A boron-nitrogen-silicon-containing compound and applications thereof

Abstract

The application provides a boron-nitrogen-silicon-containing compound and application thereof. The compound has a structure as shown in formula I or formula II. Through design of a skeleton structure and substituents and mutual coordination, the compound has good thermal stability and excellent luminescent performance, and is a blue light material with excellent performance. The compound is used in an OLED device, is suitable to be used as a light-emitting layer material, and is especially suitable to be used as a doping material in a light-emitting layer, can improve current efficiency of the OLED device, reduce a driving voltage of the OLED device, and prolong a service life of the OLED device.

Description

Technical Field

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

[0002] Organic light-emitting elements (OLEDs) are display components that utilize the phenomenon of self-emission. They have a wider viewing angle. Compared to liquid crystal display components, OLED elements are thinner and lighter, have a faster response time, and can achieve flexible displays. Therefore, they are highly anticipated for use as full-color display components or lighting equipment.

[0003] Organic light emission (OLED) typically refers to the phenomenon of converting electrical energy into light energy using organic materials. OLEDs, operating on this principle, generally consist of an anode, a cathode, and an organic layer sandwiched between them. In most cases, to improve the efficiency and stability of OLEDs, the organic layer is a multi-layered structure composed of different materials. For example, this multi-layered structure may consist of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in this OLED structure, holes from the anode are injected into the organic layer, and electrons from the cathode are injected into the organic layer. When the injected holes and electrons meet, they form excitons. When these excitons release energy and transition to the ground state, they emit photons, thus producing light emission. Such OLEDs possess characteristics such as self-illumination, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

[0004] Currently, research on OLED materials has been widely carried out in academia and industry. Among them, blue light materials are an important component of organic electroluminescent devices. The performance and luminous efficiency of blue light materials restrict the industrialization of light-emitting devices. When applied to OLEDs, they result in high driving voltage and low current efficiency. Therefore, it is urgent to find a blue light material with excellent performance as a new material for OLEDs to solve the problems of high driving voltage and current efficiency that are common in OLEDs.

[0005] Therefore, developing a high-performance blue light material with high luminous efficiency, which can improve the current efficiency of OLEDs, reduce their driving voltage, and extend their lifespan, is a key focus and future research trend in OLED materials research. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a boron-nitrogen silicon compound and its applications. Through the design and synergy of the framework structure and substituents, the obtained boron-nitrogen silicon compound exhibits excellent performance, making it suitable for light-emitting layer materials in OLEDs, especially for doping materials in the light-emitting layer. When used as a doping material in the light-emitting layer, it can improve the current efficiency of OLEDs, reduce the driving voltage, and extend the device's lifespan.

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

[0008] In a first aspect, the present invention provides a boron-nitrogen-silicon compound having a structure as shown in Formula I or Formula II:

[0009]

[0010] In Formula I and Formula II, R1 and R2 are each independently selected from any one of the following: substituted or unsubstituted C6-C50 aryl, substituted or unsubstituted C4-C50 heteroaryl, C1-C20 straight-chain or branched alkyl, and C3-C20 cycloalkyl.

[0011] In Formula I and Formula II, Ar is selected from any one of substituted or unsubstituted C6-C50 arylene or substituted or unsubstituted C4-C50 heteroarylene.

[0012] In Formula II, E is selected from any one of single bond, O, S, and Se; when E is a single bond, X2 and Y2 are directly connected through a single bond.

[0013] In Formula I, X1 and Y1 are each independently selected from any one of substituted or unsubstituted C6-C50 aryl groups and substituted or unsubstituted C3-C50 heteroaryl groups.

[0014] In Formula II, X2 and Y2 are each independently selected from any one of substituted or unsubstituted C6-C50 arylene or substituted or unsubstituted C3-C50 heteroarylene.

[0015] When Ar is phenylene, the compound has the structure shown in Formula II, and the structure in Formula II is... Cannot be In this context, the dashed lines represent the bonding sites of functional groups.

[0016] n1 represents the number of substituents R3, and n2 represents the number of substituents R4.

[0017] n1 is an integer selected from 0 to 4, for example, it can be 0, 1, 2, 3 or 4.

[0018] n2 is an integer selected from 0 to 4, for example, it can be 0, 1, 2, 3 or 4.

[0019] R3 and R4 are each independently selected from any one of the following: substituted or unsubstituted C6-C50 aryl groups, substituted or unsubstituted C4-C50 heteroaryl groups, C1-C20 straight-chain or branched alkyl groups, and C3-C20 cycloalkyl groups. When R3 appears in the formula, R3 can be the same substituent or different substituents; when R4 appears, R4 can be the same substituent or different substituents.

[0020] In Formulas I and II, the substituents of R1, R2, R3, R4, Ar, X1, and Y1 are each independently selected from at least one of halogen, cyano, unsubstituted or R'-substituted C6-C20 aryl, unsubstituted or R'-substituted C4-C20 heteroaryl, and unsubstituted or R'-substituted C1-C12 straight-chain or branched alkyl; wherein R' is selected from at least one of halogen or cyano.

[0021] The substituents described in X2 and Y2 are each independently selected from at least one of halogen, cyano, unsubstituted or R”-substituted C6-C50 aryl, unsubstituted or R”-substituted C4-C50 heteroaryl, C1-C20 straight-chain or branched alkyl, and C3-C20 cycloalkyl.

[0022] The R” is selected from at least one of halogen, cyano, unsubstituted or R”'-substituted C6-C20 aryl, unsubstituted or R”'-substituted C4-C20 heteroaryl, and unsubstituted or R”'-substituted C1-C12 straight-chain or branched alkyl; the R”' is selected from at least one of halogen or cyano.

