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

Abstract

The invention provides an organic compound and application thereof, and an organic electroluminescent device containing the organic compound, particularly relates to a boron-nitrogen-containing organic compound, belongs to the technical field of organic luminescent materials, and also relates to application of the compound in the organic electroluminescent device. The organic compound has a structure as shown in the following formula, wherein the formula (1-2) is a substituent group of Ar1 and / or Ar2 in the formula (1). The organic compound provided by the invention has good stability and steric configuration, can realize relatively high luminous efficiency by utilizing axial extension of molecules, has excellent carrier transport efficiency, and can effectively prolong the service life of the device and improve the luminous efficiency when being used as a material of a luminous layer for the organic electroluminescent device. # imgabs0 #

Description

Technical Field

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

[0002] 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 luminescent 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, which is described in detail below. Surprisingly, the compounds disclosed in the present invention are very suitable for application in OLEDs and improve device life. Summary of the invention

[0006] In order to solve the above technical problems, the purpose of the present invention is to provide a boron-nitrogen-containing organic compound and its application, and an organic electroluminescent device containing the same. Through the design of the molecular structure, the present invention provides a boron-nitrogen-containing organic compound. In the structure of this series of compounds, dibenzofuran / dibenzothiophene / fluorene and other structures are introduced outwardly on both sides of the mother nucleus. On the one hand, this structure is beneficial to suppressing the vibration of the molecular excited state, significantly narrowing the half-peak width of the material, and improving the color purity of the blue light material; on the other hand, the existence of this structure extends the axial length of the molecule, increases the horizontal transition dipole of the molecule, and is beneficial to improving the device efficiency.

[0007] More specifically, the present invention provides a boron-nitrogen-containing organic compound having a structure shown in formula (1):

[0008]

[0009] In formula (1), ring A, ring B, and ring C are each independently a C6-C50 aromatic ring or a C3-C50 heteroaromatic ring;

[0010] R a , R b , R c represents single substitution to maximum substitution, R a , R b are each 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 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 They are independently connected to each other by chemical bonds to form a ring or are not connected;

[0011] R c represents single substitution to maximum substitution, R c are each independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, cyano, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, the two R c They are connected to each other by chemical bonds to form a ring or not;

[0012] Ar 1 ,Ar 2 are independently selected from a substituted or unsubstituted C6-C50 aromatic ring, a substituted or unsubstituted C3-C50 heteroaromatic ring; wherein Ar 1 ,Ar 2 At least one substituent in is a group having a structure represented by formula (1-2),

[0013] In formula (1-2), Z 11 -Z 17 Each independently selected from CR d or N, the R dR 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 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-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C3-C60 heteroaryl; d The aromatic ring or heteroaromatic ring is not connected to the connected aromatic ring or is connected to each other by chemical bonds to form a ring;

[0014] M is O, S, NR 1 , CR 2 R 3 One of; Q is O, S, CR 4 R 5 One of;

[0015] R 1 , R 2 , R 3 R is independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; 4 , R 5 Each is independently selected from any one of hydrogen, C1-C20 straight chain or branched alkyl;

[0016] The substituents mentioned above are each independently selected from at least one of hydrogen, 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 out by “—” indicates that the connection site is at any bonding position on the ring structure, and the * indicates the connection site.

[0017] The boron-nitrogen-containing organic compound provided by the present invention has a specific molecular structure shown in formula (1). By designing the BN mother core structure and introducing dibenzofuran / dibenzothiophene / fluorene structures on both sides of the mother core (i.e., formula (1-2)), the boron-nitrogen-containing organic compound has excellent photoelectric properties, which is beneficial to suppressing the vibration of the molecular excited state, significantly narrowing the half-peak width of the material, and improving the color purity of the blue light material.

[0018] The unique connection site formula of formula (1-2) in the present invention is very important. Studies have found that other connection methods can also achieve good photoelectric properties, but there is still a gap with the related compounds containing formula (1-2). The reason is not very clear. It is speculated that it may be due to the existence of this structure that extends the axial length of the molecule and increases the horizontal transition dipole of the molecule, which is beneficial to improving the device efficiency.

[0019] The parent core structure is also very important. The boron-nitrogen-containing organic compound has good stability and spatial configuration, can utilize triplet excitons to achieve high luminous efficiency, has excellent carrier transport characteristics, and effectively avoids molecular aggregation, which has an effect on improving the stability and efficiency of the device. The study also found that other more cyclic parent core structures, such as the case where the A ring is also a benzo five-membered ring, do not match the structure of formula (1-2) ideally, probably because other similar parent core structures are not as film-forming as the specific parent core structure in the present invention.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] The heteroatom in the present invention is generally selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0025] 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.

[0026] 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.

[0027] As used herein, the term "halo" or "halogen" group is defined to include F, Cl, Br, or I.

[0028] 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.

[0029] 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.

[0030] As used herein, the term "one or more" means 1 or more than 1, such as 2, 3, 4, 5 or 10, where reasonable.

[0031] Unless otherwise indicated, as used herein, the point of attachment of a substituent may be from any suitable position of the substituent.

[0032] 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.

[0033] The term "about" means within ±10% of the stated numerical value, preferably within ±5%, more preferably within ±2%.

[0034] 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.

[0035] The above-mentioned C6-C60 aromatic ring (or C6-C50 aromatic ring) and C3-C60 heteroaromatic ring (or C6-C50 heteroaromatic ring) in the present invention, unless otherwise specified, are aromatic groups that satisfy the π conjugated system, including 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.

[0036] 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.

[0037] In the present specification, the substituted or unsubstituted C6-C60 aryl group (or C6-C50 aryl group) is preferably a C6-C30 aryl 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 (or C6-C50 aryl group) of the present invention can also be a group formed by combining the above groups by single bond connection or / and fusion.

[0038] 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, yl, 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, benzopyridazine 1,5-diazaanthenyl, 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.

