown in Table 1, when the material schemes and preparation processes of other functional layers in the structure of the organic electroluminescent device are exactly the same, compared with the comparative example, the organic electroluminescent devices prepared by the device embodiments 1-11 of the present invention are compared with the organic electroluminescent devices prepared by the comparative examples 1-7, and the operating voltage is effectively kept basically unchanged. The external quantum efficiency generally increases by 10%-20%, and it is estimated that the dibenzo-pentacyclic ring substituted by the ortho-aromatic ring or heteroaromatic ring in the lower position of the molecule restricts the rotation of the molecule. It is speculated that because CM1 and CM25 do not have the ortho-aromatic ring or heteroaromatic ring occlusion effect, the lower dibenzo-pentacyclic ring and the BN mother nucleus are coplanar in space, and the conjugation range is expanded, resulting in a red shift in the emission spectrum. Although the life span is improved, the emission spectrum is broadened and the efficiency is seriously reduced due to the serious CT state in the molecule. The presence of a dibenzopentacyclic ring substituted with an ortho-aromatic ring or a heteroaromatic ring at the lower position of the molecule of the present invention reduces the energy loss caused by non-radiative transitions, and the material life also shows a significant increase, especially for several material molecules with S atoms. There are two reasons for this: 1. The self-selective coupling effect of the S atom enhances the reverse intersystem crossing rate of the material, reduces the triplet exciton life of the material, and reduces the exciton quenching phenomenon in the device; 2. The ortho-substituted aromatic group enhances the CN bond energy in the material molecule, and inhibits the degradation of the material molecule in the device.

[0425] 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.

[0426] 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, ring B, and ring C are each independently a C6-C50 aromatic ring or a C3-C50 heteroaromatic ring; R a , R b , R c represents single substitution to maximum substitution, R a , R b , R c Each is independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C2-C10 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 a , R b , R c They are independently connected to each other by chemical bonds to form a ring or are not connected; The condition is that R b , R c At least one of them is a group represented by formula (1-2), preferably Ground, R c At least one of them is a group represented by formula (1-2), In formula (1-2), Z 12 -Z 19 are independently selected from C, CR d or N, the R d 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-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 or substituted or unsubstituted C3-C60 heteroaryl; d The aromatic rings or heteroaromatic rings connected to each other are independently connected to form a ring by chemical bonds or are not connected; The condition is, Z 12 -Z 19 At least one of them is CR d And R d Any one selected from a substituted or unsubstituted C6-C60 aryl group or a substituted or unsubstituted C3-C60 heteroaryl group; Ar 1 ,Ar 2 One selected from a substituted or unsubstituted C6-C50 aromatic ring, a substituted or unsubstituted C3-C50 heteroaromatic ring; M is O, S, NR 1 , CR 2 R 3 One of the following; Q is O, S, NR 4 , CR 5 R 6 One of; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 Each 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; The substituents mentioned above are each independently selected from any one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl. The expression of a ring structure crossed by "—" indicates that the connection site is at any bonding position on the ring structure, 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 (2-1) or formula (2-2): In formula (2-1) and formula (2-2), Ar 1 ,Ar 2 , Ring A, Ring C, M, R a , R c Having the same limited range as in formula (1); Y 1 , Y 2 , Y 3 , Y 4 Each independently is CR 11 or N; R 11 each independently selected from any one of hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, 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 or substituted or unsubstituted C3-C60 heteroaryl, R 11 Each independently is not connected to the adjacent ring structure or is connected to form a ring through a chemical bond, The substituents of the above substitutions are each independently selected from any one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl. 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. Preferably, the Y 1 , Y 2 , Y 3 and Y 4 At most one of them is N; More preferably, the Y 1 , Y 2 , Y 3 and Y 4 Each independently is CR 11 , More preferably, Y 1 , Y 2 and Y 4 are independently CH, Y 3 CR 11 , R 11 is one or a combination of two of H, fluorine, chlorine, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, phenyl and naphthyl; More preferably, Y 2 , Y 3 Each independently is CR 11 , and Y 2 , Y 3 Each R 11 Connect to form a methyl substituted cyclohexane ring.