[0023] In this invention, each of C6 to C50 can independently be C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C35, C40, C45, or C48, etc.

[0024] Each of C4 to C50 can independently be C4, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C35, C40, C45, or C48, etc.

[0025] Each of C1 to C20 can independently be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.

[0026] Each of C3 to C20 can independently be, for example, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19 etc.

[0027] Each of C3 to C50 can independently be, for example, C3, C4, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C35, C40, C45 or C48 etc.

[0028] Each of C6 to C20 can independently be, for example, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19 etc.

[0029] Each of C4 to C20 can independently be, for example, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C'17, C18 or C19 etc.

[0030] Each of C1 to C12 can independently be, for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 etc.

[0031] In the present invention, the halogen includes F, Cl, Br or I.

[0032] In the present invention, for the expression of chemical elements, if there is no special description, the concept of isotopes with the same chemical properties is included. For example, hydrogen (H) includes

[0033] ,

[0032] , 13 , ,

[0031] , 3 , , 12 ,

[0030] , 1 , , 2 H (protium), 2 H (deuterium, D), 3 H (tritium, T), or any combination of at least two of them; carbon (C) includes 12 C, 13 C etc. In the present invention, taking methyl as an example, it can be represented as -CH3, -CD3 etc.

[0033] In this invention, aryl refers to the general term for a monovalent group remaining after removing a hydrogen atom from the aromatic carbon atom of an aromatic hydrocarbon molecule. It can be a monocyclic aryl or a fused-ring aryl, and the C6 to C50 group (e.g., C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C35, C40, C4...) is used. 5 or C48 aryl groups, more preferably C6 to C20 aryl groups, exemplarily including but not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, indene, fluorenyl and their derivatives (9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, spirodifluorenyl, benzo[a]fluorenyl, etc.), fluoranyl, triphenylene, pyrene, perylene, Benzyl, tetraphenyl or benzo[phenanthrene], etc.

[0034] Preferably, the C6-C50 aryl group, more preferably the C6-C20 aryl group, is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracene, indole, fluorenyl, perylene, phenanthrene, pyrene, fluoranyl or benzophenanthrene.

[0035] The C6-C50 arylene group is a divalent group obtained by removing one hydrogen atom from the above-mentioned C6-C50 (e.g., C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C35, C40, C45 or C48, etc.) aryl group.

[0036] In this invention, heteroaryl refers to a group obtained by replacing one or more aromatic carbons in an aryl group with heteroatoms, or a general term for two aryl groups connected by a single bond and bridged by O, S, or N (for example, the aryl group formed by biphenyl bridged by O is dibenzofuranyl, and the aryl group formed by biphenyl bridged by N is carbazoleyl). The heteroatoms include, but are not limited to, O, S, N, P, or B. The heteroaryl can be a monocyclic heteroaryl or a fused-ring heteroaryl. The C3 to C50 values ​​are (e.g., C3, C4, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C35, C40, C45, or C48, etc.). Heteroaryl groups, exemplary including but not limited to: furanyl, thiopheneyl, pyrroleyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phenanthrolineyl, imidazolyl, thiazolyl, oxazolyl, benzimidazolyl, benzothiazolyl, benzoxoxazolyl, benzofuranyl, benzothiapheneyl, indolyl, dibenzofuranyl, dibenzothiapheneyl, carbazoleyl and its derivatives (N-phenylcarbazoleyl, N-naphthylcarbazoleyl, benzocarbazoleyl, dibenzocarbazoleyl, indolocarbazoleyl, azacarbazoleyl, etc.), phenothiazinyl, phenotoxazinyl, hydrogenated acridineyl, etc.; the heteroaryl groups also include monovalent groups formed by the above-listed heteroaryl groups and aryl groups linked by a single bond.

[0037] The C4-C50 (e.g., C4, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C35, C40, C45, or C48, etc.) heteroaryl groups, wherein the heteroatoms include, but are not limited to, O, S, N, P, or B, and are further preferably C4-C20 heteroaryl groups, which exemplarily include, but are not limited to: furanyl, thiopheneyl, pyrroleyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, etc. Quinazolinyl, quinoxolinyl, cenolinyl, o-phenantholinyl, imidazolyl, thiazolyl, oxazolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, benzofuranyl, benzothiophene, indolyl, dibenzofuranyl, dibenzothiophene, carbazoleyl and its derivatives (N-phenylcarbazoleyl, N-naphthylcarbazoleyl, benzocarbazoleyl, dibenzocarbazoleyl, indolocarbazoleyl, azacarbazoleyl, etc.), phenothiazinyl, phenotoxazinyl, hydrogenated acridineyl, etc.; the heteroaryl also includes monovalent groups formed by the above-listed heteroaryl and aryl groups linked by a single bond.

[0038] Preferably, the C4-C50 heteroaryl group, more preferably the C4-C20 heteroaryl group, is selected from any one or a combination of at least two of pyridyl, pyrimidinyl, pyrazinyl, triazinyl, phenanthrolinel, quinoxalinyl, quinazolinyl or triazolyl.

[0039] The C3-C50 heteroaryl group is a divalent group obtained by removing a hydrogen atom from the above-mentioned C3-C50 (e.g., C3, C4, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C35, C40, C45 or C48, etc.) heteroaryl group.

[0040] The C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.) straight-chain or branched alkyl groups, more preferably C1-C12 straight-chain or branched alkyl groups, exemplary including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, etc.