[0039] In the present specification, the substituted or unsubstituted C3-C60 heteroaryl group (or C3-C50 heteroaryl group) is preferably a C3-C30 heteroaryl group, and more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, and the like. Specific examples include: furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and its derivatives, quinolyl, isoquinolyl, quinolinyl, acridinyl, phenanthridinyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, phenothiazinyl, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalin imidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzo pyridazinyl, 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-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, 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.

[0040] 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.

[0041] 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.

[0042] 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, cycloheptyl, cyclooctyl, adamantyl and the like.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] In a preferred embodiment of the present invention, the boron-nitrogen-containing organic compound has a structure as shown in formula (2-1) or formula (2-2):

[0049]

[0050] 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);

[0051] Y 1 , Y 2 , Y 3 , Y 4 Each independently is CR 11 or N;

[0052] 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 C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, 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 Not connected to adjacent ring structures or connected to form a ring through chemical bonds,

[0053] The substituents of the above substitutions are each independently selected from at least 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. The expression of the ring structure crossed by “—” indicates that the connection site is at any position on the ring structure that can form a bond.

[0054] Preferably, the Y 1 , Y 2 , Y 3 and Y 4 At most one of them is N;

[0055] More preferably, the Y 1 , Y2 , Y 3 and Y 4 Each independently is CR 11 ,

[0056] 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, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, and phenyl,

[0057] 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.

[0058] In a preferred embodiment of the present invention, the ring C has a structure as shown in formula (f):

[0059]

[0060] Among them, the dotted lines represent the fused bonds of the groups;

[0061] Z 1 , Z 2 , Z 3 Each independently is CR 31 or N;

[0062] R 31 is independently selected from any one of hydrogen, halogen, cyano, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; said R 31 Not connected to adjacent ring structures or connected to form a ring through chemical bonds;

[0063] The substituents of the above substitutions are each independently selected from at least 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.

[0064] Preferably, the Z 1 , Z 2 , Z 3 At most one of them is N;

[0065] Preferably, the Z 1 , Z 2 , Z 3 Each independently is CR 31 Preferably, Z 1 , Z 3 for CH, the Z 2 CR 31 , the R 31 It is one or a combination of two of hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, cyclopentyl, cyclohexyl and adamantyl.

[0066] In a preferred embodiment of the present invention, Ar 1 ,Ar 2 Each is independently a group of formula (g),

[0067]

[0068] Among them, Ar 1 or Ar 2 At least one of the following groups:

[0069]

[0070] Q. Z 11 -Z 17 Same as in formula (1-2),

[0071] Z 6 -Z 10 Each independently selected from CR 32 or N, the R 32 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 C1-C20 alkylamino, 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; 32 The aromatic ring or heteroaromatic ring is not connected to the connected aromatic ring or is connected to each other by chemical bonds to form a ring;

[0072] The substituents mentioned above are each independently selected from at least 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. The expression of the ring structure crossed out by “—” indicates that the connection site is at any bonding position on the ring structure, and the * indicates the connection site.

[0073] In a preferred embodiment of the present invention, the boron-nitrogen-containing organic compound has a structure as shown in formula (3-1) or (3-2):

[0074]

[0075] In the above formulas (3-1) to (3-2), M has the same limited range as in formula (1); Y 1 , Y 2 , Y 3 , Y 4 The same limits as in formula (2-1) or (2-2), Ar 1 ,Ar 2 is a group represented by formula (g),

[0076] U 1 , U 2 , U 3 , U 4 Each independently is CR 21 or N; R 21 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 C1-C20 alkylamino, 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; 21 Not connected to adjacent ring structures or connected to form a ring through chemical bonds;

[0077] The substituents of the above substitutions are each independently selected from at least 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.

[0078] Preferably, the U 1 , U 2 , U 3 and U 4 At most one of them is N; further preferably, the U 1 , U 2 , U 3 and U 4 Each independently is CR 21 ;

[0079] More preferably, U 1 , U 4 Each independently is CH, U 2 , U 3 Each independently is CR 21 ,

[0080] More preferably, R 21 is one or a combination of two of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, and phenyl,

[0081] More preferably, U 2 , U 3 Each independently is CR 21 , and U 2 , U 3 Each R 21 Connect to form a methyl substituted cyclohexane ring.

[0082] In a preferred embodiment of the present invention, formula (g-2) is selected from one of the following groups:

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089] X is CH2, C(CH3)2, O or S, and the * sign indicates the connection site.

[0090] In a preferred embodiment of the present invention, Ar 1 ,Ar 2 One of them is a group represented by formula (g-2), and the other (formula (g) other than formula (g-2)) is selected from one of phenyl, pyridine, benzocyclohexyl, naphthyl, biphenyl, fluorenyl, dibenzofuran, dibenzothiophene, and dibenzopiperidine, wherein the phenyl, pyridine, benzocyclohexyl, naphthyl, biphenyl, dibenzofluorene, dibenzofuran, dibenzothiophene, and dibenzopiperidine may be substituted by at least one of C1-C10 straight or branched alkyl, adamantyl, benzocyclohexyl, phenyl, and biphenyl, and the substituents are not connected or connected to form a ring;

[0091] More preferably, it is one of the following groups,

[0092]

[0093]

[0094] * indicates the connection site.

[0095] In a preferred embodiment of the present invention, in formula (1-2), Z 14 -Z 17 At most one of them is N;

[0096] More preferably, the Z 14 -Z 17 Each independently is CR d , and at least one of them is R d is one of substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, more preferably one of methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, phenyl or a combination of two thereof; preferably, Z 14 -Z 17 Each independently is CR d , and one of the R d is one of substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, or substituted or unsubstituted C6-C30 aryl, and more preferably one of methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, or phenyl, or a combination of two thereof, and the other R d Both are H.

[0097] More preferably, the Z 14 -Z 17 Each is independently CH.

