Boron-containing organic compound and application thereof

Abstract

The invention provides a boron-containing organic compound and application thereof, the boron-containing organic compound has a structure as shown in a formula I, and through design and mutual compounding of a mother nucleus structure and specific groups, the boron-containing organic compound has excellent photoelectric properties, can emit dark blue light, has narrow spectrum characteristics, and can give triplet excitons to realize high luminous efficiency. The boron-containing organic compound is used for an organic electroluminescent device, can be used as a fluorescent dye of a luminescent layer, has excellent carrier transport efficiency, enables the device to realize a high-color-purity dark blue light emitting effect, can improve the light emitting efficiency of the device and prolong the service life of the device, and fully meets the requirements of current display devices and panels for high-performance materials.

Description

Technical Field

[0001] This invention belongs to the field of organic light-emitting materials technology, specifically relating to a boron-containing organic compound and its applications. Background Technology

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

[0003] The light-emitting mechanism of OLEDs involves the recombination of electrons and holes under electrical excitation to form excitons. These excitons follow a probability statistical distribution, with singlet excitons accounting for approximately 25% and triplet excitons for approximately 75%. First-generation light-emitting technologies, collectively known as fluorescence, utilize singlet excitons for emission. Second-generation technologies, collectively known as phosphorescence, utilize triplet excitons, theoretically achieving 100% internal quantum efficiency. However, the heavy metals required to construct phosphorescent dyes are not only expensive but also cause environmental pollution. Currently, the most commonly used technology is third-generation thermally excited delayed fluorescence, constructed using small organic molecules. When the energy difference between the singlet and triplet states is small, triplet excitons can undergo reverse intersystem crossing to the singlet state and then return to the ground state for emission. Red and green dyes, as the three primary colors, have become the mainstream in commercial display devices due to their high electroluminescence efficiency and low power consumption. However, the color saturation and lifespan of blue light materials do not meet current commercial display requirements, and blue light devices still use traditional fluorescent materials to achieve high color purity and long device lifespan.

[0004] In recent years, research groups led by Takuji Hatakeyama and Junji Kido in Japan have reported a series of small organic molecule materials based on boron-nitrogen resonance thermally activated delayed fluorescence (TADF), with a typical structure being DABNA-1. (Adv. Mater., 2016, 28, pp. 2777-2781; J. Mater. Chem. C, 2019, 7, pp. 3082-3089); The boron, nitrogen, and multiple phenyl groups in these compounds form a rigid polycyclic aromatic resonance framework, resulting in high fluorescence quantum yield. Compared to traditional blue fluorescent dyes, these compounds exhibit a narrower emission bandgap and higher color purity. However, the rigid planar structure also leads to a large energy difference between singlet and triplet states, slow anti-intersystem crossing from triplet to singlet states, and severe efficiency roll-off after exciton recombination on the dye, resulting in a short device lifetime. Furthermore, the overly planar rigid structure often leads to adverse effects such as broadening of the emission spectrum and redshift due to excessive doping concentration.

[0005] Existing organic electroluminescent materials still have significant room for improvement in luminescent performance, and the industry urgently needs to develop new luminescent material systems to meet commercialization demands. Boron-nitrogen resonance materials possess advantages such as high color purity and high luminescent efficiency, attracting widespread attention from the scientific and industrial communities. However, because the peripheral substituents have little impact on their energy levels, it is difficult to control the material's emission color, which remains limited to the sky-blue region, significantly restricting their further application in high-resolution displays, full-color displays, and white light illumination. As OLED products gradually enter the market, increasingly higher performance requirements are being placed on these products. Current OLED materials and devices cannot fully address the issues of efficiency, lifespan, and cost associated with OLED products. Therefore, developing a wider variety of organic luminescent materials with better electroluminescent performance is a key research focus in this field. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a boron-containing organic compound and its applications. Through molecular structure design, the boron-containing organic compound possesses excellent photoelectric properties and can emit deep blue light. When used in organic electroluminescent devices, it not only achieves excellent deep blue light emission but also effectively improves the luminous efficiency and lifespan of the device.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a boron-containing organic compound having a structure as shown in Formula I:

[0009]

[0010] In Formula I, rings A, B, and C are each independently selected from any one of substituted or unsubstituted C6-C60 aromatic rings or substituted or unsubstituted C3-C60 heteroaromatic rings.

[0011] In Formula I, X1 and X2 are each independently selected from O, S, or NAr.

[0012] In Formula I, Ar is selected from any one of substituted or unsubstituted C6-C60 aryl groups and substituted or unsubstituted C3-C60 heteroaryl groups; the Ar is not connected to the adjacent ring structure or is connected to the ring structure by chemical bonds.

[0013] In this invention, "Ar is not connected to adjacent ring structures" means that Ar is only connected to N atoms through single bonds; "Ar is connected to adjacent ring structures through chemical bonds to form a ring" means that in addition to being connected to N atoms through chemical bonds, Ar is also connected to adjacent rings (e.g., ring A, ring B) through chemical bonds, thereby forming a fused ring junction. The same descriptions will have the same meaning in the following text and will not be repeated hereafter.

[0014] In formula I, R X It has a structure as shown in any one of equations a, b, or c:

[0015]

[0016] -* represents the linkage site of a functional group; R X Ring D is connected to ring C via a single bond, meaning ring D is not connected to ring C, and ring E is not connected to ring C.

[0017] X3 is selected from N and CR. 11 or SiR 12 Any one of them.

[0018] X4 is selected from NR 13 O, S, CR 11 R 14 or SiR 12 R 15 Any one of them.

[0019] Ring D is selected from any one of the following: a C15-C60 aromatic ring composed of at least four (e.g., four, five, six, etc.) benzene rings fused together, or a C14-C60 heteroaromatic ring composed of at least four (e.g., four, five, six, etc.) benzene rings fused together and / or heteroaromatic rings.

[0020] In this invention, the C14-C60 heteroaromatic ring is formed by the fusion of at least four aromatic rings, wherein the aromatic ring includes a combination of heteroaromatic rings and optionally benzene rings.

[0021] Ring E is selected from any one of substituted or unsubstituted C6-C60 aromatic rings or substituted or unsubstituted C3-C60 heteroaromatic rings.

[0022] Dashed lines indicate Existence or non-existence; when When present, it indicates that a chemical bond in ring D, a chemical bond in ring E, together with X3 and Y1 form a ring structure, and the rings containing ring D, ring E, and X3 together form a fused ring structure; when If X3 is not present, it means that ring D and ring E are connected through X3 and are not fused together.

[0023] when When present, Y1 is selected from single bond, O, S, NR. 16 CR 17 R 18 or SiR 19 R 20 Any one of the following. When Y1 is a single bond, it means that X3 and Y1 together form a pentagonal ring; when Y1 is O, S, NR... 16 CR 17 R 18 or SiR 19 R 20 When X3 and Y1 together form a six-membered ring, it means that X3 and Y1 together form a six-membered ring.