[0041] The C3 to C20 (e.g., C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.) cycloalkyl groups, exemplary including but not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0042] In this invention, the halogen can be F, Cl, Br or I.

[0043] In this invention, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents (at least two), the multiple (at least two) substituents can be the same or different groups. The substituents can be attached to any position within the group. The same expressions used below have the same meaning.

[0044] The boron-nitrogen silicon compound provided by this invention has the structure shown in Formula I or Formula II. Through the structural design of the boron-nitrogen silicon compound, the obtained boron-nitrogen silicon compound has good thermal stability and excellent light-emitting performance, and can be used in OLEDs, especially as a light-emitting layer material in OLEDs. It can effectively reduce the driving voltage of OLEDs, improve the current efficiency of OLEDs, and extend the service life of OLEDs.

[0045] 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.

[0046] As a preferred technical solution, R1 and R2 are each independently selected from C6-C20 aryl, C1-C10 straight-chain or branched alkyl groups.

[0047] Each of C6 to C20 can independently be C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.

[0048] Each of C1 to C10 can independently be C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10, etc.

[0049] Preferably, R1 and R2 are each independently selected from methyl or phenyl.

[0050] As a preferred technical solution, the Ar is selected from C6 to C20 arylene, and more preferably C6 to C12 arylene.

[0051] Each of C6 to C20 can independently be C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.

[0052] Each of C6 to C12 can independently be C6, C7, C8, C9, C10, C11, or C12, etc.

[0053] Preferably, the Ar is selected from any one of the following groups:

[0054] in,

[0055] The linking site of the representative group.

[0056] Preferably, X1 and Y1 are each independently selected from any one of the following groups:

[0057]

[0058] In this context, the dashed lines represent the bonding sites of functional groups.

[0059] R 11 It is selected from any one of halogen, cyano, unsubstituted or R'-substituted C6-C20 aryl, unsubstituted or R'-substituted C4-C20 heteroaryl, and unsubstituted or R'-substituted C1-C12 straight-chain or branched alkyl; wherein R' is selected from at least one of halogen or cyano.

[0060] m1, m2, m3, m4, and m5 represent substituents R. 11 The number.

[0061] m1 is selected from integers from 0 to 5, for example, it can be 0, 1, 2, 3, 4 or 5.

[0062] m2 is selected from integers from 0 to 4, for example, it can be 0, 1, 2, 3 or 4.

[0063] m3 is selected from integers from 0 to 3, for example, it can be 0, 1, 2 or 3.

[0064] m4 is selected from integers between 0 and 2, for example, it can be 0, 1 or 2.

[0065] Preferably, X1 and Y1 are each independently selected from any one of the following groups:

[0066]

[0067] In this context, the dashed lines represent the bonding sites of functional groups.

[0068] As a preferred technical solution, X2 and Y2 are each independently selected from any one of the following groups: In this context, the dashed lines represent the bonding sites of functional groups.

[0069] R 12 It is selected from at least one of halogen, cyano, unsubstituted or R”-substituted C6-C50 aryl, unsubstituted or R”-substituted C4-C50 heteroaryl, C1-C20 straight-chain or branched alkyl, and C3-C20 cycloalkyl. The R on the same group in the above formula... 12 It can represent the same substituent or different substituents.

[0070] The R” is selected from at least one of halogen, cyano, unsubstituted or R”'-substituted C6-C20 aryl, unsubstituted or R”'-substituted C4-C20 heteroaryl, and unsubstituted or R”'-substituted C1-C12 straight-chain or branched alkyl; the R”' is selected from at least one of halogen or cyano.

[0071] m6, m7, and m8 represent substituent R. 12 The number.

[0072] m6 is selected from integers from 0 to 6, for example, it can be 0, 1, 2, 3, 4, 5 or 6.

[0073] m7 is selected from integers from 0 to 4, for example, it can be 0, 1, 2, 3 or 4.

[0074] m8 is selected from integers from 0 to 3, for example, it can be 0, 1, 2 or 3.

[0075] Preferably, X2 and Y2 are each independently selected from any one of the following groups:

[0076] In this context, the dashed lines represent the bonding sites of functional groups.

[0077] Preferably, the formula II is described Selected from any one of the following groups:

[0078] In this context, the dashed lines represent the bonding sites of functional groups.

[0079] R 13 R 14 Each is independently selected from at least one of halogen, cyano, unsubstituted or R”-substituted C6-C50 aryl, unsubstituted or R”-substituted C4-C50 heteroaryl, C1-C20 straight-chain or branched alkyl, and C3-C20 cycloalkyl.

[0080] The R” is selected from at least one of halogen, cyano, unsubstituted or R”'-substituted C6-C20 aryl, unsubstituted or R”'-substituted C4-C20 heteroaryl, and unsubstituted or R”'-substituted C1-C12 straight-chain or branched alkyl; the R”' is selected from at least one of halogen or cyano. In the formula, R… 13 When it appears, R 13 R can represent the same substituent or different substituents. 14 When it appears, R 14 It can represent the same substituent or different substituents.

[0081] m9、m 10 m 11 Represents substituent R 13 R 14 The number.

[0082] m9 is selected from integers from 0 to 4, for example, it can be 0, 1, 2, 3 or 4.

[0083] m 10 Integers selected from 0 to 3, for example, can be 0, 1, 2 or 3.

[0084] m 11 Integers selected from 0 to 6, for example, 0, 1, 2, 3, 4, 5 or 6.

[0085] As a preferred technical solution, Ar is The above in Formula II Selected from any one of the following groups:

[0086]

[0087] in, Both dashed lines and dashed lines represent the connection sites of functional groups.

