Organic compound containing boron and nitrogen and application of organic compound in organic electronic device

Abstract

The invention provides an organic compound containing boron and nitrogen and application of the organic compound in an organic electronic device, the organic compound containing boron and nitrogen has a structure represented by a chemical formula (I)-a chemical formula (IV), and the organic compound containing boron and nitrogen is applied to the organic electronic device. The device using the organic compound containing boron and nitrogen has high luminous efficiency, narrow luminescent spectrum FWHM, long service life and the like.

Description

A boron-nitrogen-containing organic compound and its application in organic electronic devices Technical Field

[0001] The present invention relates to the technical field of organic electronic materials and devices, and in particular to an organic compound containing boron and nitrogen, a polymer, a mixture, a composition containing the same, and applications thereof in organic electronic devices, in particular in organic electroluminescent devices. Background Art

[0002] Organic light-emitting diodes (OLEDs) have great application potential in the display field due to their excellent optoelectronic properties, such as fast response, high contrast, low production cost, and diversity in chemical synthesis.

[0003] Traditional OLED materials: The full width at half maximum (FWHM) of the emission spectrum of fluorescent materials is about 40nm to 60nm, the FWHM of phosphorescent materials is about 60nm to 90nm, and the FWHM of thermally activated delayed fluorescence (TADF) materials is about 70nm to 100nm. Therefore, traditional OLED materials have a large full width at half maximum and exhibit low color purity, which does not meet the newly proposed BT.2020 standard. To improve color purity, it is necessary to use optical filters in the display to remove unwanted colors from the self-luminous spectrum, which greatly reduces the luminous efficiency.

[0004] In 2016, boron-nitrogen TADF compounds (DOI: 10.1002 / adma.201505491) exhibiting the multi-resonance (MR) effect garnered widespread attention. These molecules not only efficiently emit light through reverse intersystem crossing (RISC), but also exhibit a narrow full width at half maximum (FWHM). They are currently one of the hottest topics in the field of OLED luminescent materials.

[0005] However, the stability of boron nitride compounds still needs to be improved. Furthermore, boron nitride compounds often have a planar core structure, typically represented by the compound shown in the following chemical formula ae. Due to strong intermolecular interactions, MR boron nitride compounds can still aggregate at low doping concentrations of approximately 3wt%, resulting in a red-shifted emission spectrum. This intermolecular accumulation also significantly reduces device efficiency and impacts device lifetime. Therefore, there is still room for improvement in developing boron nitride compounds with higher luminous efficiency, narrower full width at half maximum (FWHM), and longer device lifetimes.

[0006] Summary of the Invention

[0007] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide an organic compound containing boron and nitrogen, or a polymer, mixture, composition, organic electronic device and application thereof, aiming to solve the problems of efficiency and life span of existing OLEDs.

[0008] The technical solutions of the present invention are as follows:

[0009] A boron-nitrogen-containing organic compound having a structure shown by one of chemical formulas (I) to (IV):

[0010] Wherein: Q1 ring and Q2 ring, when each occurs, are independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted fused ring structure;

[0011] X is selected from B, N, P, P═O or Al;

[0012] Y1 and Y2, at each occurrence, are independently selected from C=O, N-R1, O, S, Se, P, P=O or P=S;

[0013] V0, at each occurrence, is independently selected from C-R2 or N;

[0014] V1, V2, and V3, at each occurrence, are independently selected from C-R3 or N;

[0015] R, R1, R2, R3, at each occurrence, are selected, identically or differently, from H or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a halide group, or a halogen group. formyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups, and one or more groups of R3 can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which the groups are bonded.

[0016] The present invention also relates to a polymer comprising at least one first repeating unit, wherein the first repeating unit comprises at least one structure corresponding to the boron-nitrogen-containing organic compound as described above.

[0017] The present invention also relates to a composition comprising at least one organic solvent and at least one boron-nitrogen-containing organic compound as described above or at least one polymer as described above.