[0024] R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 Each is independently selected from any one of hydrogen, substituted or unsubstituted C1-C20 straight-chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl.

[0025] Ring A, Ring B, Ring C, Ring D, Ring E, Ar, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20The substituents described herein are each independently selected from any one of the following: halogen, unsubstituted or R'-substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, cyano, nitro, hydroxyl, amino, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl.

[0026] In this invention, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents (at least two), they can be the same or different substituents; the same expression used below has the same meaning. Unless otherwise specified, the selection range of substituents is as shown above and will not be repeated.

[0027] R' is independently selected from any one or a combination of at least two of the following: halogen, cyano, nitro, hydroxyl, amino, C1-C20 straight-chain or branched alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl.

[0028] In this invention, the "unsubstituted or R'-substituted" group can replace one substituent R' or multiple substituents R'. When there are multiple substituents R' (at least two), they can be the same or different substituents; the same expression used below has the same meaning. Unless otherwise specified, the selection range of R' is as shown above and will not be repeated.

[0029] The boron-containing organic compound provided by this invention has a molecular structure as shown in Formula I, and its parent core contains B-X1 and B-X2 structures. The B atom has a resonance effect with the X1 / X2 atoms in the same ring, making the boron-containing organic compound a resonance fluorescent material with excellent luminescence performance. At the same time, a group R containing a fused ring structure is introduced into the ring C of the molecular structure. XThis increases the steric hindrance of the compound, suppresses its aggregation and quenching, and is beneficial to improving device lifetime and efficiency. Simultaneously, it lowers the triplet energy level of the compound, further enhancing device lifetime. Through the design and mutual compounding of the core structure and specific functional groups, this invention endows the boron-containing organic compound with excellent photoelectric properties, emitting deep blue light with narrow spectral characteristics and high luminous efficiency. When used as a fluorescent dopant material (fluorescent guest material, fluorescent dye) in the luminescent layer, it enables the device to exhibit high color purity and deep blue luminescence, while also possessing excellent carrier transport efficiency, thus improving device luminous efficiency and lifetime. Furthermore, the preparation process of the boron-containing organic compound described in this invention is simple and easy to implement, with readily available raw materials, making it suitable for mass production scale-up.

[0030] It should be noted that, for ease of explanation, the possible effects of each group / feature have been described separately in this invention, but this does not mean that these groups / features act in isolation. In fact, the essential reason for obtaining good performance is the optimized combination of the entire molecular structure, the result of the synergistic effect between various groups, rather than the effect of a single group / feature.

[0031] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0032] In this invention, the halogen can be fluorine, chlorine, bromine, or iodine. The same descriptions used below have the same meaning.

[0033] In this invention, unless otherwise specified, the description of chemical elements includes the concept of isotopes with the same chemical properties. For example, hydrogen (H) includes 1H (protium). 2 H (deuterium, D) 3 H (tritium, T), etc.; carbon (C) includes 12 C 13 C, etc.

[0034] In this invention, unless otherwise specified, the heteroatoms of the heteroaryl group are selected from N, O, S, P, B, Si or Se, preferably N, O or S.

[0035] In this invention, the way the ring structure is represented by "—" indicates that the connection point is located at any position on the ring structure where bonding can occur.

[0036] In this invention, "-*" and "*" both represent the linking site of a group.

[0037] In this invention, the expression Ca-Cb represents that the group has ab carbon atoms. Unless otherwise specified, the number of carbon atoms does not include the number of carbon atoms of the substituents.

[0038] In this invention, "each independently" means that when there are multiple subjects, they can be the same or different from each other.

[0039] C6-C60 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56 or C58, etc.

[0040] C3-C60 can all be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56, or C58, etc.

[0041] The C15-C60 can all be C15, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56 or C58, etc.

[0042] The C14-C60 can all be C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56 or C58, etc.

[0043] C1-C20 can all be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19, etc.

[0044] C3-C20 can all be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19, etc.

[0045] C2-C20 can all be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19, etc.

[0046] C6-C30 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.

[0047] C3-C30 can all be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.

[0048] In this invention, the C6-C60 aryl (C6-C60 aromatic ring), preferably C6-C30 aryl (C6-C30 aromatic ring), and more preferably C6-C20 aryl (C6-C30 aromatic ring), includes monocyclic aryl and fused-ring aryl groups; the monocyclic aryl means that the group contains at least one phenyl group, and when it contains at least two phenyl groups, the phenyl groups are linked by single bonds, exemplarily including but not limited to: phenyl, biphenyl, terphenyl, tetraphenyl, etc.; the fused-ring aryl means that the group contains At least two aromatic rings, wherein the aromatic rings share two adjacent carbon atoms fused together, exemplary including but not limited to: naphthyl, anthraceneyl, phenanthryl, indene, fluorenyl and their derivatives (9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, spirodifluorenyl, benzo[a]fluorenyl, etc.), fluoranyl, triphenylene, pyrene, perylene, Aryl, tetraphenyl, acenaphthene, benzo[a]acenaphthene, etc. It should be noted that monocyclic aryl and fused-ring aryl groups linked by single bonds also fall under the aryl group category, such as phenylnaphthyl, naphthylphenyl, naphthylnaphthyl, phenylnaphthylphenyl, etc.

[0049] The C3-C60 heteroaryl group (C3-C60 heteroaryl ring), preferably C6-C30 heteroaryl group (C3-C30 heteroaryl ring), and more preferably C3-C20 heteroaryl group (C3-C20 heteroaryl ring), includes monocyclic heteroaryl groups or fused-ring heteroaryl groups. A monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, etc.), the heteroaryl group and other groups are connected by a single bond, exemplarily including but not limited to: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furanyl, thiophene, pyrroleyl, bipyridinyl, phenylpyridinyl, pyridylphenyl, etc. The term "fused-ring heteroaryl" refers to a molecule containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring), with the two sharing two adjacent atoms fused together in a group. Exemplary examples include, but are not limited to: quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, isobenzothiopheneyl, indolyl, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl and its derivatives (N-phenylcarbazoleyl, N-naphthylcarbazoleyl, benzocarbazoleyl, dibenzocarbazoleyl, indolocarbazoleyl, azacarbazoleyl, etc.), acridineyl, phenothiazinyl, phenothiazinyl, hydrogenated acridineyl, etc. It should be noted that heteroaryl groups linked by single bonds, and aryl groups linked by single bonds, also fall within the scope of heteroaryl groups, such as phenylpyridinyl, phenylpyrimidinyl, diphenylpyridinyl, diphenylpyrimidinyl, etc.

[0050] In this invention, the C6-C30 aryloxy group is a monovalent group formed by connecting the above-mentioned aryl group with O, and the C3-C30 heteroaryloxy group is a monovalent group formed by connecting the above-mentioned heteroaryl group with O.