[0088] R 15 R 16 Each is independently selected from at least one of halogen, cyano, unsubstituted or R”-substituted C6-C50 aryl, unsubstituted or R”-substituted C4-C50 heteroaryl, C1-C20 straight-chain or branched alkyl, and C3-C20 cycloalkyl.

[0089] The R” is selected from at least one of halogen, cyano, unsubstituted or R”'-substituted C6-C20 aryl, unsubstituted or R”'-substituted C4-C20 heteroaryl, and unsubstituted or R”'-substituted C1-C12 straight-chain or branched alkyl; the R”' is selected from at least one of halogen or cyano. In the formula, R… 15 When it appears, R 15 R can represent the same substituent or different substituents. 16 When it appears, R 16 It can represent the same substituent or different substituents.

[0090] m 12 m 13 m 14 Represents substituent R 15 R 16 The number.

[0091] m 12 Integers selected from 0 to 4, for example, 0, 1, 2, 3 or 4.

[0092] m 13 Integers selected from 0 to 3, for example, can be 0, 1, 2 or 3.

[0093] m 14 Integers selected from 0 to 6, for example, 0, 1, 2, 3, 4, 5 or 6.

[0094] As a preferred technical solution, the compound includes any one of 1 to 306:

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] As a preferred technical solution, the intermediate of the compound includes the following compounds:

[0113]

[0114]

[0115] The intermediate is a compound that reacts with the portion of the raw material containing B to obtain the structure shown in Formula I or Formula II of this invention.

[0116] In a second aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode; the material of the organic layer comprises a boron-nitrogen silicon compound as described in the first aspect.

[0117] As a preferred technical solution, the organic layer includes a light-emitting layer; the material of the light-emitting layer includes boron-nitrogen silicon compounds as described in the first aspect.

[0118] Preferably, the doping material of the light-emitting layer is the boron-nitrogen silicon compound described in the first aspect.

[0119] Thirdly, the present invention provides a display device comprising the organic electroluminescent device as described in the second aspect.

[0120] Compared with the prior art, the present invention has the following beneficial effects:

[0121] This invention designs the structure of boron-nitrogen silicon compounds to obtain compounds with excellent light-emitting properties, which can be used to prepare OLEDs, especially as dopant materials for the light-emitting layer of OLEDs. This can effectively reduce the driving voltage of organic electroluminescent devices, improve the current efficiency of OLEDs, and extend the lifespan of OLEDs. Detailed Implementation

[0122] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0123] The sources of some components in the following examples and comparative examples are as follows:

[0124] (1) Preparation of intermediate 0

[0125]

[0126] The preparation method of the intermediate 0 is as follows:

[0127] ① Dissolve 0.1 mol of O-A1 in 300 mL of tetrahydrofuran (THF), cool to -10℃, and add 88 mL of 2.5 mol / L (0.22 mol) butyllithium dropwise at -5 to 0℃. After the addition is complete, react at -5 to 0℃ for 1 h. Then add 27.8 g (0.11 mol) of diphenyldichlorosilane in THF solution (diluted with 100 mL of THF) dropwise, maintaining the temperature at -5 to 0℃ during the addition. After the addition is complete, maintain the temperature for 0.5 h, then slowly raise the temperature to room temperature and continue stirring for 2 h. Then slowly pour the reaction solution into an ice-water mixture to quench the reaction. Afterward, separate the liquid and wash with water, and extract twice with 200 mL of ethyl acetate. Combine the organic phases and dry them. Filter the organic phase through 50 g of ethyl acetate. 200-300 mesh silica gel was used, and then concentrated to dryness. The resulting solid was heated and refluxed with 50 mL toluene and 100 mL ethanol for 1 h. After cooling to room temperature, it was filtered to obtain intermediate 0-A2 with an HPLC purity of 98.8% and a yield of 60%.

[0128] ② Add 0.05 mol of intermediate O-A2 to a hydrogenation reactor, along with 100 mL of ethanol, 100 mL of ethyl acetate, 100 mL of dichloromethane, and 1 g of palladium on carbon (Pd content 5%). The hydrogen pressure is 0.1 MPa, the reaction temperature is 30 °C, and the reaction is carried out for 48 h. After the raw materials have basically reacted, add 10 mL of water, then filter to remove the palladium on carbon. Concentrate the filtrate to dryness, reflux with 50 mL of ethanol for 1 h, cool to room temperature, and filter to obtain intermediate O with an HPLC purity of 98.3% and a yield of 40%.

[0129] The intermediate 0 was subjected to mass spectrometry, and the mass spectrometry m / z was 349.13.

[0130] Theoretical element content (%) C 24 H 19 NSi: C, 82.48; H, 5.48; N, 4.01; Si, 8.04; Measured element content (%): C, 82.46; H, 5.49; N, 4.02.

[0131] (2) Preparation of intermediate 1

[0132] The preparation method of intermediate 1 is as follows:

[0133]

[0134] In a 500 mL three-necked flask, 60 mL of xylene, 5.77 g (0.06 mol) of sodium tert-butoxide, 9 g of 1-Al, 28.3 g of m-bromoiodobenzene, 0.002 g of Pd2(dba)3, and 0.014 g of a 10% toluene solution of tri-tert-butylphosphine were added. The mixture was refluxed for 4 h. When the remaining starting material was <0.5%, the reaction was stopped, the mixture was cooled to room temperature, and 50 mL of water and 50 mL of ethanol were added. The mixture was heated to 60 °C and stirred for 0.5 h. After the product precipitated, it was filtered. The obtained solid was dissolved in toluene and passed through 50 g of 200-300 mesh silica gel. The filtrate was concentrated until solid precipitated. After cooling to room temperature, it was filtered to obtain intermediate 1 with an HPLC purity of 99.5% and a yield of 20%.