[0018] The present invention further relates to a mixture comprising an organic compound containing boron and nitrogen as described above or a polymer as described above, and at least one organic functional material, wherein the organic functional material can be selected from at least one of a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminophore and a host material.

[0019] The present invention further relates to an organic electronic device comprising at least one boron-nitrogen-containing organic compound as described above, or a polymer as described above, or a mixture as described above.

[0020] Beneficial Effects: By incorporating the boron-nitrogen-containing organic compound into an organic light-emitting device (OLED), the present invention enables the OLED to achieve high luminous efficiency, high color purity, high device stability, and a long device lifespan. The OLED, according to the present invention, primarily utilizes a large conjugated group as a modifying group to improve the optical properties of the boron-nitrogen backbone. By introducing a large conjugated group, i.e., the Q1 ring is fused to the BN core structure via a pentacyclic ring, the conjugation length of the boron-nitrogen molecule can be extended, thereby improving molecular stability. Furthermore, by introducing different conjugated groups, the electron cloud density around adjacent B atoms can be adjusted, facilitating the adjustment of the molecule's luminescence spectrum. Furthermore, the large conjugated group improves the planar stacking effect of the molecule to a certain extent, reducing exciton annihilation in the device, thereby achieving the effect of adjusting the luminescent color of the organic compound and improving the efficiency and lifespan of the luminescent device. The inventors surprisingly discovered that, in certain cases, even with an increased conjugated structure, blue light emission can be maintained, resulting in an OLED with high luminous efficiency, high color purity, and a long device lifespan. DETAILED DESCRIPTION

[0021] The present invention provides an organic compound containing boron and nitrogen, which can be used as an organic light-emitting material in an organic light-emitting device, but is not limited thereto. The organic compound containing boron and nitrogen is optimized to have high luminous efficiency, narrow luminous spectrum FWHM and long luminous lifetime.

[0022] In order to make the purpose, technical solutions and effects of the present invention clearer and more specific, the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. The data ranges involved in the present invention should include end values ​​unless otherwise specified.

[0023] In the present invention, main body material, matrix material, host material and matrix material have the same meaning and can be interchanged.

[0024] In the present invention, guest material, luminescent material and emitter material have the same meaning and can be interchanged.

[0025] In the present invention, color converter, color conversion layer and CCL have the same meaning and can be interchanged.

[0026] In the present invention, composition, printing ink, ink and ink have the same meaning and can be interchanged.

[0027] In the present invention, "substituted" means that a hydrogen atom in a compound is replaced by a substituent.

[0028] In the present invention, when the same substituent appears multiple times, each substituent may be independently selected from different groups.

[0029] In the present invention, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted with a substituent, it is understood that it is optionally substituted with a substituent acceptable in the art, and the substituent may be further substituted with a substituent acceptable in the art.

[0030] In the present invention, the "number of ring atoms" refers to the number of atoms that constitute the ring itself in a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, or a heterocyclic compound) formed by atoms bonded together to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below also applies unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5.

[0031] An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group containing at least one heteroatom. The heteroatom is preferably selected from Si, N, P, O, S and / or Ge, and particularly preferably selected from Si, N, P, O and / or S. A fused ring aromatic group refers to an aromatic group having two or more rings, wherein two carbon atoms are shared by two adjacent rings, i.e., a fused ring. A fused heterocyclic aromatic group refers to a fused heterocyclic aromatic hydrocarbon group containing at least one heteroatom. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic ring systems, but also non-aromatic ring systems. Thus, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, and carbene are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused aromatic or fused heteroaromatic ring systems include not only systems containing aromatic or heteroaromatic groups, but also systems in which multiple aromatic or heteroaromatic groups are interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc. are also considered aromatic ring systems for the purposes of this invention.

[0032] In the embodiments of the present invention, the energy level structure of the organic material, the singlet energy level S1, the triplet energy level T1, the HOMO, and the LUMO play a key role. The determination of these energy levels is described below.