[0051] In this invention, specific examples of the C6-C60 arylamino group are monovalent groups obtained by substituting at least one hydrogen atom in the -NH2 group with the aforementioned aryl group, including but not limited to: phenylamino, methylphenylamino, naphthylamino, anthraceneylamino, phenanthreneamino, biphenylamino, etc. Specific examples of the C3-C60 heteroarylamino group are monovalent groups obtained by substituting at least one hydrogen atom in the -NH2 group with the aforementioned heteroaryl group, including but not limited to: pyridinylamino, pyrimidinylamino, dibenzofuranylamino, etc.

[0052] The C1-C20 straight-chain or branched alkyl group, preferably C1-C16 straight-chain or branched alkyl group, and more preferably C1-C10 straight-chain or branched alkyl group, includes, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, 2-ethylhexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, etc.

[0053] Specific examples of the C1-C20 alkoxy groups can be exemplified by the monovalent groups obtained by connecting the above-mentioned straight-chain or branched alkyl groups to O.

[0054] The C3-C20 cycloalkyl group, preferably C3-C10 cycloalkyl group, includes monocycloalkyl or polycycloalkyl groups. Monocycloalkyl refers to an alkyl group containing a single ring structure, while polycycloalkyl refers to a structure formed by two or more cycloalkyl groups sharing one or more carbon atoms on a ring; exemplary examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl.

[0055] The C2-C20 alkenyl group, preferably C2-C10 alkenyl group, contains at least one C=C, and includes, but is not limited to: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, butadienyl, pentadienyl, etc.

[0056] Preferably, the ring C is The dashed lines represent the fused bonds of the ring C.

[0057] Preferably, X1 and X2 are selected from NAr, thereby giving the boron-containing organic compound a BN resonance structure and achieving excellent photoelectric properties.

[0058] Preferably, the boron-containing organic compound has the structure shown in Formula II:

[0059]

[0060] In Equation II, rings A and B have the same defined range as in Equation I.

[0061] In Equation II, Z1, Z2, and Z3 are each independently selected from CR. 1 CR X Or N, and at least one of Z1, Z2 and Z3 is CR X Preferably, one of Z1, Z2 and Z3 is CR. X Multiple (e.g., 2) CRs 1 R in 1 These can be the same or different groups.

[0062] R 1 Each is independently selected from any one of hydrogen, halogen, unsubstituted or R'-substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, cyano, nitro, hydroxyl, amino, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl; wherein R 1Each ring is independent and not connected to the adjacent ring structure or is connected to form a ring by chemical bonds.

[0063] In Formula II, Ar1 and Ar2 are each independently selected from any one of substituted or unsubstituted C6-C60 aryl groups and substituted or unsubstituted C3-C60 heteroaryl groups; Ar1 ​​and Ar2 are each independently not connected to the adjacent ring structure or connected to form a ring by chemical bonds.

[0064] Preferably, ring A and ring B are each independently selected from... The dashed lines represent the fused bonds of the ring.

[0065] Preferably, at least one of ring A and ring B is

[0066] Preferably, the boron-containing organic compound has a structure as shown in Formula IIIA or Formula IIIB:

[0067]

[0068] M is selected from O or S.

[0069] U1, U2, U3, U4, U5, U6, U7, and U8 are each independently selected from CR. 2 Or N, multiple (e.g., 2, 3, 4, 5, 6, 7, 8) CR 2 R in 2 These can be the same or different groups.

[0070] R 2 Each is independently selected from any one of hydrogen, halogen, unsubstituted or R'-substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, cyano, nitro, hydroxyl, amino, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl; wherein R 2 Each ring is independent and not connected to the adjacent ring structure or is connected to form a ring by chemical bonds.

[0071] Z1, Z2, Z3, Ar1, and Ar2 have the same range of definition as in Equation II.

[0072] Preferably, at most one of U1, U2, U3 and U4 (0 or 1) is N; and / or, at most one of U5, U6, U7 and U8 (0 or 1) is N.

[0073] Preferably, U1, U2, U3, U4, U5, U6, U7, and U8 are each independently selected from CR. 2 .

[0074] Preferably, U1, U4, U5, and U8 are CH; U2, U3, U6, and U7 are each independently selected from CR. 2 .

[0075] Preferably, the R 2 Each of the following is independently selected from hydrogen, unsubstituted or R'-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl, unsubstituted or R'-substituted C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl, unsubstituted or R'-substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C15, C16, or C18, etc.) aryl, and unsubstituted or R'-substituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, or C18, etc.) heteroaryl, and more preferably hydrogen, C1-C6 straight-chain or branched alkyl, C6-C12 aryl, and C3-C12 heteroaryl.

[0076] Preferably, the R 2 Each is independently selected from hydrogen, methyl, and isopropyl. tert-butyl tert-amyl Any one of phenyl, benzothiophene, or benzofuranyl; -* represents the linking site of the group.

[0077] Preferably, Z1, Z2, and Z3 are each independently selected from CR. 1 or CR X And at least one of Z1, Z2 and Z3 is CR X Preferably, one of Z1, Z2 and Z3 is CR. X .

[0078] Preferably, Z1 and Z3 are CH, and Z2 is CR. X .

[0079] Preferably, Ar1 and Ar2 are each independently selected from any one of substituted or unsubstituted C6-C30 (e.g., C6, C9, C10, C12, C14, C15, C16, C18, C20, C22, C25 or C28, etc.) aryl groups and substituted or unsubstituted C3-C30 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, C18, C20, C22, C25 or C28, etc.) heteroaryl groups; and Ar1 and Ar2 are each independently not connected to the adjacent ring structure or connected to form a ring by chemical bonds.

[0080] Preferably, the substituents in Ar1 and Ar2 are each independently selected from halogens, unsubstituted or R'-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl groups, unsubstituted or R'-substituted C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl groups, unsubstituted or R'-substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C15, C16, or C18, etc.) aryl groups, and unsubstituted or R'-substituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, or C18, etc.) heteroaryl groups. More preferably, they are selected from C1-C6 straight-chain or branched alkyl groups and C6-C12 aryl groups.

[0081] Preferably, Ar1 and Ar2 are each independently selected from any one of substituted or unsubstituted phenyl and substituted or unsubstituted biphenyl; the substituents in Ar1 and Ar2 are each independently selected from any one of C1-C6 straight-chain or branched alkyl groups.

[0082] Preferably, Ar1 and Ar2 are each independently selected from... The carbon atom at position 1 is either not connected to the adjacent ring (e.g., ring A, ring B) or is connected to it by a chemical bond to form a ring; when the carbon atom at position 1 is connected to the adjacent ring (e.g., ring A, ring B) to form a ring, a carbazole-like fused ring structure can be formed.