[0135] Mass spectrometry was performed on intermediate 1, and the two largest m / z peaks were found to be 381.04 and 379.04.

[0136] Theoretical element content (%) C 20 H 18 BrNSi: C, 63.16; H, 4.77; Br, 21.01; N, 3.68; Si, 7.38; Measured elemental content (%): C, 63.14; H, 4.78; Br, 21.03; N, 3.66.

[0137] (3) Preparation of intermediate 2

[0138] The preparation method of the intermediate 2 is as follows:

[0139]

[0140] The preparation method of intermediate 2 differs from that of intermediate 1 only in that 1-A1 and m-bromoiodobenzene in the raw materials for intermediate 1 are replaced with 2-A1 and o-bromoiodobenzene. The other raw materials, reaction conditions and reaction steps are the same as those for intermediate 1. The intermediate 2 obtained has an HPLC purity of 98.6% and a yield of 19%.

[0141] (4) Preparation of intermediate 3

[0142] The preparation method of the intermediate 3 is as follows:

[0143]

[0144] The preparation method of intermediate 3 differs from that of intermediate 1 only in that 1-A1 and m-bromoiodobenzene in the raw materials for preparing intermediate 1 are replaced with 3-A1 and 1-bromo-4-iodonaphthalene. The other raw materials, reaction conditions and reaction steps are the same as those for intermediate 1. The intermediate 3 obtained has an HPLC purity of 99.2% and a yield of 24%.

[0145] (5) Preparation of intermediate 4

[0146] The preparation method of the intermediate 4 is as follows:

[0147]

[0148] The preparation method of intermediate 4 differs from that of intermediate 1 only in that 1-A1 and m-bromoiodobenzene in the raw materials for preparing intermediate 1 are replaced with 4-A1 and 1-bromo-5-iodonaphthalene. The other raw materials, reaction conditions and reaction steps are the same as those for intermediate 1. The intermediate 4 obtained has an HPLC purity of 99.5% and a yield of 21%.

[0149] (6) Preparation of intermediate 5

[0150] The intermediate 5 is prepared as follows:

[0151]

[0152] The preparation method of intermediate 5 differs from that of intermediate 1 only in that 1-A1 and m-bromoiodobenzene in the raw materials of intermediate 1 are replaced with 5-A1 and 2-bromo-6-iodonaphthalene. The other raw materials, reaction conditions and reaction steps are the same as those of intermediate 1. The intermediate 5 obtained has an HPLC purity of 99.6% and a yield of 24%.

[0153] (7) Preparation of intermediate 6

[0154] The intermediate 6 is prepared as follows:

[0155]

[0156] The preparation method of intermediate 6 differs from that of intermediate 1 only in that 1-A1 and m-bromoiodobenzene in the raw materials for preparing intermediate 1 are replaced with 6-A1 and p-bromoiodobenzene. The other raw materials, reaction conditions and reaction steps are the same as those for intermediate 1. The intermediate 6 obtained has an HPLC purity of 99.5% and a yield of 29%.

[0157] (8) Preparation of intermediate 7

[0158] The intermediate 7 is prepared as follows:

[0159]

[0160] The preparation method of intermediate 7 differs from that of intermediate 1 only in that 1-A1 in the raw materials of intermediate 1 is replaced with 7-A1. The other raw materials, reaction conditions and reaction steps are the same as those of intermediate 1. The intermediate 7 obtained has an HPLC purity of 99.6% and a yield of 26%.

[0161] (9) Preparation of intermediate 8

[0162] The intermediate 8 is prepared as follows:

[0163]

[0164] The preparation method of intermediate 8 differs from that of intermediate 1 only in that 1-A1 and m-bromoiodobenzene in the raw materials of intermediate 1 are replaced with 8-A1 and o-bromoiodobenzene. The other raw materials, reaction conditions and reaction steps are the same as those of intermediate 1. The intermediate 8 obtained has an HPLC purity of 99.7% and a yield of 20%.

[0165] (10) Preparation of intermediate 9

[0166] The preparation method of intermediate 9 is as follows:

[0167]

[0168] The preparation method of intermediate 9 differs from that of intermediate 1 only in that 1-A1 and m-bromoiodobenzene in the raw materials for intermediate 1 are replaced with 9-A1 and 1-bromo-4-iodonaphthalene. The other raw materials, reaction conditions and reaction steps are the same as those for intermediate 1. The intermediate 9 obtained has an HPLC purity of 99.5% and a yield of 30%.

[0169] (11) Preparation of intermediate 10

[0170] The intermediate 10 is prepared as follows:

[0171]

[0172] The preparation method of intermediate 10 differs from that of intermediate 1 only in that 1-A1 and m-bromoiodobenzene in the raw materials for preparing intermediate 1 are replaced with 10-A1 and 1-bromo-5-iodonaphthalene. The other raw materials, reaction conditions and reaction steps are the same as those for intermediate 1. The obtained intermediate 10 has an HPLC purity of 99.6% and a yield of 31%.

[0173] (12) Preparation of intermediate 11

[0174] The intermediate 11 is prepared as follows:

[0175]

[0176] The preparation method of intermediate 11 differs from that of intermediate 1 only in that 1-A1 and m-bromoiodobenzene in the raw materials for preparing intermediate 1 are replaced with 11-A1 and 2-bromo-6-iodonaphthalene. The other raw materials, reaction conditions and reaction steps are the same as those for preparing intermediate 1. The intermediate 11 obtained has an HPLC purity of 99.5% and a yield of 29%.