[0033] HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), or by cyclic voltammetry (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0034] The singlet energy level S1 of an organic material can be determined by luminescence spectroscopy, and the triplet energy level T1 can be measured by low-temperature time-resolved luminescence spectroscopy. S1 and T1 can also be obtained by quantum simulation calculations (e.g., by time-dependent DFT), such as using the commercial software Gaussian 09W (Gaussian Inc.). Specific simulation methods can be found in WO2011141110 or described below in the Examples. ΔE ST Defined as (S1-T1).

[0035] It should be noted that the absolute values ​​of HOMO, LUMO, S1, and T1 depend on the measurement or calculation method used. Even for the same method, different evaluation methods, such as the onset and peak points on a CV curve, can give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement and evaluation methods. The values ​​of HOMO, LUMO, S1, and T1 described in the embodiments of the present invention are based on time-dependent DFT simulations, but this does not affect the application of other measurement or calculation methods.

[0036] In the present invention, (HOMO-1) is defined as the second-highest occupied molecular orbital energy level, (HOMO-2) is the third-highest occupied molecular orbital energy level, and so on. (LUMO+1) is defined as the second-lowest unoccupied molecular orbital energy level, (LUMO+2) is the third-lowest occupied molecular orbital energy level, and so on.

[0037] The present invention relates to an organic compound containing boron and nitrogen, having a structure as shown in one of chemical formulas (I) to (IV):

[0038] wherein: Q1 ring and Q2 ring, at each occurrence, are independently selected from substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, or substituted or unsubstituted fused ring structure; X is selected from B, N, P, P=O or Al; Y1 and Y2, at each occurrence, are independently selected from C=O, N-R1, O, S, Se, P, P=O or P=S; V0, at each occurrence, is independently selected from C-R2 or N; V1, V2, V3, at each occurrence, are independently selected from C-R3 or N; R, R1, R2, R3, at each occurrence, are the same or different and are selected from H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms; R3 is an alkyl, alkoxy, thioalkoxy or silyl group, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups, and one or more groups of R3 can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded.

[0039] In some embodiments, in the boron-nitrogen-containing organic compound, the Q1 ring and the Q2 ring are independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted.

[0040] In some embodiments, each occurrence of Q1 ring and Q2 ring may be the same or different and selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 6 to 50 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 50 ring atoms, or a combination of these groups. In some embodiments, each occurrence of Q1 ring and Q2 ring may be the same or different and selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 6 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 40 ring atoms, or a combination of these groups. In some embodiments, each occurrence of Q1 ring and Q2 ring may be the same or different and selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 6 to 30 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 30 ring atoms, or a combination of these groups. In some preferred embodiments, the Q1 ring and the Q2 ring, when each occurs, may be the same or different and selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 6 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 20 ring atoms, or a combination of these groups. In some more preferred embodiments, the Q1 ring and the Q2 ring, when each occurs, may be the same or different and selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 6 to 15 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 15 ring atoms, or a combination of these groups.

[0041] In some embodiments, X is selected from B or N.

[0042] In some preferred embodiments, the boron-nitrogen-containing organic compound has a structure as shown in one of Chemical Formula (I-1) to Chemical Formula (IV-1):

[0043] wherein Y1, Y2, R, V0, V1, V2, V3, Q1 ring, and Q2 ring are as defined above.

[0044] In some preferred embodiments, the boron-nitrogen-containing organic compound has a structure as shown in one of Chemical Formula (I-2) to Chemical Formula (IV-2):

[0045] Wherein, Y1, Y2, R, V0, V1, V2, V3, and Q1 ring are defined as above, and V4 is defined as V1.