[0083] R 3 The term indicates any of the following: unsubstituted, monosubstituted, or with the most permissible substitution, selected from hydrogen (unsubstituted), halogen, unsubstituted or R'-substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, cyano, nitro, hydroxy, amino, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl, preferably halogen or unsubstituted or R'-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain. The aryl group is selected from the following: branched alkyl, unsubstituted or R'-substituted C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl, unsubstituted or R'-substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C15, C16, or C18, etc.) aryl, unsubstituted or R'-substituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, or C18, etc.) heteroaryl, preferably C1-C6 straight-chain or branched alkyl, or C6-C12 aryl, and even more preferably methyl, ethyl, or isopropyl. tert-butyl tert-amyl Any of the following: phenyl groups.

[0084] Preferably, the boron-containing organic compound has a structure as shown in formula VA or formula VB:

[0085]

[0086] In this context, dashed lines represent single bonds or no connection. When a dashed line represents a single bond, it indicates that the rings are connected by single bonds to form a ring; when a dashed line represents no connection, it means that the chemical bond shown by the dashed line does not exist.

[0087] M is selected from O or S.

[0088] R 21 R 22 R 31 R 32 Each can be used independently to represent no substitution, single substitution, or the maximum permissible substitution.

[0089] Among them, R 21 Indicates no substitution (R) 21 (e.g., hydrogen), monosubstituted, disubstituted, or trisubstituted; when R 21 When indicating di- or tri-substituted, multiple Rs 21 For the same or different groups; R 22 R 31 R 32 The same applies to the other two expressions; for the sake of brevity, I will not repeat them.

[0090] R 21 R 22 R 31 R 32 Each is independently selected from any one of hydrogen, halogen, unsubstituted or R'-substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, cyano, nitro, hydroxy, amino, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl.

[0091] R X It has the same defined range as in Equation I.

[0092] Preferably, the R X It is attached to the parasite of the C atom to which B is attached.

[0093] Preferably, the R 21 R 22 R 31 R 32Each is independently selected from hydrogen, unsubstituted or R'-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl groups, unsubstituted or R'-substituted C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl groups, and unsubstituted or R'-substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C15, etc.) cycloalkyl groups. The aryl group is selected from any one of the following: aryl (C16 or C18, etc.), unsubstituted or R'-substituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16 or C18, etc.), further preferably hydrogen, C1-C6 straight-chain or branched alkyl, C6-C12 aryl, C3-C12 heteroaryl, and even more preferably methyl, ethyl, or isopropyl. tert-butyl tert-amyl Any one of phenyl, benzothiophene, or benzofuranyl.

[0094] Preferably, the R X Selected from any one of the following groups:

[0095]

[0096] Preferably, the R X Selected from

[0097] Preferably, X3 is selected from N and CR. 11 or SiR 12 Any one of them; the X4 is selected from NR 13 O, S, CR 11 R 14 or SiR 12 R 15 Any one of them.

[0098] The R 11 R 12 R 13 R 14 R 15Each is independently selected from hydrogen, substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl, substituted or unsubstituted C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl, substituted or unsubstituted C6-C200 (e.g., C6, C9, C10, C12, C14, C15, C16 or C18, etc.) aryl, substituted or unsubstituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16 or C18, etc.) heteroaryl, and more preferably hydrogen or C1-C6 straight-chain or branched alkyl.

[0099] Preferably, X3 is selected from N or CR. 11 X4 is selected from NR 13 O, S or CR 11 R 14 Of any one of them, O or S is preferred.

[0100] Preferably, the ring D is selected from any one of the following: substituted or unsubstituted C15-C30 aromatic rings formed by the fusion of at least four benzene rings (e.g., C16, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27 or C28, etc.); substituted or unsubstituted C14-C30 heteroaromatic rings formed by the fusion of at least four benzene rings and / or heteroaromatic rings (e.g., C15, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27 or C28, etc.).

[0101] Preferably, the ring D is selected from any one of the following fused ring structures, whether substituted or unsubstituted:

[0102]

[0103] Preferably, the ring D is selected from any one of the following fused ring structures, whether substituted or unsubstituted:

[0104]

[0105] X3, X4, optional It can be connected to any chemically permissible site in the aforementioned fused ring structure.

[0106] Preferably, the ring E is selected from one of substituted or unsubstituted C6-C20 (e.g., C6, C9, C10, C12, C14, C15, C16 or C18, etc.) aromatic rings, substituted or unsubstituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16 or C18, etc.) heteroaromatic rings, and more preferably one of substituted or unsubstituted benzene rings, substituted or unsubstituted pyridine rings.

[0107] Preferably, the substituents in ring D and ring E are each independently selected from halogens, unsubstituted or R'-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl groups, unsubstituted or R'-substituted C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl groups, unsubstituted or R'-substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C15, C16, or C18, etc.) aryl groups, and unsubstituted or R'-substituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, or C18, etc.) heteroaryl groups, and more preferably any one of C1-C6 straight-chain or branched alkyl groups.

[0108] Preferably, the R X Selected from any one of the following groups:

[0109]

[0110] Where -* represents the linking site of the group;

[0111] R 11 Each is independently selected from any one of hydrogen, substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl, substituted or unsubstituted C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl, substituted or unsubstituted C6-C20 (e.g., C6, C9, C10, C12, C14, C15, C16, or C18, etc.) aryl, substituted or unsubstituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, or C18, etc.) heteroaryl, further preferably hydrogen, any one of C1-C6 straight-chain or branched alkyl, and even more preferably methyl.

[0112] R 41 This indicates no substitution, single substitution, or the maximum permissible substitution.

[0113] Among them, R 41 Indicates no substitution (R) 41 (for hydrogen), monosubstituted, disubstituted, trisubstituted, or tetrasubstituted, etc.; when R 41 When indicating di-, tri-, or tetra-substituted substitutions, multiple Rs 41 These can be the same or different groups.

[0114] R 41 Each is independently selected from any one of hydrogen, unsubstituted or R'-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl groups, unsubstituted or R'-substituted C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl groups, unsubstituted or R'-substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C15, C16, or C18, etc.) aryl groups, and unsubstituted or R'-substituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, or C18, etc.) heteroaryl groups, further preferably any one of C1-C6 straight-chain or branched alkyl groups, and even more preferably methyl, ethyl, or isopropyl. tert-butyl tert-amyl Any one of them.

[0115] Preferably, the R X Selected from any one of the following groups:

[0116]

[0117]

[0118] Preferably, the boron-containing organic compound has the structure shown in any one of M1-M80:

[0119]

[0120]

[0121]

[0122]

[0123]

[0124] In a second aspect, the present invention provides an application of the boron-containing organic compound as described in the first aspect, wherein the boron-containing organic compound is applied to organic electronic devices.

[0125] 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 more preferably an organic electroluminescent device.

[0126] Preferably, the boron-containing organic compound is used in an organic electroluminescent device.