[0177] The following are exemplary examples of the preparation of boron-nitrogen silicon compounds described in this invention.

[0178] Example 1

[0179] A boron-nitrogen-silicon compound 1 has the following structure: The preparation method of compound 1 is as follows:

[0180]

[0181] Add 0.1 mol of intermediate 12 to a 1 L three-necked flask and dissolve and clarify it with 400 mL of THF. Under nitrogen protection, lower the temperature to -80 to -75 °C and add 48 mL of 2.5 mol / L n-butyllithium (0.12 mol) dropwise, maintaining the temperature between -80 and -75 °C during the addition. After the addition is complete, keep the reaction at this temperature for 1 h. Then add 22.2 g of 9-isopropylether-9-boronfluorene (0.1 mol) dropwise. After the addition is complete, slowly raise the temperature to room temperature and stir for 1 h. Then quench the reaction with water, separate the liquid and aqueous phase, extract twice with 200 mL × 2 toluene, combine the organic phases and dry them, then pass them through 50 g of 200-300 mesh silica gel. Concentrate the resulting chromatogram to dryness and recrystallize once with 50 g of ethanol and 100 g of toluene to obtain compound 1 with a mass of 22 g and a purity of 99.7%.

[0182] The mass spectrometry of compound 1 was performed, and the mass spectrum m / z was 463.19.

[0183] Theoretical element content (%) C 32 H 26 BNSi: C, 82.93; H, 5.65; B, 2.33; N, 3.02; Si, 6.06, Measured element content (%): C, 82.91; H, 5.64; B, 2.34; N, 3.02; Si, 6.08.

[0184] Example 2

[0185] A boron-nitrogen-silicon compound 109 has the following structure: The preparation method of compound 109 is as follows:

[0186]

[0187] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 2, while other raw materials, amounts and process parameters are the same as in Example 1, to obtain the boron-nitrogen silicon compound 109.

[0188] The mass spectrometry of compound 109 was performed, and the mass spectrum m / z was 463.19.

[0189] Example 3

[0190] A boron-nitrogen-silicon compound 163 has the following structure: The preparation method of compound 163 is as follows:

[0191]

[0192] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 3, while other raw materials, amounts and process parameters are the same as in Example 1, to obtain the boron-nitrogen silicon compound 163.

[0193] The mass spectrometry of compound 163 was performed, and the mass spectrum m / z was 513.21.

[0194] Example 4

[0195] A boron-nitrogen-silicon compound 217 has the following structure: The preparation method of compound 217 is as follows:

[0196]

[0197] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 4, while other raw materials, amounts and process parameters are the same as in Example 1, to obtain the boron-nitrogen silicon compound 217.

[0198] The mass spectrometry of compound 217 was performed, and the mass spectrum m / z was 513.21.

[0199] Example 5

[0200] A boron-nitrogen-silicon compound 271 has the following structure: The preparation method of compound 271 is as follows:

[0201]

[0202] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 5, while other raw materials, amounts and process parameters are the same as in Example 1, to obtain the boron-nitrogen silicon compound 271.

[0203] The mass spectrometry of compound 271 was performed, and the mass spectrum m / z was 513.21.

[0204] Example 6

[0205] A boron-nitrogen-silicon compound 4 has the following structure: The preparation method of compound 4 is as follows:

[0206]

[0207] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 6, while other raw materials, amounts and process parameters are the same as in Example 1, to obtain the boron-nitrogen silicon compound 4.

[0208] The mass spectrometry of compound 4 was performed, and the mass spectrum m / z was 587.22.

[0209] Example 7

[0210] A boron-nitrogen-silicon compound 58 has the following structure: The preparation method of compound 58 is as follows:

[0211]

[0212] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 7. All other raw materials, amounts and process parameters are the same as in Example 1, and the boron-nitrogen silicon compound 58 is obtained.

[0213] The mass spectrometry of compound 58 was performed, and the mass spectrum m / z was 587.22.

[0214] Example 8

[0215] A boron-nitrogen-silicon compound 112 has the following structure: The preparation method of compound 112 is as follows:

[0216]

[0217] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 8, while other raw materials, amounts and process parameters are the same as in Example 1, to obtain the boron-nitrogen silicon compound 112.

[0218] The mass spectrometry of compound 112 was performed, and the mass spectrum m / z was 587.22.

[0219] Example 9

[0220] A boron-nitrogen-silicon compound 166 has the following structure: The preparation method of compound 166 is as follows:

[0221]

[0222] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 9, while other raw materials, amounts and process parameters are the same as in Example 1, to obtain the boron-nitrogen silicon compound 166.

[0223] The mass spectrometry of compound 166 was performed, and the mass spectrum m / z was 637.24.

[0224] Example 10

[0225] A boron-nitrogen-silicon compound 220 has the following structure: The preparation method of compound 220 is as follows:

[0226]

[0227] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 10, while other raw materials, amounts and process parameters are the same as in Example 1, to obtain the boron-nitrogen silicon compound 220.

[0228] The mass spectrometry of compound 220 was performed, and the mass spectrum m / z was 637.24.

[0229] Example 11

[0230] A boron-nitrogen-silicon compound 274 has the following structure: The preparation method of compound 274 is as follows:

[0231]

[0232] The only difference from Example 1 is that intermediate 12 in Example 1 is replaced with an equimolar amount of intermediate 11, while other raw materials, amounts and process parameters are the same as in Example 1, to obtain the boron-nitrogen silicon compound 274.