[0046] In some preferred embodiments, in Formula (I-2) to Formula (IV-2), the substituent R4 on V4 is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups. More preferably, the substituent R4 on V4 is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 6 to 30 ring atoms, or an aryloxy group or heteroaryloxy group having 6 to 30 ring atoms, or a combination of these groups. Further preferably, the substituent R4 on V4 is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 10 to 30 ring atoms, or an aryloxy group or heteroaryloxy group having 10 to 30 ring atoms, or a combination of these groups. More preferably, the substituent R4 on V4 is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 13 to 30 ring atoms, or an aryloxy group or heteroaryloxy group having 13 to 30 ring atoms, or a combination of these groups.

[0047] In some preferred embodiments, in the boron-nitrogen-containing organic compound, the Q1 ring, when it appears each time, is independently selected from one or more combinations of the following structures:

[0048] wherein V is independently selected from C-R4 or N at each occurrence; W is independently selected from B-R5, C(=O), N-R6, O, S, P, P=O or P=S at each occurrence; R4-R6 are the same or different when they occur and are selected from H, D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 carbon atoms, or a keto group having 1 to 20 carbon atoms, or a 2 to 20 carbon atoms; or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, where one or more of the groups can form a ring system with one another and / or the groups to which they are bonded.

[0049] In certain embodiments, the Q1 ring is selected from an aromatic ring system, a heteroaromatic ring system, or a fused-ring aromatic group.

[0050] In a preferred embodiment, the aromatic or heteroaromatic ring system is selected from the following groups:

[0051] Wherein, the definitions of W and V are the same as above.

[0052] More preferably, the aromatic or heteroaromatic ring system is selected from:

[0053] Wherein, the definitions of W and V are the same as above.

[0054] In a preferred embodiment, the condensed-ring aromatic group is selected from the group consisting of benzene, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the condensed-ring heteroaromatic group is selected from the group consisting of benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, and derivatives thereof.

[0055] In certain embodiments, R1, R2, and R3, at each occurrence, may be independently selected from the following groups:

[0056] wherein: W and V are as defined above; n2, n3, n4, and n5 are all integers greater than or equal to 1. Preferably, each occurrence of R4-R6 in W and V is identically or differently selected from H, D, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, or a substituted keto group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, or an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups. Preferably, each occurrence of R4-R6 in W and V is the same or different and is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups. More preferably, each occurrence of R4-R6 in W and V is the same or different and is selected from an unsubstituted aromatic group or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups.

[0057] Furthermore, R1, R2, and R3, when each occurs, are independently selected from the following groups:

[0058] Among them: The H atoms on the ring can be further substituted.

[0059] In certain preferred embodiments, in the above-mentioned boron-nitrogen-containing organic compound, R1, R2, R4, R6, R8, and R9 may be further selected from the following structural units or combinations thereof:

[0060] Where n1 is 1 or 2 or 3 or 4.

[0061] In a more preferred embodiment, at least part of the H in the boron-nitrogen-containing organic compound is deuterated, preferably 10% or more of the H is deuterated, more preferably 20% or more of the H is deuterated, very preferably 30% or more of the H is deuterated, and most preferably 40% or more of the H is deuterated.

[0062] In some preferred embodiments, the molecular weight of the substituent R on the boron-nitrogen-containing organic compound is less than 500, preferably less than 400, more preferably less than 300, and most preferably less than 200.

[0063] In a more preferred embodiment, the molecular weight of the substituent on "V4" on the boron-nitrogen-containing organic compound is greater than 500, preferably greater than 400, more preferably greater than 300, very preferably greater than 200, and most preferably greater than 75.

[0064] Specific examples of the boron-nitrogen-containing organic compounds according to the present invention are listed below, but are not limited thereto:

[0065] For the purposes of the present invention, when Y2 is N-R1, R1 does not contain a cyclic alkyl group, particularly adamantane.