[0127] Preferably, the boron-containing organic compound is used as a light-emitting layer material in an organic electroluminescent device.

[0128] Preferably, the boron-containing organic compound is used as a dye (also known as "doping material", "dopant", or "guest material") in the light-emitting layer of the organic electroluminescent device.

[0129] In addition, the boron-containing organic compound can also be used as a sensitizer to achieve a good luminescent layer together with the host material and dye.

[0130] Thirdly, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode; the organic layer comprising at least one boron-containing organic compound as described in the first aspect.

[0131] Preferably, the organic layer includes at least one boron-containing organic compound with the structure shown in M1-M80.

[0132] Preferably, the organic layer includes a light-emitting layer, which includes at least one boron-containing organic compound as described in the first aspect, and more preferably includes at least one boron-containing organic compound with the structure shown in M1-M80.

[0133] Preferably, the light-emitting layer comprises a host material and a dye, wherein the dye is at least one boron-containing organic compound as described in the first aspect.

[0134] Preferably, the boron-containing organic compound provided by the present invention, as a dye (fluorescent dopant) for the luminescent layer, has excellent luminescence performance, can achieve narrow-spectrum deep blue emission, and can provide triplet excitons to achieve high luminescence efficiency. Based on its excellent carrier transport efficiency, it improves the luminescence efficiency and lifetime of the device.

[0135] Preferably, the dye content in the luminescent layer is 0.1-10% by mass, for example, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, and more preferably 0.3-4%.

[0136] Preferably, the organic layer further includes a hole transport region and an electron transport region.

[0137] Preferably, the hole transport region includes any one or a combination of at least two of the following: a hole injection layer, a hole transport layer, and an electron blocking layer.

[0138] Preferably, the electron transport region includes any one or a combination of at least two of the electron injection layer, electron transport layer, and hole blocking layer.

[0139] In a preferred embodiment, the organic light-emitting device (OLED device) includes a first electrode and a second electrode, and an organic layer located between the electrodes. The organic layer can be further divided into multiple regions, such as a hole transport region, a light-emitting layer, and an electron transport region; the light-emitting layer contains at least one boron-containing organic compound as described in the first aspect, and more preferably contains at least one boron-containing organic compound with the structure shown in M1-M80.

[0140] In a preferred embodiment, the organic electroluminescent device includes a first electrode, a plurality of light-emitting functional layers (organic layers), and a second electrode arranged sequentially. The organic layers include a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer arranged sequentially, with the hole injection layer in contact with the first electrode (anode). The organic layer (preferably the light-emitting layer) contains at least one boron-containing organic compound as described in the first aspect, and more preferably contains at least one boron-containing organic compound with a structure shown in M1-M80.

[0141] In a preferred embodiment, a substrate can be used below the first electrode or above the second electrode. The substrate is typically made of glass or polymer material possessing excellent mechanical strength, thermal stability, water resistance, and transparency. Furthermore, the substrate used for a display may also incorporate thin-film transistors (TFTs).

[0142] The first electrode can be formed by sputtering or depositing the material to be used as the first electrode on a substrate. When the first electrode is used as the anode, it can be a transparent conductive oxide material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof. When the first electrode is used as the cathode, it can be 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), or any combination thereof.

[0143] Organic layers can be formed on electrodes using methods such as vacuum thermal evaporation, spin coating, and printing. The compounds used as organic layers can be small organic molecules, large organic molecules, or polymers, as well as combinations thereof.

[0144] The hole transport region is located between the anode and the emissive layer. The hole transport region can be a single-layer hole transport layer (HTL), including single-layer hole transport layers containing only one compound and single-layer hole transport layers containing multiple compounds. Alternatively, the hole transport region can be a multilayer structure including at least one 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 emissive layer.

[0145] The material for the hole transport region may be selected from, but is 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 compounds shown in HT-1 to HT-51 below; or any combination thereof.

[0146]

[0147]

[0148]

[0149] 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 be one or more compounds of HT-1 to HT-51 described above, or one or more compounds of HI-1 to HI-3 described below; it can also be one or more compounds of HT-1 to HT-51 doped with one or more compounds of HI-1 to HI-3 described below.

[0150]

[0151] The emissive layer consists of a luminescent dye (i.e., a dopant) that emits different wavelengths of light and a host material. The emissive layer can be a monochromatic layer emitting a single color such as red, green, or blue. Multiple monochromatic emissive layers of different colors can be arranged in a planar pattern according to pixel design, or they can be stacked together to form a colored emissive layer. When different colored emissive layers are stacked together, they can be separated from each other or connected to each other. The emissive layer can also be a single colored emissive layer that simultaneously emits different colors such as red, green, and blue.

[0152] Depending on the technology used, the light-emitting layer material can be various, including fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescence materials. An OLED device can employ a single light-emitting technology or a combination of different technologies. These different light-emitting materials, categorized by technology, can emit light of the same color or different colors.

[0153] In one aspect of the invention, the light-emitting layer employs fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer may be selected from, but is not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0154]

[0155] In one aspect of the invention, the blocking layer surrounding the light-emitting layer may be selected from, but is not limited to, one or more combinations of PH-1 to PH-85.

[0156]

[0157]

[0158]

[0159]

[0160] 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 employ, but is not limited to, one or more compounds of HT-1 to HT-51 described above, or one or more compounds of PH-47 to PH-77 described above; or a mixture of one or more compounds of HT-1 to HT-51 and one or more compounds of PH-47 to PH-77 may be employed.

[0161] The organic layer of an OLED may also include an electron transport region between the light-emitting layer and the cathode. The electron transport region can be a single-layer electron transport layer (ETL), including single-layer electron transport layers containing only one compound and single-layer electron transport layers containing multiple compounds. Alternatively, the electron transport region can be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0162] In one aspect of the present invention, the electron transport layer material may be selected from, but not limited to, one or more combinations of ET-1 to ET-73 listed below.

[0163]

[0164]

[0165]

[0166]

[0167] 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 employ, but is 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 may be employed.

[0168] 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, Yb.

[0169] Fourthly, the present invention provides a display device comprising the organic electroluminescent device as described in the third aspect.

[0170] Preferably, the display device includes a display screen or a display panel.

[0171] The present invention also provides an electronic device, which includes the aforementioned display device.

[0172] Compared with the prior art, the present invention has the following beneficial effects:

[0173] The boron-containing organic compound provided by this invention has the structure shown in Formula I. Through the design and mutual compounding of the core structure and specific groups, it exhibits excellent photoelectric properties, emits deep blue light, has narrow spectral characteristics, and can provide triplet excitons to achieve high luminous efficiency. When used in organic electroluminescent devices, the boron-containing organic compound can be used as a fluorescent dye in the luminescent layer, exhibiting excellent carrier transport efficiency, enabling the device to achieve a high-purity deep blue luminescence effect, while simultaneously improving the luminous efficiency and lifespan of the device, fully meeting the current requirements of display devices and panels for high-performance materials. Detailed Implementation

[0174] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0175] The boron-containing organic compounds represented by Formula I of this invention can be synthesized using organic synthesis methods known in the art. Exemplary synthetic routes are given below, but those skilled in the art can also obtain them using other known methods.