3. The boron-nitrogen-containing organic compound according to claim 1, characterized in that: Ring A is a structure represented by formula (1-3); wherein the double bond is the position fused with formula (1), M is the same as defined in formula (1), and ring F is one of a substituted or unsubstituted C6-C50 aromatic ring and a substituted or unsubstituted C3-C50 heteroaromatic ring, The substituents mentioned above are each independently selected from any one of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl, or a combination of at least two thereof.

4. The boron-nitrogen-containing organic compound according to claim 1, characterized in that: The ring C has a structure as shown in formula (f): Among them, the dotted lines represent the fused bonds of the groups; Z 1 , Z 2 , Z 3 Each independently is CR 31 or N; R 31 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-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 or substituted or unsubstituted C3-C60 heteroaryl; 31 Not connected to adjacent ring structures or connected to form a ring through chemical bonds; The substituents substituted above are each independently selected from any one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl, provided that at least one R 31 One selected from formula (1-2a) to formula (1-2d): Among them, Z 12 -Z 18 Each independently selected from CR d or N; said R d 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-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 or substituted or unsubstituted C3-C60 heteroaryl; Q has the same scope as that of claim 1, R 0 One selected from the following groups, 5. 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 any one of the following formulas (3-1) to (3-5): Among them, Z 1 ~Z 3 , Y 1 ~Y 4 , Z 4’ ~Z 7’ , Z 8 ~Z 11 Each independently selected from CR 21 or N, where R 21 One selected from hydrogen, halogen, unsubstituted or R'substituted C1-C20 straight or branched alkyl, unsubstituted or R'substituted C3-C20 cycloalkyl, unsubstituted or R'substituted C2-C10 alkenyl, unsubstituted or R'substituted C1-C20 alkoxy, unsubstituted or R'substituted C1-C20 alkylsilyl, unsubstituted or R'substituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, unsubstituted or R'substituted C6-C30 arylamino, unsubstituted or R'substituted C3-C30 heteroarylamino, unsubstituted or R'substituted C6-C30 aryloxy, unsubstituted or R'substituted C3-C30 heteroaryloxy, unsubstituted or R'substituted C6-C60 aryl, unsubstituted or R'substituted C3-C60 heteroaryl, wherein the R's are not connected or connected to form a ring by chemical bonds; M and M' are respectively the same as the definitions of M in formula (1), preferably M and M' are respectively independently selected from O or S, more preferably selected from S; R' is independently selected from any one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl, and more preferably at least one of the following groups:

6. The boron-nitrogen-containing organic compound according to any one of claims 1 to 4, characterized in that: Ar 1 ,Ar 2 Each is independently a group of formula (g), U 6 ~U 10 Each independently is CR 51 or N; R 51 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-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 or substituted or unsubstituted C3-C60 heteroaryl; 51 Each independently is not connected to the adjacent ring structure or is connected to form a ring through a chemical bond; The substituents of the above substitutions are each independently selected from any one of halogen, C1-C20 straight or branched alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl, or a combination of at least two thereof; It is further preferred that formula (g) is selected from any one of substituted phenyl, substituted benzocyclohexyl, substituted naphthyl, and substituted biphenyl, wherein the substituent is selected from one or a combination of two of halogen, amino, alkyl substituted amino, C1-C6 straight or branched alkyl, phenyl, biphenyl, and benzocyclohexyl; It is further preferred that formula (g) is one of the following groups, 7. The boron-nitrogen-containing organic compound according to claim 5, characterized in that: In formulas (3-1) to (3-5), Z 1 ~Z 3 , Y 1 ~Y 4 , Z 4’ ~Z 7’ , Z 8 ~Z 11 At most one of them is N; Preferably, the Z 1 ~Z 3 , Y 1 ~Y 4 , Z 4’ ~Z 7’ , Z 8 ~Z 11 Each independently is CR 21 , and at least one of them is R 21 is any one of C1-C6 straight chain or branched chain alkyl substituted or unsubstituted C1-C20 straight chain or branched chain alkyl, C1-C6 straight chain or branched chain alkyl substituted or unsubstituted C3-C20 cycloalkyl, preferably R 21 It is one or a combination of two of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl and cyclohexyl.

8. The boron-nitrogen-containing organic compound according to claim 1, comprising the following specific compounds:

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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