[0098] 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:

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125] The preparation process of the boron-nitrogen-containing organic compound is simple and easy, the raw materials are easily available, and it is suitable for mass production and expansion. It is used as a material for the light-emitting layer in an organic electroluminescent device, so that the device can achieve high-quality blue light emitting effect, effectively prolong the life of the device, and improve the luminous efficiency.

[0126] 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.

[0127] 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.

[0128] Preferably, the organic compound is used as a light-emitting layer material in an organic electroluminescent device.

[0129] Preferably, the organic compound is used as a luminescent dye of a light-emitting layer in an organic electroluminescent device.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] In a fourth aspect, the present invention provides a display device, comprising the organic electroluminescent device as described in the third aspect.

[0137] The OLED device prepared by using the compound of the present invention has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel and display manufacturers for high-performance materials. DETAILED DESCRIPTION

[0138] The technical solution of the present invention is further described in more detail below.

[0139] Synthesis methods of compounds

[0140] In a specific embodiment, the boron-nitrogen-containing organic compound can be prepared by the following synthetic route:

[0141]

[0142] Among them, ring A, ring B, ring C, Ar 1 ,Ar 2 , R a , R b , R c Has the same limited range as formula (1); Hal 1 Hal 2 Hal 3 Each is independently a halogen, more preferably Cl or Br.

[0143] In a specific embodiment, the representative synthesis route of the boron-nitrogen-containing organic compound is as follows:

[0144]

[0145] Among them, Ar 1 ,Ar 2 , U 1 , U 2 , U 3 , U 4 , Z 1 , Z 2 , Z 3 , M, Y 1 , Y 2 , Y 3 , Y 4 Having the same definitions as above; Pd(dppf)Cl2 is 1,1'-bis(diphenylphosphinoferrocene)palladium dichloride, NaOtBu is sodium tert-butoxide, Pd2(dba)3 is tris(dibenzylideneacetone)dipalladium, P-tBu3 is tri-tert-butylphosphine, tBu-Li is tert-butyllithium, and NEt(i-Pr)2 is N,N-diisopropylethylamine.

[0146] It should be noted that obtaining the boron-nitrogen-containing organic compound is not limited to the synthesis method and raw materials used in the present invention, and those skilled in the art may also select other methods or routes to obtain the boron-nitrogen-containing organic compound proposed in the present invention. The compounds for which the synthesis method is not mentioned in the present invention are all raw materials obtained from commercial channels, or are prepared by themselves according to known methods using these raw materials.

[0147] The following synthesis examples of the present invention illustratively provide specific synthesis methods for representative compounds. The solvents and reagents, intermediates, ethyl acetate, methanol, ethanol and other chemical reagents used in the following synthesis examples can all be purchased or customized from the domestic chemical product market.

[0148] 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.

[0149] In addition, although representative exemplary synthetic routes of the compounds of the present invention are described in the examples, those skilled in the art can also obtain the compounds by other methods known in the art.

[0150] Organic EL devices

[0151] 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.

[0152] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157]

[0158]

[0159]

[0160]

[0161] 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.

[0162]

[0163] 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.

[0164] 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.

[0165] 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.

[0166]

[0167] 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.

[0168]

[0169]

[0170]

[0171]

[0172] 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.

[0173] 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).

[0174] 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.

[0175]

[0176]

[0177]

[0178]

[0179] 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.

[0180] 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.

[0181] 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.

[0182] Example

[0183] Synthesis of compounds

[0184] 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 raw materials and intermediates used in the present invention are all obtained through commercial channels. The solvents and reagents used in the present invention, such as chemical reagents such as dichloromethane, petroleum ether, ethanol, tert-butylbenzene, boron tribromide, diphenylamine, etc., can be purchased from the domestic chemical product market, such as purchased from Sinopharm Group Reagent Company, TCI Company, Shanghai Bid Pharmaceutical Company, Bailingwei Reagent Company, etc. The analysis and detection of the intermediates and compounds in the present invention uses an ABSCIEX mass spectrometer (4000QTRAP). The structural analysis and detection of the intermediates and raw materials in the present invention uses a gas chromatography-mass spectrometer (GC-MS, Shimadzu QP2010 SE).

[0185] Synthesis Example 1: Synthesis of M6

[0186]

[0187] Synthesis of intermediate A1:

[0188] Intermediate A1 was prepared according to the above synthetic route, and was a commercially customized raw material provided by Puyang Huicheng.

[0189] The molecular ion mass determined by mass spectrometry was: 447.12 (theoretical value: 447.17).

[0190] Synthesis of intermediate M6-1:

[0191] At room temperature, M6-0 (20.0 g), 5-tert-butyl-2,3-dichlorobromobenzene (16.8 g), Pd2(dba)3 (2.7 g), tri-tert-butylphosphine (2.2 g), sodium tert-butoxide (11.5 g), and toluene (500 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100°C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated and subjected to column chromatography (PE:DCM=10:1, v:v, (the same below)) to obtain a crude product, and ethanol was added to slurry to obtain 25 g of a white solid with a yield of 78.4%.

[0192] The molecular ion mass determined by mass spectrometry was: 535.22 (theoretical value: 535.28).

[0193] Synthesis of intermediate M6-2:

[0194] At room temperature, M6-1 (20.0 g), A1 (16.7 g), Pd2 (dba) 3 (1.7 g), tri-tert-butyl phosphine (1.2 g), sodium tert-butoxide (7.2 g), and toluene (400 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100 ° C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE: DCM = 10: 1), and ethanol was added to slurry to obtain 30 g of a white solid with a yield of 84.9%.

[0195] The molecular ion mass determined by mass spectrometry was: 946.42 (theoretical value: 946.47).