[0176] In one specific embodiment, the boron-containing organic compound can be prepared via the synthetic route shown below:

[0177]

[0178] Among them, ring A, ring B, ring C, X1, X2, and R X It has the same definition as in Formula I; Hal1, Hal2, and Hal3 are each independently selected from any one of F, I, Br, or Cl. When R X When the structure shown in formula a is given, and X3 is N, the starting material for reaction IV is HR. X When X3 is not N, the starting material for reaction IV is X. 11 -R X X 11 Selected from The order of reactions I and II can be adjusted according to the synthesis situation. That is, reaction I can be carried out first and then reaction II, or reaction II can be carried out first and then reaction I, or they can be carried out simultaneously (X1 and X2 are the same, and ring A and ring B are the same); reactions I and II are carried out in the presence of palladium catalyst.

[0179] The specific preparation methods of the boron-containing organic compounds of the present invention will be described in detail below using several synthetic examples, but the preparation methods of the present invention are not limited to these synthetic examples.

[0180] It should be noted that obtaining the boron-containing organic compounds is not limited to the synthetic methods and raw materials used in this invention. Those skilled in the art can also select other methods or routes to obtain the boron-containing organic compounds proposed in this invention. The compounds, solvents, and reagents used in the synthetic methods not mentioned in this invention are all commercially available raw material products, which can be purchased from the domestic chemical product market or prepared in-house using these raw material products according to known methods.

[0181] The intermediates and target products in the following synthesis examples of the present invention were analyzed and detected using an ABSCIEX mass spectrometer (4000QTRAP) and matrix-assisted laser desorption / ionization (MALDI) technology.

[0182] Synthesis Example 1: Synthesis of Boron-Containing Organic Compound M1

[0183]

[0184]

[0185] (1) Synthesis of intermediate M1-1:

[0186] 30 g of 5-chloro-1,3-dibromobenzene, 62.46 g of di(4-tert-butylphenyl)amine, 3.94 g of palladium catalyst (Pd132), and 42.66 g of sodium tert-butoxide were added to a 2000 mL flask. 600 mL of toluene was added, and the mixture was heated to reflux under nitrogen protection for 2 h. The solvent was evaporated, and the mixture was subjected to silica gel column chromatography with stirring to obtain 53.4 g of a white solid. The molecular weight was determined by mass spectrometry to be 670.46 (theoretical value 670.41).

[0187] (2) Synthesis of intermediate M1-2:

[0188] 20 g of intermediate M1-1, 74.63 g of boron tribromide, and 200 mL of o-dichlorobenzene were added to a 1000 mL pressure-resistant bottle. The mixture was heated to 180 °C under nitrogen protection and reacted for 12 h. The mixture was extracted with dichloromethane and water, and the organic phases were combined. The solvent was evaporated, and the mixture was subjected to silica gel column chromatography with stirring to obtain 2.39 g of yellow solid. The molecular weight was determined by mass spectrometry to be 678.41 (theoretical value 678.39).

[0189] (3) Synthesis of target product M1

[0190] 2g of intermediate M1-2, 3g of N(1-pyrene)aniline, 0.1g of Pd132, and 0.56g of sodium tert-butoxide were added to a 100mL flask. 20mL of toluene was added, and the mixture was heated to reflux under nitrogen protection for 2 hours. The solvent was evaporated, and the mixture was subjected to silica gel column chromatography to obtain 1.79g of yellow solid, which was the target product M1. The molecular weight was determined by mass spectrometry to be 935.48 (theoretical value 935.53).

[0191] Synthesis Example 2: Synthesis of Boron-Containing Organic Compound M8

[0192]

[0193] The synthesis method of boron-containing organic compound M1 was followed, except that di(4-tert-butylphenyl)amine was replaced with an equimolar amount of N-(4-tert-butylphenyl)benzidine, and N(1-pyrene)aniline was replaced with an equimolar amount of [2,1]pyreneindole, to obtain the target product M8, with a molecular weight of 973.52 (theoretical value 973.46) as determined by mass spectrometry.

[0194] Synthesis Example 3: Synthesis of Boron-Containing Organic Compound M27

[0195]

[0196] Following the synthetic method of boron-containing organic compound M1, the only difference was that the di(4-tert-butylphenyl)amine was replaced with an equimolar amount of 3,6-di-tert-butylcarbazole, resulting in the target product M27, with a molecular weight of 931.51 (theoretical value 931.50) as determined by mass spectrometry.

[0197] Synthesis Example 4: Synthesis of Boron-Containing Organic Compound M59

[0198] Synthesis of intermediate A

[0199]

[0200] 20 g of 2-bromobenzo[a]pyrene-furan, 20.5 g of pinacol diboronic acid ester, 1.97 g of palladium catalyst Pd(dppf)Cl2, and 10.57 g of potassium acetate KOAc were added to a 1000 mL reaction flask. 400 mL of dioxane was added, and the mixture was heated to reflux and reacted for 12 h. The solvent was evaporated, and the mixture was subjected to silica gel column chromatography with stirring. 17.17 g of white solid was obtained, which is intermediate A. The molecular weight was determined by mass spectrometry to be 418.18 (theoretical value 418.17).

[0201]

[0202] The synthesis method of boron-containing organic compound M1 was followed, except that di(4-tert-butylphenyl)amine was replaced with an equimolar amount of di(3-methylphenyl)amine, N(1-pyrene)aniline was replaced with an equimolar amount of intermediate A, sodium tert-butoxide was replaced with an equimolar amount of potassium carbonate, and the solvent was replaced with an equal volume of dioxane:water in a 5:1 ratio, to obtain the target product M59, whose molecular weight was determined by mass spectrometry to be 766.35 (theoretical value 766.32).

[0203] Device Example 1

[0204] An organic electroluminescent device includes 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) stacked sequentially. The fabrication method of this organic electroluminescent device is as follows:

[0205] (1) The glass substrate coated with ITO transparent conductive layer was ultrasonically treated in commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in acetone / ethanol mixed solvent, baked in a clean environment until the moisture was completely removed, cleaned with ultraviolet light and ozone, and bombarded with low-energy cation beam.

[0206] (2) Place the glass substrate with the anode into a vacuum chamber and evacuate to <1×10⁻⁶. -5Pa, a mixture of HT-4:HI-3 (97 / 3, w / w) was vacuum-deposited on the above-mentioned anodic layer as a hole injection layer, and the thickness of the deposited film was 10 nm.