[0233] The mass spectrometry of compound 274 was performed, and the mass spectrum m / z was 637.24.

[0234] Example 12

[0235] A boron-nitrogen-silicon compound 91 has the following structure: The preparation method of compound 91 is as follows:

[0236]

[0237] The only difference from Example 1 is that intermediate 12 and 9-isopropyl ether-9-boronfluorene in Example 1 are replaced with equimolar amounts of intermediate 2 and... The other raw materials, dosages, and process parameters were the same as in Example 1, resulting in the boron-nitrogen silicon compound 91.

[0238] The mass spectrometry of compound 91 was performed, and the mass spectrum m / z was 465.21.

[0239] Example 13

[0240] A boron-nitrogen-silicon compound 145 has the following structure: The preparation method of compound 145 is as follows:

[0241]

[0242] The only difference from Example 12 is that intermediate 2 in Example 12 is replaced with an equimolar amount of intermediate 3, while other raw materials, amounts and process parameters are the same as in Example 12, to obtain the boron-nitrogen silicon compound 145.

[0243] The mass spectrometry of compound 145 was performed, and the mass spectrum m / z was 515.22.

[0244] Example 14

[0245] A boron-nitrogen-silicon compound 199 has the following structure: The preparation method of compound 199 is as follows:

[0246]

[0247] The only difference from Example 12 is that intermediate 2 in Example 12 is replaced with an equimolar amount of intermediate 4. All other raw materials, amounts and process parameters are the same as in Example 12, and the boron-nitrogen silicon compound 199 is obtained.

[0248] The mass spectrometry of compound 199 was performed, and the mass spectrum m / z was 515.22.

[0249] Example 15

[0250] A boron-nitrogen-silicon compound 253 has the following structure: The preparation method of compound 253 is as follows:

[0251]

[0252] The only difference from Example 12 is that intermediate 2 in Example 12 is replaced with an equimolar amount of intermediate 5. All other raw materials, amounts and process parameters are the same as in Example 12, and the boron-nitrogen silicon compound 253 is obtained.

[0253] The mass spectrometry of compound 253 was performed, and the mass spectrum m / z was 515.22.

[0254] Example 16

[0255] A boron-nitrogen-silicon compound 46 has the following structure: The preparation method of compound 46 is as follows:

[0256]

[0257] The only difference from Example 12 is that intermediate 2 in Example 12 is replaced with an equimolar amount of intermediate 7, while other raw materials, amounts and process parameters are the same as in Example 12, to obtain the boron-nitrogen silicon compound 46.

[0258] The mass spectrometry of compound 46 was performed, and the mass spectrum m / z was 589.24.

[0259] Example 17

[0260] A boron-nitrogen-silicon compound 100 has the following structure: The preparation method of compound 100 is as follows:

[0261]

[0262] The only difference from Example 12 is that intermediate 2 in Example 12 is replaced with an equimolar amount of intermediate 8, while other raw materials, amounts and process parameters are the same as in Example 12, to obtain the boron-nitrogen silicon compound 100.

[0263] The mass spectrometry of compound 100 was performed, and the mass spectrum m / z was 589.24.

[0264] Example 18

[0265] A boron-nitrogen-silicon compound 154 has the following structure: The preparation method of compound 154 is as follows:

[0266]

[0267] The only difference from Example 12 is that intermediate 2 in Example 12 is replaced with an equimolar amount of intermediate 9, while other raw materials, amounts and process parameters are the same as in Example 12, to obtain the boron-nitrogen silicon compound 154.

[0268] The mass spectrometry of compound 154 was performed, and the mass spectrum m / z was 639.26.

[0269] Example 19

[0270] A boron-nitrogen-silicon compound 208 has the following structure: The preparation method of compound 208 is as follows:

[0271]

[0272] The only difference from Example 12 is that intermediate 2 in Example 12 is replaced with an equimolar amount of intermediate 10. All other raw materials, amounts and process parameters are the same as in Example 12, resulting in boron-nitrogen silicon compound 208.

[0273] The mass spectrometry of compound 208 was performed, and the mass spectrum m / z was 639.26.

[0274] Example 20

[0275] A boron-nitrogen-silicon compound 262 has the following structure: The preparation method of compound 262 is as follows:

[0276]

[0277] The only difference from Example 12 is that intermediate 2 in Example 12 is replaced with an equimolar amount of intermediate 11. All other raw materials, amounts and process parameters are the same as in Example 12, resulting in boron-nitrogen silicon compound 262.

[0278] The mass spectrometry of compound 262 was performed, and the mass spectrum m / z was 639.26.

[0279] The following are some examples of applications of the boron-nitrogen silicon compounds described in this invention in organic light-emitting devices (OLED devices):

[0280] Device Application Example 1

[0281] An organic electroluminescent device, wherein the organic electroluminescent device has the following structure:

[0282] ITO / HT (40nm) / BH-1: Dopant material = 1:3% (35nm) / TPBI (30nm) / LiF (0.5nm) / Al (150nm); The dopant material is a boron-nitrogen silicon compound provided by this invention.

[0283] The method for fabricating the organic electroluminescent device includes the following steps:

[0284] (1) The glass substrate coated with an indium tin oxide (ITO) transparent conductive layer (as anode) was ultrasonically treated in a cleaning agent, then rinsed in deionized water, then ultrasonically degreased in a mixed solvent of acetone and ethanol, then dried in a clean environment, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam to improve the surface properties and enhance the bonding ability with the hole injection layer.