[0196] Synthesis of compound M6:

[0197] At room temperature, M6-2 (20.0 g) was dissolved in 120 mL of xylene. After nitrogen replacement three times, the reaction system was cooled to -20 ° C, and then tert-butyl lithium (30 mL, 1.6 M) was added, and stirring was continued at low temperature for 30 minutes. Then the temperature was gradually raised to 60 ° C and heated for 2 hours. Finally, the temperature of the reaction system was lowered to -20 ° C again, and boron tribromide (7 mL) was added under nitrogen protection. After stirring for 30 minutes, diisopropylethylamine (24 mL) was added. Finally, the reaction system was heated to 120 ° C and reacted for 8 hours. After the reaction was cooled to room temperature, the organic phase was decompressed and dried. Dichloromethane (200 mL) was extracted three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was mixed with silica gel and concentrated, and the crude product was obtained by column chromatography (PE: DCM = 20: 1), and then recrystallized to obtain 2.9 g of yellow solid, with a yield of 14.9%.

[0198] The molecular ion mass determined by mass spectrometry was: 920.35 (theoretical value: 920.49).

[0199] Synthesis Example 2: Synthesis of M24

[0200]

[0201] Synthesis of intermediate M24-0:

[0202] The intermediate M24-0 was prepared according to the above synthetic route and was a commercially customized raw material provided by Puyang Huicheng.

[0203] The molecular ion mass determined by mass spectrometry was: 523.39 (theoretical value: 523.42).

[0204] Synthesis of intermediate M24-1:

[0205] At room temperature, M24-0 (20.0 g), 5-tert-butyl-2,3-dichlorobromobenzene (10.8 g), Pd2(dba)3 (1.8 g), tri-tert-butylphosphine (0.8 g), sodium tert-butoxide (7.3 g), and toluene (500 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100°C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated, extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to perform column chromatography (PE:DCM=10:1) to obtain a crude product, which was slurried with ethanol to obtain 23.5 g of a white solid with a yield of 84.8%.

[0206] The molecular ion mass determined by mass spectrometry was: 723.40 (theoretical value: 723.43).

[0207] Synthesis of intermediate M24-2:

[0208] At room temperature, M24-1 (20.0 g), A1 (12.4 g), Pd2 (dba) 3 (1.3 g), tri-tert-butyl phosphine (0.6 g), sodium tert-butoxide (5.3 g), and toluene (400 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100 ° C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE: DCM = 10: 1), and ethanol was added to slurry to obtain 27.2 g of a white solid with a yield of 86.8%.

[0209] The molecular ion mass determined by mass spectrometry was: 1134.60 (theoretical value: 1134.62).

[0210] Synthesis of compound M24:

[0211] At room temperature, M24-2 (20.0 g) was dissolved in 120 mL of xylene. After nitrogen replacement three times, the reaction system was cooled to -20 ° C, and then tert-butyl lithium (30 mL, 1.6 M) was added, and stirring was continued at low temperature for 30 minutes. Then the temperature was gradually raised to 60 ° C and heated for 2 hours. Finally, the temperature of the reaction system was lowered to -20 ° C again, and boron tribromide (7 mL) was added under nitrogen protection. After stirring for 30 minutes, diisopropylethylamine (24 mL) was added. Finally, the reaction system was heated to 120 ° C and reacted for 8 hours. After the reaction was cooled to room temperature, the organic phase was decompressed and dried. Dichloromethane (200 mL) was extracted three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was mixed with silica gel and concentrated, and the crude product was obtained by column chromatography (PE: DCM = 20: 1), and then 3.2 g of yellow solid was obtained by recrystallization, with a yield of 16.4%.

[0212] The molecular ion mass determined by mass spectrometry was: 1108.63 (theoretical value: 1108.65).

[0213] Synthesis Example 3: Synthesis of M69

[0214]

[0215] Synthesis of intermediate A2:

[0216] Intermediate A2 was prepared according to the above synthetic route and was a commercially customized raw material provided by Puyang Huicheng.

[0217] The molecular ion mass determined by mass spectrometry was: 473.26 (theoretical value: 473.22).

[0218] Synthesis of intermediate M24-1:

[0219] At room temperature, M24-0 (20.0 g), 5-tert-butyl-2,3-dichlorobromobenzene (10.8 g), Pd2(dba)3 (1.8 g), tri-tert-butylphosphine (0.8 g), sodium tert-butoxide (7.3 g), and toluene (500 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100°C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated, extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE:DCM=10:1), and ethanol was added to slurry to obtain 22.8 g of a white solid with a yield of 82.4%.

[0220] The molecular ion mass determined by mass spectrometry was: 723.40 (theoretical value: 723.43).

[0221] Synthesis of intermediate M69-2:

[0222] At room temperature, M24-1 (20.0 g), A2 (13.1 g), Pd2 (dba) 3 (1.3 g), tri-tert-butyl phosphine (0.6 g), sodium tert-butoxide (5.3 g), and toluene (400 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100 ° C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE: DCM = 10: 1), and ethanol was added to slurry to obtain 28.2 g of a white solid with a yield of 88.0%.

[0223] The molecular ion mass determined by mass spectrometry was: 1160.58 (theoretical value: 1160.67).

[0224] Synthesis of compound M69:

[0225] At room temperature, M69-2 (20.0 g) was dissolved in 120 mL of xylene. After nitrogen replacement three times, the reaction system was cooled to -20 ° C, and then tert-butyl lithium (30 mL, 1.6 M) was added, and stirring was continued at low temperature for 30 minutes. Then the temperature was gradually raised to 60 ° C and continued to heat for 2 hours. Finally, the temperature of the reaction system was lowered to -20 ° C again, and boron tribromide (7 mL) was added under nitrogen protection. After stirring for 30 minutes, diisopropylethylamine (24 mL) was added. Finally, the reaction system was heated to 120 ° C and reacted for 8 hours. After the reaction was cooled to room temperature, the organic phase was decompressed and dried. Dichloromethane (200 mL) was extracted three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was mixed with silica gel and concentrated, and the crude product was obtained by column chromatography (PE: DCM = 20: 1), and then 3.5 g of yellow solid was obtained by recrystallization, with a yield of 17.9%.