[0207] (3) A 60 nm layer of compound HT-4 was vacuum-deposited on the hole injection layer as a hole transport layer;

[0208] (4) A 5 nm layer of compound HT-14 was vacuum-deposited on the hole transport layer as an electron blocking layer;

[0209] (5) A light-emitting layer is vacuum-deposited on the electron blocking layer. The light-emitting layer comprises a binary mixture of the host material BFH-4 and the dye (the boron-containing organic compound M1 provided by the present invention), BFH-4:M1 (100:3, w / w), and the total film thickness of the vapor-deposited layer is 20 nm.

[0210] (6) A 5 nm layer of compound ET-23 was vacuum-deposited on the light-emitting layer as a hole-blocking layer;

[0211] (7) A mixture of compound ET-69:ET-57 (50 / 50, w / w) was vacuum-deposited on the hole blocking layer as an electron transport layer, with a total film thickness of 25 nm.

[0212] (8) Vacuum evaporation of 1 nm of LiF on the electron transport layer as an electron injection layer;

[0213] (9) A 150 nm thick Al layer is vacuum-deposited on the electron injection layer as the cathode of the device. The total deposition rate of all organic layers and LiF is controlled at 0.1 nm / s, and the deposition rate of aluminum is 1 nm / s, thus obtaining the organic electroluminescent device.

[0214] Device Examples 2-17, Device Comparative Examples 1-6

[0215] An organic electroluminescent device is disclosed, which differs from device example 1 only in that the fluorescent 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 in device example 1.

[0216] The structures of the fluorescent dyes in Comparative Examples 1-6 are as follows:

[0217]

[0218] In C1, Ph represents phenyl and tBu represents tert-butyl.

[0219] Device performance testing:

[0220] The external quantum efficiency (EQE, %) of the device was measured using the integrating sphere method.

[0221] Under the same brightness, the lifetime of organic electroluminescent devices was determined using a digital source meter and a PR650 spectroradiometer, as follows: The radiometer was used at 40 mA / cm². 2 The initial brightness value of the device under current density is measured. The current is kept constant, and the time it takes for the device brightness to drop to 97% of the initial brightness is measured in hours. The LT97 lifetime test value of device Comparative Example 1 is recorded as 1.0. The ratio of the LT97 lifetime test value of other devices to the LT97 lifetime test value of device Comparative Example 1 is calculated.

[0222] The test results are shown in Table 1:

[0223] Table 1

[0224]

[0225]

[0226] As can be seen from the performance data in Table 1, the boron-containing organic compound provided by this invention, as a dye for organic electroluminescent devices, can effectively improve the external quantum efficiency of the device and extend its working life.

[0227] Comparing the boron-containing organic compounds provided by this invention with comparative compounds C1-C6, it can be seen that the compounds of this invention exhibit higher efficiency and longer lifetime compared to compounds C1 and C2. This may be due to the presence of a fused-ring aromatic amine group R in this invention. X The connection site is the benzene ring below the B atom. This position is more conducive to improving device lifetime and efficiency, while other sites are more likely to cause exciton quenching, thus affecting device efficiency and lifetime.

[0228] Compared to the comparative compound C3, the boron-containing organic compound of the present invention exhibits higher efficiency and longer lifetime as a dye. This may be due to the poor stability of the sulfur-containing fused ring in C3, which causes decomposition products to increase additional exciton quenching, resulting in lower device efficiency and lifetime.

[0229] Compared to the comparative compounds C4-C6, devices containing the compounds of this invention exhibit higher efficiency and longer lifetime, mainly due to the fused ring structure contained in C4-C6 being different from the R group in this invention. X Compared to phenanthrene or anthracene groups in C4-C6, the fused ring structure of the compounds in this invention has a lower triplet energy level, which can slow down the rate at which triplet excitons of fluorescent dyes are quenched, thereby improving efficiency and lifetime.

[0230] The applicant declares that the above embodiments illustrate the boron-containing organic compounds and their applications, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A boron-containing organic compound, characterized in that, The boron-containing organic compound has the structure shown in Formula I: Among them, ring A, ring B, and ring C are each independently selected from any one of substituted or unsubstituted C6-C60 aromatic rings and substituted or unsubstituted C3-C60 heteroaromatic rings; X1 and X2 are each independently selected from O, S or NAr; Ar is selected from any one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl; the Ar is not connected to the adjacent ring structure or is connected to the ring by chemical bonds; R X It has a structure as shown in any one of equations a, b, or c: -* represents the linkage site of a functional group; R X Connected to ring C via a single bond; X3 is selected from N and CR. 11 or SiR 12 Any one of them; X4 is selected from NR 13 O, S, CR 11 R 14 or SiR 12 R 15 Any one of them; Ring D is selected from any one of the following: a C15-C60 aromatic ring composed of at least four benzene rings fused together, or a C14-C60 heteroaromatic ring composed of at least four benzene rings fused together, or a heteroaromatic ring composed of at least four benzene rings fused together; Ring E is selected from any one of substituted or unsubstituted C6-C60 aromatic rings and substituted or unsubstituted C3-C60 heteroaromatic rings; Dashed lines indicate Whether it exists or not, Y1 is selected from single bond, O, S, NR. 16 CR 17 R 18 or SiR 19 R 20 Any one of them; R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 Each is independently selected from any one of hydrogen, substituted or unsubstituted C1-C20 straight-chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl; Ring A, Ring B, Ring C, Ring D, Ring E, Ar, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 The substituents described herein are each independently selected from any one of the following: halogen, unsubstituted or R'-substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, cyano, nitro, hydroxyl, amino, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl; R' is independently selected from any one or a combination of at least two of the following: halogen, cyano, nitro, hydroxyl, amino, C1-C20 straight-chain or branched alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl.

2. The boron-containing organic compound according to claim 1, characterized in that, The boron-containing organic compound has the structure shown in Formula II: Among them, rings A and B have the same limited range as in equation I; Z1, Z2, and Z3 are each independently selected from CR 1 CR X Or N, and at least one of Z1, Z2 and Z3 is CR X Preferably, one of Z1, Z2 and Z3 is CR. X ; R 1 Each is independently selected from any one of hydrogen, halogen, unsubstituted or R'-substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, cyano, nitro, hydroxyl, amino, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl; wherein R 1 Each ring is independent and not connected to the adjacent ring structure or is connected to form a ring by chemical bonds; Ar1 and Ar2 are each independently selected from any one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl; Ar1 ​​and Ar2 are each independently not connected to the adjacent ring structure or connected to form a ring by chemical bonds.

3. The boron-containing organic compound according to claim 2, characterized in that, The boron-containing organic compound has a structure as shown in formula IIIA or IIIB: Where M is selected from O or S; U1, U2, U3, U4, U5, U6, U7, and U8 are each independently selected from CR. 2 Or N; R 2 Each is independently selected from any one of hydrogen, halogen, unsubstituted or R'-substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, cyano, nitro, hydroxyl, amino, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl; wherein R 2 Each ring is independent and not connected to the adjacent ring structure or is connected to form a ring by chemical bonds; Z1, Z2, Z3, Ar1, and Ar2 have the same range of definition as in Equation II.