[0066] In certain preferred embodiments, the boron-nitrogen-containing organic compounds of the present invention are mainly divided into two categories. One category is to modify the boron-nitrogen ring structure by using indolecarbazole as a modifying group to adjust the optical properties of the existing boron-nitrogen skeleton; at the same time, it can effectively adjust the frontier orbital energy level of the organic compound and enhance the multiple resonance effect of the rigid conjugated plane of the boron-nitrogen ring structure, thereby achieving the effect of adjusting the luminescent color of the organic compound and narrowing the FWHM of the luminescence spectrum; in addition, compared with the traditional aromatic amine-type skeleton, the carbazole-type skeleton has stronger rigidity, which can effectively enhance the oscillator strength of the compound, and N and B are located in the para position of the conjugated six-membered ring and will not rotate freely, thereby improving the planarity of the boron-nitrogen-containing organic compound molecule, which is conducive to further narrowing the FWHM of the luminescence spectrum of the new organic compound.

[0067] The other type is to modify the boron-nitrogen ring structure by introducing carbazole and furan as modifying groups in the boron-nitrogen ring skeleton. Since furan has a poorer electron-donating ability than carbazole, it can reduce the electron cloud density around the B atom and improve the luminescence efficiency of the boron-nitrogen-containing organic compound; it can also extend the conjugation length of the entire molecule and improve the stability of the compound.

[0068] The boron-nitrogen-containing organic compounds of the present invention can be used as functional materials in electronic devices, particularly light-emitting devices. These light-emitting devices can be selected from color converters, OLEDs, OLEECs, and organic light-emitting field-effect transistors; OLED devices are particularly preferred. Organic functional materials can be categorized as color conversion materials (CCMs), hole injection materials (HIMs), hole transport materials (HTMs), electron transport materials (ETMs), electron injection materials (EIMs), electron blocking materials (EBMs), hole blocking materials (HBMs), luminescent materials (Emitters), host materials (Hosts), and organic dyes. In a preferred embodiment, the boron-nitrogen-containing organic compounds of the present invention can be used as luminescent materials.

[0069] In a preferred embodiment, the light emitting device has a light emission wavelength of 300 nm-1500 nm, preferably 400 nm-1000 nm, and more preferably 400 nm-800 nm.

[0070] In a preferred embodiment, the boron and nitrogen-containing organic compound according to the present invention can be used as a fluorescent guest material (ie, a fluorescent light-emitting material).

[0071] As a fluorescent guest material, it must have an appropriate singlet energy level, i.e., S1. In certain embodiments, the boron-nitrogen-containing organic compound according to the present invention has S1 ≥ 2.1 eV, preferably ≥ 2.3 eV, more preferably ≥ 2.5 eV, even more preferably ≥ 2.7 eV, and most preferably ≥ 2.8 eV.

[0072] As a fluorescent guest material, it must have a high photoluminescence quantum efficiency (PLQY). In certain embodiments, the boron-nitrogen-containing organic compound according to the present invention has a PLQY of ≥40%, preferably ≥50%, more preferably ≥60%, and most preferably ≥70%.

[0073] In a preferred embodiment, the boron-nitrogen-containing organic compound according to the present invention has a narrow full width at half maximum (FWHM), generally ≤35 nm, preferably ≤32 nm, more preferably ≤30 nm, particularly preferably ≤28 nm, most preferably ≤26 nm.

[0074] As an organic functional material, it is desirable to have good thermal stability. Generally, the boron-nitrogen-containing organic compound according to the present invention has a glass transition temperature (Tg) ≥ 100°C, preferably Tg ≥ 140°C, and more preferably Tg ≥ 180°C.

[0075] In certain preferred embodiments, the boron-nitrogen-containing organic compound according to the present invention has (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.3 eV, more preferably ≥ 0.4 eV, and most preferably ≥ 0.5 eV.

[0076] In other preferred embodiments, the boron-nitrogen-containing organic compound according to the present invention has ((LUMO+1)-LUMO) ≥ 0.2 eV, preferably ≥ 0.3 eV, more preferably ≥ 0.4 eV, most preferably ≥ 0.5 eV.