[0226] The molecular ion mass determined by mass spectrometry was: 1134.62 (theoretical value: 1134.70).

[0227] Synthesis Example 4: Synthesis of M121

[0228]

[0229] Synthesis of intermediate M121-0:

[0230] The intermediate M121-0 was prepared according to the above synthetic route and was a commercially customized raw material provided by Puyang Huicheng.

[0231] The molecular ion mass determined by mass spectrometry was: 523.37 (theoretical value: 523.42).

[0232] Synthesis of intermediate A3:

[0233] Intermediate A3 was prepared according to the above synthetic route, and was a commercially customized raw material provided by Puyang Huicheng.

[0234] The molecular ion mass determined by mass spectrometry was: 517.12 (theoretical value: 517.19).

[0235] Synthesis of intermediate M121-1:

[0236] At room temperature, M121-0 (20.0 g), 5-tert-butyl-2,3-dichlorobromobenzene (10.8 g), Pd2(dba)3 (1.8 g), tri-tert-butylphosphine (0.8 g), sodium tert-butoxide (7.3 g), and toluene (500 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100°C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated, extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE:DCM=10:1), and ethanol was added to slurry to obtain 23.3 g of a white solid with a yield of 84.2%.

[0237] The molecular ion mass determined by mass spectrometry was: 723.40 (theoretical value: 723.43).

[0238] Synthesis of intermediate M121-2:

[0239] At room temperature, M121-1 (20.0 g), A3 (14.3 g), Pd2 (dba) 3 (1.3 g), tri-tert-butyl phosphine (0.6 g), sodium tert-butoxide (5.3 g), and toluene (400 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100 ° C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE: DCM = 10: 1), and ethanol was added to slurry to obtain 28.6 g of a white solid with a yield of 85.9%.

[0240] The molecular ion mass determined by mass spectrometry was: 1204.61 (theoretical value: 1204.65).

[0241] Synthesis of compound M121:

[0242] At room temperature, M121-2 (20.0 g) was dissolved in 120 mL of xylene. After nitrogen replacement three times, the reaction system was cooled to -20 ° C, and then tert-butyl lithium (30 mL, 1.6 M) was added, and stirring was continued at low temperature for 30 minutes. Then the temperature was gradually raised to 60 ° C and heated for 2 hours. Finally, the temperature of the reaction system was lowered to -20 ° C again, and boron tribromide (7 mL) was added under nitrogen protection. After stirring for 30 minutes, diisopropylethylamine (24 mL) was added. Finally, the reaction system was heated to 120 ° C and reacted for 8 hours. After the reaction was cooled to room temperature, the organic phase was decompressed and dried. Dichloromethane (200 mL) was extracted three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was mixed with silica gel and concentrated, and the crude product was obtained by column chromatography (PE: DCM = 20: 1), and then 3.6 g of yellow solid was obtained by recrystallization, with a yield of 18.4%.

[0243] The molecular ion mass determined by mass spectrometry was: 1178.64 (theoretical value: 1178.67).

[0244] Synthesis Example 5: Synthesis of M181

[0245]

[0246] Synthesis of intermediate M181-0:

[0247] The intermediate M181-0 was prepared according to the above synthetic route and was a commercially customized raw material provided by Puyang Huicheng.

[0248] The molecular ion mass determined by mass spectrometry was: 689.41 (theoretical value: 689.46).

[0249] Synthesis of intermediate M181-1:

[0250] At room temperature, M181-0 (20.0 g), 5-tert-butyl-2,3-dichlorobromobenzene (8.2 g), Pd2(dba)3 (1.3 g), tri-tert-butylphosphine (0.6 g), sodium tert-butoxide (5.6 g), and toluene (500 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100°C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, the organic phase was dried and concentrated, and column chromatography (PE:DCM=10:1) was performed to obtain a crude product, and ethanol was added to slurry to obtain 21.2 g of a white solid with a yield of 82.1%.

[0251] The molecular ion mass determined by mass spectrometry was: 889.42 (theoretical value: 889.48).

[0252] Synthesis of intermediate M181-2:

[0253] At room temperature, M181-1 (20.0 g), A4 (7.6 g), Pd2 (dba) 3 (1.0 g), tri-tert-butyl phosphine (0.5 g), sodium tert-butoxide (4.3 g), and toluene (400 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100 ° C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE: DCM = 10: 1), and ethanol was added to slurry to obtain 20.4 g of a white solid with a yield of 76.2%.

[0254] The molecular ion mass determined by mass spectrometry was: 1190.65 (theoretical value: 1190.69).

[0255] Synthesis of compound M181:

[0256] At room temperature, M181-2 (20.0 g) was dissolved in 120 mL of xylene. After nitrogen replacement three times, the reaction system was cooled to -20 ° C, and then tert-butyl lithium (30 mL, 1.6 M) was added, and stirring was continued at low temperature for 30 minutes. Then the temperature was gradually raised to 60 ° C and heated for 2 hours. Finally, the temperature of the reaction system was lowered to -20 ° C again, and boron tribromide (7 mL) was added under nitrogen protection. After stirring for 30 minutes, diisopropylethylamine (24 mL) was added. Finally, the reaction system was heated to 120 ° C and reacted for 8 hours. After the reaction was cooled to room temperature, the organic phase was decompressed and dried. Dichloromethane (200 mL) was extracted three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was mixed with silica gel and concentrated, and the crude product was obtained by column chromatography (PE: DCM = 20: 1), and then 3.2 g of yellow solid was obtained by recrystallization, with a yield of 16.4%.

[0257] The molecular ion mass determined by mass spectrometry was: 1164.65 (theoretical value: 1164.71).

[0258] Synthesis Example 6: Synthesis of M290

[0259]

[0260] Synthesis of intermediate M290-0:

[0261] The intermediate M290-0 was prepared according to the above synthetic route and was a commercially customized raw material provided by Puyang Huicheng.