4. The boron-containing organic compound according to claim 3, characterized in that, U1, U2, U3, U4, U5, U6, U7, and U8 are each independently selected from CR. 2 ; Preferably, U1, U4, U5, and U8 are CH; U2, U3, U6, and U7 are each independently selected from CR. 2 ; Preferably, the R 2 Each of the following is independently selected from hydrogen, unsubstituted or R'-substituted C1-C10 straight-chain or branched alkyl, unsubstituted or R'-substituted C3-C10 cycloalkyl, unsubstituted or R'-substituted C6-C20 aryl, and unsubstituted or R'-substituted C3-C20 heteroaryl, and is further preferably selected from hydrogen, C1-C6 straight-chain or branched alkyl, C6-C12 aryl, and C3-C12 heteroaryl; Preferably, the R 2 Each is independently selected from hydrogen, methyl, Any one of phenyl, benzothiophene, or benzofuranyl; -* represents the linking site of the group; Preferably, Z1, Z2, and Z3 are each independently selected from CR. 1 or CR X And at least one of Z1, Z2 and Z3 is CR X Preferably, one of Z1, Z2 and Z3 is CR. X ; Preferably, Z1 and Z3 are CH, and Z2 is CR. X .

5. The boron-containing organic compound according to claim 2 or 3, characterized in that, Ar1 and Ar2 are each independently selected from any one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; Ar1 ​​and Ar2 are each independently not connected to the adjacent ring structure or connected to form a ring by chemical bonds; Preferably, the substituents in Ar1 and Ar2 are each independently selected from any one of halogens, unsubstituted or R'-substituted C1-C10 straight-chain or branched alkyl groups, unsubstituted or R'-substituted C3-C10 cycloalkyl groups, unsubstituted or R'-substituted C6-C20 aryl groups, and unsubstituted or R'-substituted C3-C20 heteroaryl groups. More preferably, they are any one of C1-C6 straight-chain or branched alkyl groups and C6-C12 aryl groups.

6. The boron-containing organic compound according to claim 1, characterized in that, The boron-containing organic compound has a structure as shown in formula VA or formula VB: In this context, dashed lines represent single keys or no connection. M is selected from O or S; R 21 R 22 R 31 R 32 Each can be used independently to represent no substitution, single substitution, or the maximum permissible substitution. R 21 R 22 R 31 R 32 Each is independently selected from any one of hydrogen, halogen, unsubstituted or R'-substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, cyano, nitro, hydroxy, amino, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl; R X It has the same limiting range as in Equation I; Preferably, the R X Connected to the parasite of the C atom to which B is attached; Preferably, the R 21 R 22 R 31 R 32 Each of the following is independently selected from hydrogen, unsubstituted or R'-substituted C1-C10 straight-chain or branched alkyl, unsubstituted or R'-substituted C3-C10 cycloalkyl, unsubstituted or R'-substituted C6-C20 aryl, and unsubstituted or R'-substituted C3-C20 heteroaryl, and is further preferably selected from hydrogen, C1-C6 straight-chain or branched alkyl, C6-C12 aryl, and C3-C12 heteroaryl.

7. The boron-containing organic compound according to any one of claims 1-6, characterized in that, The R X Selected from any one of the following groups: Preferably, X3 is selected from N and CR. 11 or SiR 12 Any one of them; the X4 is selected from NR 13 O, S, CR 11 R 14 or SiR 12 R 15 Any one of them; The R 11 R 12 R 13 R 14 R 15 Each is independently selected from any one of hydrogen, substituted or unsubstituted C1-C10 straight-chain or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, and more preferably any one of hydrogen and C1-C6 straight-chain or branched alkyl; Preferably, X3 is selected from N or CR. 11 X4 is selected from NR 13 O, S or CR 11 R 14 Any one of them.

8. The boron-containing organic compound according to any one of claims 1-6, characterized in that, The ring D is selected from any one of the following: a C15-C30 aromatic ring composed of at least four benzene rings fused together, or a C14-C30 heteroaromatic ring composed of at least four benzene rings fused together, or a heteroaromatic ring composed of at least four benzene rings fused together; Preferably, the ring D is selected from any one of the following fused ring structures, whether substituted or unsubstituted: Preferably, the ring E is selected from one of substituted or unsubstituted C6-C20 aromatic rings and substituted or unsubstituted C3-C20 heteroaromatic rings, and more preferably one of substituted or unsubstituted benzene rings and substituted or unsubstituted pyridine rings; Preferably, the substituents in ring D and ring E are each independently selected from any one of halogens, unsubstituted or R'-substituted C1-C10 straight-chain or branched alkyl groups, unsubstituted or R'-substituted C3-C10 cycloalkyl groups, unsubstituted or R'-substituted C6-C20 aryl groups, and unsubstituted or R'-substituted C3-C20 heteroaryl groups, and more preferably any one of C1-C6 straight-chain or branched alkyl groups.

9. The boron-containing organic compound according to any one of claims 1-6, characterized in that, The R X Selected from any one of the following groups: Where -* represents the linking site of the group; R 11 Each is independently selected from any one of hydrogen, substituted or unsubstituted C1-C10 straight-chain or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, and more preferably any one of hydrogen and C1-C6 straight-chain or branched alkyl; R 41 Indicates no substitution, single substitution, and the maximum permissible substitution; R 41 Each is independently selected from any one of hydrogen, unsubstituted or R'-substituted C1-C10 straight-chain or branched alkyl, unsubstituted or R'-substituted C3-C10 cycloalkyl, unsubstituted or R'-substituted C6-C20 aryl, and unsubstituted or R'-substituted C3-C20 heteroaryl, and more preferably any one of C1-C6 straight-chain or branched alkyl; Preferably, the R X Selected from any one of the following groups:

10. The boron-containing organic compound according to claim 1, characterized in that, The boron-containing organic compound has the structure shown in any one of M1-M80:

11. The application of a boron-containing organic compound as described in any one of claims 1-10, characterized in that, The boron-containing organic compound is used in organic electronic devices; Preferably, the organic electronic device includes an organic electroluminescent device; Preferably, the boron-containing organic compound is used as a light-emitting layer material in an organic electroluminescent device.

12. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode; the organic layer includes at least one boron-containing organic compound as described in any one of claims 1-10; Preferably, the organic layer includes a light-emitting layer, wherein the light-emitting layer includes at least one boron-containing organic compound as described in any one of claims 1-10; Preferably, the light-emitting layer comprises a host material and a dye, wherein the dye comprises at least one boron-containing organic compound as described in any one of claims 1-10.

13. A display device, characterized in that, The display device includes the organic electroluminescent device as described in claim 12.

Images