[0077] The present invention also provides a polymer, which comprises at least one first repeating unit, wherein the first repeating unit comprises at least one structure corresponding to the boron-nitrogen-containing organic compound described in the present invention.

[0078] In some embodiments, the polymer further comprises at least one second repeating unit that is different from the first repeating unit.

[0079] In certain embodiments, the polymer is a conjugated polymer; in some preferred embodiments, the conjugated polymer comprises a second repeating unit selected from one of the following repeating units:

[0080] wherein R' is independently selected from H, D, C1-C20 straight-chain alkyl, C1-C20 alkoxy, C1-C20 thioalkoxy, C3-C20 branched-chain alkyl, C3-C20 cyclic alkyl, C3-C20 branched-chain alkoxy, C3-C20 cyclic alkoxy, C3-C20 branched-chain thioalkoxy, C3-C20 cyclic thioalkoxy, silyl, C1-C20 keto, C2-C20 alkoxycarbonyl, C7-C20 aryloxycarbonyl, cyano, carbamoyl , haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I, a cross-linkable group, a substituted aryl group having 5 to 60 ring atoms, an unsubstituted aryl group having 5 to 60 ring atoms, a substituted heteroaryl group having 5 to 60 ring atoms, an unsubstituted heteroaryl group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, and a heteroaryloxy group having 5 to 60 ring atoms.

[0081] In other preferred embodiments, the polymer comprises a polymer backbone and side chains connected to the polymer backbone, wherein the side chains are derived from the boron-nitrogen-containing organic compound of the present invention. More preferably, the polymer is a non-conjugated polymer comprising a third repeating unit selected from one of the following repeating units:

[0082] wherein R" is independently selected from H, D, C1-C20 straight-chain alkyl, C1-C20 alkoxy, C1-C20 thioalkoxy, C3-C20 branched-chain alkyl, C3-C20 cyclic alkyl, C3-C20 branched-chain alkoxy, C3-C20 cyclic alkoxy, C3-C20 branched-chain thioalkoxy, C3-C20 cyclic thioalkoxy, silyl, C1-C20 keto, C2-C20 alkoxycarbonyl, C7-C20 aryloxycarbonyl, cyano, carbamoyl , haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I, a cross-linkable group, a substituted aryl group having 5 to 60 ring atoms, an unsubstituted aryl group having 5 to 60 ring atoms, a substituted heteroaryl group having 5 to 60 ring atoms, an unsubstituted heteroaryl group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, and a heteroaryloxy group having 5 to 60 ring atoms.

[0083] In a preferred embodiment, the polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

[0084] In a preferred embodiment, the polymer according to the present invention has a glass transition temperature (Tg) ≥ 100°C, preferably ≥ 120°C, more preferably ≥ 140°C, even more preferably ≥ 160°C, and most preferably ≥ 180°C.

[0085] In a preferred embodiment, the molecular weight distribution (PDI) of the polymer according to the present invention is preferably in the range of 1 to 5, more preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2, and most preferably 1 to 1.5.

[0086] In a preferred embodiment, the weight average molecular weight (Mw) of the polymer according to the present invention is preferably in the range of 10,000 to 1,000,000, more preferably 50,000 to 500,000, more preferably 100,000 to 400,000, even more preferably 150,000 to 300,000, and most preferably 200,000 to 250,000.

[0087] In certain embodiments, the boron-nitrogen-containing organic compounds or polymers according to the present invention have luminescence capabilities, and the luminescence wavelength is between 300 nm and 1000 nm, preferably between 350 nm and 900 nm, and more preferably between 400 nm and 800 nm. The luminescence referred to herein refers to photoluminescence or electroluminescence.