[0262] The molecular ion mass determined by mass spectrometry was: 661.45 (theoretical value: 661.46).

[0263] Synthesis of intermediate M290-1:

[0264] At room temperature, M290-0 (20.0 g), 5-tert-butyl-2,3-dichlorobromobenzene (8.5 g), Pd2(dba)3 (1.4 g), tri-tert-butylphosphine (0.6 g), sodium tert-butoxide (5.8 g), and toluene (500 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100°C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, the organic phase was dried and concentrated, and column chromatography (PE:DCM=10:1) was performed to obtain a crude product, and ethanol was added to slurry to obtain 22.3 g of a white solid with a yield of 80.5%.

[0265] The molecular ion mass determined by mass spectrometry was: 861.42 (theoretical value: 861.48).

[0266] Synthesis of intermediate M290-2:

[0267] At room temperature, M290-1 (20.0 g), A4 (7.8 g), Pd2 (dba) 3 (1.0 g), tri-tert-butyl phosphine (0.5 g), sodium tert-butoxide (4.5 g), and toluene (400 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100 ° C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated and column chromatography (PE: DCM = 10: 1) was performed to obtain a crude product, and ethanol was added to slurry to obtain 23.2 g of a white solid with a yield of 86.0%.

[0268] The molecular ion mass determined by mass spectrometry was: 1162.65 (theoretical value: 1162.69).

[0269] Synthesis of compound M290:

[0270] At room temperature, M290-2 (20.0 g) was dissolved in 120 mL of xylene. After nitrogen replacement three times, the reaction system was cooled to -20 ° C, and then tert-butyl lithium (30 mL, 1.6 M) was added, and stirring was continued at low temperature for 30 minutes. Then the temperature was gradually raised to 60 ° C and heated for 2 hours. Finally, the temperature of the reaction system was lowered to -20 ° C again, and boron tribromide (7 mL) was added under nitrogen protection. After stirring for 30 minutes, diisopropylethylamine (24 mL) was added. Finally, the reaction system was heated to 120 ° C and reacted for 8 hours. After the reaction was cooled to room temperature, the organic phase was decompressed and dried. Dichloromethane (200 mL) was extracted three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was mixed with silica gel and concentrated, and the crude product was obtained by column chromatography (PE: DCM = 20: 1), and then 3.7 g of yellow solid was obtained by recrystallization, with a yield of 18.9%.

[0271] The molecular ion mass determined by mass spectrometry was: 1136.64 (theoretical value: 1136.72).

[0272] Synthesis Example 7: Synthesis of M367

[0273]

[0274] Synthesis of intermediate M367-0:

[0275] The intermediate M367-0 was prepared according to the above synthetic route and was a commercially customized raw material provided by Puyang Huicheng.

[0276] The molecular ion mass determined by mass spectrometry was: 501.24 (theoretical value: 501.30).

[0277] Synthesis of intermediate M367-1:

[0278] At room temperature, M367-0 (20.0 g), 5-tert-butyl-2,3-dichlorobromobenzene (11.2 g), Pd2(dba)3 (1.8 g), tri-tert-butylphosphine (0.8 g), sodium tert-butoxide (7.7 g), and toluene (500 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100°C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated, extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE:DCM=10:1), and ethanol was added to slurry to obtain 23.4 g of a white solid with a yield of 83.5%.

[0279] The molecular ion mass determined by mass spectrometry was: 701.30 (theoretical value: 701.32).

[0280] Synthesis of intermediate M367-2:

[0281] At room temperature, M367-1 (20.0 g), A5 (15.0 g), Pd2 (dba) 3 (1.3 g), tri-tert-butyl phosphine (0.6 g), sodium tert-butoxide (5.5 g), and toluene (400 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100 ° C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE: DCM = 10: 1), and ethanol was added to slurry to obtain 28.4 g of a white solid with a yield of 83.7%.

[0282] The molecular ion mass determined by mass spectrometry was: 1190.60 (theoretical value: 1190.69).

[0283] Synthesis of compound M367:

[0284] At room temperature, M367-2 (20.0 g) was dissolved in 120 mL of xylene. After nitrogen replacement three times, the reaction system was cooled to -20 ° C, and then tert-butyl lithium (30 mL, 1.6 M) was added, and stirring was continued at low temperature for 30 minutes. Then the temperature was gradually raised to 60 ° C and heated for 2 hours. Finally, the temperature of the reaction system was lowered to -20 ° C again, and boron tribromide (7 mL) was added under nitrogen protection. After stirring for 30 minutes, diisopropylethylamine (24 mL) was added. Finally, the reaction system was heated to 120 ° C and reacted for 8 hours. After the reaction was cooled to room temperature, the organic phase was decompressed and dried. Dichloromethane (200 mL) was extracted three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was mixed with silica gel and concentrated, and the crude product was obtained by column chromatography (PE: DCM = 20: 1), and then 3.6 g of yellow solid was obtained by recrystallization, with a yield of 18.5%.

[0285] The molecular ion mass determined by mass spectrometry was: 1164.60 (theoretical value: 1164.71).

[0286] Synthesis Example 8: Synthesis of M370

[0287]

[0288] Synthesis of intermediate M370-0:

[0289] The intermediate M370-0 was prepared according to the above synthetic route and was a commercially customized raw material provided by Puyang Huicheng.

[0290] The molecular ion mass determined by mass spectrometry was: 633.41 (theoretical value: 633.40).

[0291] Synthesis of intermediate M370-1:

[0292] At room temperature, M370-0 (20.0 g), 5-tert-butyl-2,3-dichlorobromobenzene (8.2 g), Pd2(dba)3 (1.3 g), tri-tert-butylphosphine (0.6 g), sodium tert-butoxide (5.6 g), and toluene (500 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100°C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated, extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE:DCM=10:1), and ethanol was added to slurry to obtain 20.2 g of a white solid with a yield of 78.2%.

[0293] The molecular ion mass determined by mass spectrometry was: 833.40 (theoretical value: 833.41).