[0285] (2) Place the glass substrate in a vacuum chamber and evacuate it to 1×10⁻⁶. -5 ~9×10 -3 Pa, HT was vacuum-deposited on the ITO anode as a hole transport layer at a deposition rate of 0.1 nm / s and a film thickness of 40 nm.

[0286] (3) The glass substrate in which the hole transport layer has been deposited in step (2) is transferred to a glove box filled with nitrogen. BH-1 and 3% by mass of the boron-nitrogen silicon compound 1 provided by the present invention are dissolved as dopants in 4-cyclohexylbenzene:chlorobenzene = 3:1 (volume ratio) to prepare a solution. The solution is then spin-coated on the hole transport layer as a light-emitting layer. By adjusting the concentration of BH-1 and the boron-nitrogen silicon compound 1 provided by the present invention in the solvent, the thickness of the light-emitting layer is 35 nm. The spin-coating speed is 1000 r / min and the time is 60 s. Then the glass substrate is heated at 80 °C for 2 h and the solvent is removed under vacuum.

[0287] (4) Transfer the glass substrate with the light-emitting layer spin-coated in step (3) to the vacuum chamber, and vacuum evaporate TPBI on the light-emitting layer as the electron transport layer of the device. The evaporation rate is 0.1 nm / s and the total film thickness is 30 nm.

[0288] (5) A 0.5 nm thick LiF layer was vacuum-deposited on the electron transport layer as an electron injection layer;

[0289] (6) Vacuum evaporation of 150 nm Al on the electron injection layer as a cathode to obtain the organic electroluminescent device.

[0290] The material structure used in the organic electroluminescent device is as follows:

[0291]

[0292]

[0293] Device Application Example 2-22

[0294] An organic electroluminescent device differs from Device Application Example 1 only in that the boron-nitrogen silicon compound 1 in step (3) is replaced with equal amounts of compounds 109, 271, 91, 253, 262, 25, 27, 38, 39, 45, 48, 54, 64, 79, 85, 92, 99, 102, 127, 150, and 156; the structure, thickness, other materials, and preparation method of the device are the same as those of Device Application Example 1.

[0295] Device Comparison Examples 1-6

[0296] An organic electroluminescent device, which differs from device application example 1 only in that the doping material in step (3) is replaced with equal amounts of BD-1, BD-2, BD-3, BD-4, BD-5 and BD-6 respectively; the structure, thickness, other materials and preparation method of the device are the same as those of device application example 1.

[0297] Performance evaluation of organic electroluminescent devices:

[0298] The driving voltage, current efficiency, and lifetime (LT90) of OLED devices were tested using the OLED-1000 multi-channel accelerated aging lifetime and color performance analysis system manufactured by Hangzhou Yuanfang. LT90 refers to the time required for the brightness to decrease to 90% of its original brightness while maintaining an initial brightness of 1000 nits at a constant current density. The driving voltage, current efficiency, and LT90 data for the OLED devices were all based on a brightness of 1000 cd / m². 2 The ratio of the measured data to the actual brightness of 1000 cd / m² is the value of the measured data. 2 The relative value of the test data at that time.

[0299] Taking the test data of drive voltage, current efficiency, and LT90 of Device Comparison Example 1 as a reference, the drive voltage, current efficiency, and LT90 of Device Application Examples 1-23 and Device Comparison Examples 2-6 are the ratios of their respective test data to the test data of Device Comparison Example 1, which are the relative values ​​compared to Device Comparison Example 1.

[0300] The performance test results of the organic electroluminescent devices are shown in Table 1 below.

[0301] Table 1

[0302]

[0303]

[0304] As shown in Table 1, compared with the device comparison example, the boron-nitrogen silicon compound provided by the present invention can be used as a doping material for the light-emitting layer of OLED light-emitting devices, and can enable OLED light-emitting devices to have lower driving voltage, higher current efficiency and longer lifespan.

[0305] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A boron-nitrogen-silicon compound, characterized in that, The compound has the structure shown in Formula II; Formula II; R1 and R2 are each independently selected from any one of C1 to C20 straight-chain or branched alkyl groups; Ar is selected from any one of the following groups: 、 、 ； The linking site of the representative group; The formula described in Formula II Selected from any one of the following groups: 、 、 ； In this context, the dashed lines represent the connection sites of functional groups; R 13 R 14 Each is independently selected from at least one of halogen, cyano, unsubstituted or R''-substituted C6-C50 aryl, unsubstituted or R''-substituted C4-C50 heteroaryl, C1-C20 straight-chain or branched alkyl, and C3-C20 cycloalkyl; The R'' is selected from at least one of halogen, cyano, unsubstituted or R'''-substituted C6-C20 aryl, unsubstituted or R'''-substituted C4-C20 heteroaryl, and unsubstituted or R'''-substituted C1-C12 straight-chain or branched alkyl; the R''' is selected from at least one of halogen or cyano. m9 is selected from integers between 0 and 4, m 10 Integers selected from 0 to 3.

2. The compound according to claim 1, characterized in that, R1 and R2 are each independently selected from any one of C1 to C10 straight-chain or branched alkyl groups.

3. The compound according to claim 2, characterized in that, R1 and R2 are each independently selected from methyl groups.

4. The compound according to claim 1, characterized in that, The compound includes any one of the following structures: 。 5. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode; the material of the organic layer includes the boron-nitrogen silicon compound as described in any one of claims 1 to 4.

6. The organic electroluminescent device according to claim 5, characterized in that, The organic layer includes a light-emitting layer; the material of the light-emitting layer includes a boron-nitrogen silicon compound as described in any one of claims 1 to 4.

7. A display device, characterized in that, The display device includes the organic electroluminescent device as described in claim 5 or 6.

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