[0088] The present invention also relates to a mixture comprising one of the aforementioned boron-nitrogen-containing organic compounds or polymers and at least one organic functional material. The organic functional material comprises at least one of a color conversion material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminophore, and a host material; the luminophore is selected from a singlet luminophore (fluorescent luminophore), a triplet luminophore (phosphorescent luminophore), and an organic thermally excited delayed fluorescence (TADF) material. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of which are hereby incorporated by reference. The organic functional material can be a small molecule or a polymeric material.

[0089] In some preferred embodiments, the mixture comprises at least one boron-nitrogen-containing organic compound or polymer according to the present invention and a fluorescent host material. The boron-nitrogen-containing organic compound according to the present invention can serve as a fluorescent guest material, wherein the weight percentage of the fluorescent guest is ≤ 10 wt %, preferably ≤ 9 wt %, more preferably ≤ 8 wt %, particularly preferably ≤ 7 wt %, and most preferably ≤ 5 wt %.

[0090] Detailed descriptions of the host material, fluorescent light-emitting material, TADF material and other organic functional materials are given in WO2018095395. The entire contents of this patent document are hereby incorporated herein by reference.

[0091] One object of the present invention is to provide a material solution for vapor deposition type OLEDs.

[0092] In certain embodiments, the boron-nitrogen-containing organic compound according to the present invention has a molecular weight of ≤1200 g / mol, preferably ≤1100 g / mol, very preferably ≤1000 g / mol, more preferably ≤950 g / mol, and most preferably ≤900 g / mol.

[0093] Another object of the present invention is to provide a material solution for printed OLEDs.

[0094] In certain embodiments, the boron-nitrogen-containing organic compound according to the present invention has a molecular weight of ≥800 g / mol, preferably ≥1000 g / mol, more preferably ≥1100 g / mol, and most preferably ≥1200 g / mol.

[0095] In other embodiments, the boron-nitrogen-containing organic compound according to the present invention has a solubility in toluene of ≥10 mg / mL at 25° C., preferably ≥15 mg / mL, and most preferably ≥20 mg / mL.

[0096] The present invention further relates to a composition or ink comprising at least one boron-nitrogen-containing organic compound or polymer according to the present invention and at least one organic solvent.

[0097] When used in printing processes, ink viscosity and surface tension are important parameters. The appropriate surface tension parameters of the ink are suitable for a specific substrate and a specific printing method.

[0098] In a preferred embodiment, the surface tension of the ink according to the present invention at operating temperature or at 25°C is approximately in the range of 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; and most preferably in the range of 25 dyne / cm to 33 dyne / cm.

[0099] In another preferred embodiment, the viscosity of the ink according to the present invention at operating temperature or 25° C. is in the range of about 1 cps to 100 cps; more preferably, in the range of 1 cps to 50 cps; more preferably, in the range of 1.5 cps to 20 cps; and most preferably, in the range of 4.0 cps to 20 cps. Such a formulated composition will facilitate inkjet printing.

[0100] Viscosity can be adjusted by various methods, such as by selecting the appropriate solvent and the concentration of the functional material in the ink. The ink containing the boron-nitrogen-containing organic compound or polymer according to the present invention facilitates adjustment of the printing ink within an appropriate range according to the printing method used. Generally, the weight ratio of the functional material contained in the composition according to the present invention is in the range of 0.3 wt% to 30 wt%, preferably in the range of 0.5 wt% to 20 wt%, more preferably in the range of 0.5 wt% to 15 wt%, even more preferably in the range of 0.5 wt% to 10 wt%, and most preferably in the range of 1 wt% to 5 wt%.

[0101] In some embodiments, according to the ink of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents, in particular aliphatic chain / ring substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

[0102] Examples of solvents suitable for the present invention include, but are not limited to: aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1 ,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvents: 1-tetralone, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4- Methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-nonanone, fenchone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, phorone, di-n-amyl ketone; aromatic ether solvents: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylhexyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethylbenzene Oxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; ester solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc.

[0103] Further, according to the ink of the present invention, the at least one organic solvent can be selected from: aliphatic ketones, for example, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, phorone, di-n-amyl ketone, etc.; or aliphatic ethers, for example, amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.