[0294] Synthesis of intermediate M370-2:

[0295] At room temperature, M370-1 (20.0 g), A5 (11.8 g), Pd2 (dba) 3 (1.0 g), tri-tert-butyl phosphine (0.5 g), sodium tert-butoxide (4.3 g), and toluene (400 mL) were added to a 1L single-mouth bottle, replaced with nitrogen three times, and heated to 100 ° C for overnight reaction. The reaction solution was cooled to room temperature, the reaction system was concentrated and extracted with dichloromethane, washed with a large amount of water, and the organic phase was dried and concentrated to obtain a crude product by column chromatography (PE: DCM = 10: 1), and ethanol was added to slurry to obtain 25.2 g of a white solid with a yield of 81.3%.

[0296] The molecular ion mass determined by mass spectrometry was: 1322.75 (theoretical value: 1322.78).

[0297] Synthesis of compound M370:

[0298] At room temperature, M370-2 (20.0 g) was dissolved in 120 mL of xylene. After nitrogen replacement three times, the reaction system was cooled to -20 ° C, and then tert-butyl lithium (30 mL, 1.6 M) was added, and stirring was continued at low temperature for 30 minutes. Then the temperature was gradually raised to 60 ° C and continued to heat for 2 hours. Finally, the temperature of the reaction system was lowered to -20 ° C again, and boron tribromide (7 mL) was added under nitrogen protection. After stirring for 30 minutes, diisopropylethylamine (24 mL) was added. Finally, the reaction system was heated to 120 ° C and reacted for 8 hours. After the reaction was cooled to room temperature, the organic phase was decompressed and dried. Dichloromethane (200 mL) was extracted three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was mixed with silica gel and concentrated, and the crude product was obtained by column chromatography (PE: DCM = 20: 1), and then 3.7 g of yellow solid was obtained by recrystallization, with a yield of 19.7%.

[0299] The molecular ion mass determined by mass spectrometry was: 1296.65 (theoretical value: 1296.80).

[0300] Device Example 1

[0301] The following organic electroluminescent device is prepared, comprising an anode (ITO), a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode (Al) arranged in sequence. The preparation method of the organic electroluminescent device is as follows:

[0302] (1) a glass substrate coated with an ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone / ethanol mixed solvent, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0303] (2) Place the glass substrate with the anode in a vacuum chamber and evacuate the chamber to a vacuum of less than 1×10 -5Pa, vacuum evaporating a mixture of compound 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;

[0304] (3) vacuum evaporating compound HT-4 on the hole injection layer as a hole transport layer, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 60 nm;

[0305] (4) vacuum evaporating compound HT-14 on the hole transport layer as an electron blocking layer, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 5 nm;

[0306] (5) vacuum evaporating a light-emitting layer on the electron blocking layer, wherein the light-emitting layer comprises a binary mixture of a main material BFH-4 and a dye (boron-nitrogen-containing organic compound M6 provided by the present invention), BFH-4:M6 (100:3, w / w), with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 20 nm;

[0307] (6) vacuum evaporating compound ET-23 on the light-emitting layer as a hole blocking layer, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 5 nm;

[0308] (7) vacuum evaporating a mixture of compounds ET-69:ET-57 (50 / 50, w / w) on the hole blocking layer as an electron transport layer, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 25 nm;

[0309] (8) Vacuum evaporation of LiF as an electron injection layer on the electron transport layer at a rate of 0.1 nm / s and a thickness of 1 nm;

[0310] (9) Vacuum-evaporating an Al layer with a thickness of 150 nm on the electron injection layer as the cathode of the device at a deposition rate of 1 nm / s to obtain the organic electroluminescent device.

[0311] Device Examples 2-11, Device Comparative Examples 1-5

[0312] The following organic electroluminescent device was prepared. The only difference between it and device example 1 is that the dyes of the light-emitting layer are the compounds shown in Table 1; the other layers, thicknesses, materials and preparation methods are the same as those of device example 1.

[0313] Device Comparative Example 1, using the following prior art compound or a compound obtained by a similar preparation process according to the synthesis example of the present invention as the dye of the light-emitting layer, the specific structural formula is as follows:

[0314]

[0315] Device performance test:

[0316] (1) LT97 life: 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 the device comparative 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 the device comparative example 1 is calculated;

[0317] (2) Half peak width: at 10mA / cm 2 Tested under current density;

[0318] (3) External quantum efficiency: The external quantum efficiency (EQE, %) of the device was measured using the integrating sphere method.

[0319] The test results are shown in Table 1.

[0320] Table 1:

[0321] Example No. Dye material number FWHM(nm) LT97 EQE(%) Device Example 1 M6 22 1.7 6.2 Device Example 2 M24 21 2.1 6.6 Device Example 3 M69 21 2.0 6.3 Device Example 4 M121 21 2.0 6.5 Device Example 5 M173 21 1.9 6.6 Device Example 6 M181 20 2.1 6.7 Device Example 7 M190 21 1.8 6.4 Device Example 8 M238 20 2.0 6.6 Device Example 9 M296 21 1.9 6.4 Device Example 10 M367 20 2.1 6.8 Device Example 11 M370 20 2.0 6.5 Device Comparison Example 1 C-1 24 1 4.3 Device Comparison Example 2 C-2 23 0.8 3.4 Device Comparison Example 3 CM61 22 1.6 5.4 Device Comparison Example 4 CM62 22 1.6 5.4 Device Comparison Example 5 CM173 22 0.6 6.1

[0322] Combined with the data in Table 1, it can be seen that the boron-nitrogen-containing organic compound provided by the present invention, as a light-emitting layer dye of an organic electroluminescent device, can significantly extend the life of the device, significantly improve the luminous efficiency, and the device has more excellent stability and efficiency.

[0323] Compared with compounds C-1, C-2, CM61, and CM62, the compounds of the present invention have obvious advantages in light color and efficiency, indicating that the introduction of dibenzofuran / dibenzothiophene / fluorene and other structures on both sides of the parent core can indeed enhance the rigidity of the molecule, increase the horizontal transition dipole of the molecule, and is beneficial to improving device performance.

[0324] Compared with compound CM173, the compound of the present invention has a more significant advantage in lifespan, and the mother core with a single benzothiophene structure is obviously more stable in device performance.

[0325] 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.

[0326] 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 represents single substitution to maximum substitution, R a , R b are each 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 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 They are independently connected to each other by chemical bonds to form a ring or are not connected; R c represents single substitution to maximum substitution, R c are each independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, cyano, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, the two R c They are connected to each other by chemical bonds to form a ring or not; Ar 1 ,Ar 2 are independently selected from a substituted or unsubstituted C6-C50 aromatic ring, a substituted or unsubstituted C3-C50 heteroaromatic ring; wherein, Ar 1 ,Ar 2 At least one substituent in is a group having a structure represented by formula (1-2), In formula (1-2), Z 11 -Z 17 Each independently selected from 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 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-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C3-C60 heteroaryl; d The aromatic ring or heteroaromatic ring is not connected to the connected aromatic ring or is connected to each other by chemical bonds to form a ring; M is O, S, NR 1 , CR 2 R 3 One of; Q is O, S, CR 4 R 5 One of; R 1 , R 2 , R 3 R is independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; 4 , R 5 Each is independently selected from any one of hydrogen, C1-C20 straight chain or branched alkyl; The substituents mentioned above are each independently selected from at least 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. 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.

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 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 C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, 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 Not connected to adjacent ring structures or connected to form a ring through chemical bonds, The substituents of the above substitutions are each independently selected from at least 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. The expression of the ring structure crossed by "—" indicates that the connection site is at any position on the ring structure that can form a bond. 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, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, and phenyl, 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: 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 is independently selected from any one of hydrogen, halogen, cyano, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; said R 31 Not connected to adjacent ring structures or connected to form a ring through chemical bonds; The substituents of the above substitutions are each independently selected from at least 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. Preferably, the Z 1 , Z 2 , Z 3 At most one of them is N; Preferably, the Z 1 , Z 2 , Z 3 Each independently is CR 31 ; Preferably, Z 1 , Z 3 for CH, the Z 2 CR 31 , the R 31 It is one or a combination of two of hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, cyclopentyl, cyclohexyl and adamantyl.

4. The boron-nitrogen-containing organic compound according to claim 1, characterized in that: Ar 1 ,Ar 2 Each is independently a group of formula (g), Among them, Ar 1 or Ar 2 At least one of the following groups: Q. Z 11 -Z 17 Same as in formula (1-2), Z 6 -Z 10 Each independently selected from CR 32 or N, the R 32 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 C1-C20 alkylamino, 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; 32 The aromatic ring or heteroaromatic ring is not connected to the connected aromatic ring or is connected to each other by chemical bonds to form a ring; The substituents mentioned above are each independently selected from at least 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. 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.

5. The boron-nitrogen-containing organic compound according to any one of claims 1 to 4, characterized in that: The boron-nitrogen-containing organic compound has a structure as shown in formula (3-1) or (3-2): In the above formulas (3-1) to (3-2), M has the same limited range as in formula (1); Y 1 , Y 2 , Y 3 , Y 4 The same limits as in formula (2-1) or (2-2), Ar 1 ,Ar 2 is a group represented by formula (g), U 1 , U 2 , U 3 , U 4 Each independently is CR 21 or N; R 21 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 C1-C20 alkylamino, 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; 21 Not connected to adjacent ring structures or connected to form a ring through chemical bonds; The substituents of the above substitutions are each independently selected from at least 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. Preferably, the U 1 , U 2 , U 3 and U 4 At most one of them is N; further preferably, the U 1 , U 2 , U 3 and U 4 Each independently is CR 21 ; More preferably, U 1 , U 4 Each independently is CH, U 2 , U 3 Each independently is CR 21 , More preferably, R 21 is one or a combination of two of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, phenyl, and diphenylamino, More preferably, U 2 , U 3 Each independently is CR 21 , and U 2 , U 3 Each R 21 Connect to form a methyl substituted cyclohexane ring.

6. The boron-nitrogen-containing organic compound according to claim 4, characterized in that: Formula (g-2) is selected from one of the following groups: X is CH2, C(CH3)2, O or S, and the * sign indicates the connection site.

7. The boron-nitrogen-containing organic compound according to claim 6, characterized in that: Ar 1 ,Ar 2 One of them is a group represented by formula (g-2), and the other is selected from one of phenyl, pyridine, benzocyclohexyl, naphthyl, biphenyl, fluorenyl, dibenzofuran, dibenzothiophene, and dibenzopiperidine, wherein the phenyl, pyridine, benzocyclohexyl, naphthyl, biphenyl, fluorenyl, dibenzofuran, dibenzothiophene, and dibenzopiperidine may be substituted by at least one of C1-C10 straight or branched alkyl, adamantyl, benzocyclohexyl, phenyl, and biphenyl, and the substituents are not connected or connected to form a ring; More preferably, it is one of the following groups, * indicates the connection site.

8. The boron-nitrogen-containing organic compound according to claim 1, characterized in that: In formula (1-2), Z 14 -Z 17 At most one of them is N; More preferably, the Z 14 -Z 17 Each independently is CR d , and at least one of them is R d Any one of C1-C6 alkyl substituted or unsubstituted C1-C20 straight or branched alkyl, C1-C6 alkyl substituted or unsubstituted C3-C20 cycloalkyl, C1-C6 alkyl substituted or unsubstituted C6-C30 aryl, further one of methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, phenyl or a combination of at least two thereof; More preferably, the Z 14 -Z 17 Each is independently CH.

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

10. Use of the organic compound according to any one of claims 1 to 9 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.

11. 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 9; 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 9. 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 9.

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

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