[0104] In some other embodiments, the printing ink further comprises another organic solvent. Examples of the other organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetralin, decalin, indene, and / or mixtures thereof.

[0105] In a preferred embodiment, the composition according to the present invention is a solution.

[0106] In another preferred embodiment, the composition according to the present invention is a suspension.

[0107] The composition in the embodiment of the present invention may include 0.01wt% to 20wt% of the boron-nitrogen-containing organic compound or its mixture according to the present invention, preferably 0.1wt% to 15wt%, more preferably 0.2wt% to 10wt%, and most preferably 0.25wt% to 5wt% of the boron-nitrogen-containing organic compound or its mixture.

[0108] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, and particularly preferably a preparation method by printing or coating.

[0109] Suitable printing or coating techniques include, but are not limited to, gravure printing, inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot extrusion coating, and the like. Inkjet printing, nozzle printing, and gravure printing are preferred. The solution or suspension may further include one or more components, such as a surfactant, lubricant, wetting agent, dispersant, hydrophobic agent, adhesive, etc., to adjust viscosity, film-forming properties, and improve adhesion. For more information on printing techniques and their requirements for solutions, such as solvent concentration and viscosity, please refer to "Handbook of Print Media: Technologies and Production Methods," edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0110] Based on the above-mentioned boron-nitrogen-containing organic compound or polymer, the present invention further provides an application of the above-mentioned boron-nitrogen-containing organic compound or polymer, i.e., applying the boron-nitrogen-containing organic compound or polymer to an organic electronic device. The organic electronic device may be selected from, but not limited to, a color converter, an organic light-emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light-emitting cell (OLEEC), an organic field-effect transistor (OFET), an organic light-emitting field-effect transistor (OLED), an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode (OPED). Organic electroluminescent devices, such as OLEDs, OLEECs, and organic light-emitting field-effect transistors (OLEDs), are particularly preferred. In an embodiment of the present invention, the boron-nitrogen-containing organic compound is preferably used in the light-emitting layer of an electroluminescent device.

[0111] The present invention further relates to an organic electronic device comprising at least one boron-nitrogen-containing organic compound, polymer, or mixture as described above. Generally, such an organic electronic device comprises at least a cathode, an anode, and a functional layer disposed between the cathode and the anode, wherein the functional layer comprises at least one boron-nitrogen-containing organic compound, polymer, or mixture as described above. The organic electronic device may be selected from, but is not limited to, color converters, organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light-emitting cells (OLEECs), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors (OLEDs), organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes (OPDs). Organic electroluminescent devices, such as OLEDs, OLEECs, and OLEDs, are particularly preferred.

[0112] In some particularly preferred embodiments, the organic electronic device comprises a light-emitting layer, which comprises an organic compound containing boron and nitrogen, or comprises an organic compound containing boron and nitrogen and a host material, or comprises an organic compound containing boron and nitrogen, a phosphorescent light-emitting body and a host material.

[0113] In some particularly preferred embodiments, the organic electronic device is an organic light-emitting device, which comprises a light-emitting layer, wherein the guest material of the light-emitting layer comprises at least one boron-nitrogen-containing organic compound, polymer or mixture as described above.

[0114] The organic electronic device described above, especially the OLED, includes a substrate, an anode, at least one light-emitting layer, and a cathode.

[0115] The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting device. For example, see Bulovic et al. Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. It is best if the substrate has a smooth surface. Substrates without surface defects are particularly ideal. In a preferred embodiment, the substrate is flexible and can be selected from a polymer film or plastic with a glass transition temperature (Tg) of above 150°C, preferably above 200°C, more preferably above 250°C, and most preferably above 300°C. Examples of suitable flexible substrates are polyethylene terephthalate (PET) and polyethylene (2,6-naphthalene) (PEN).

[0116] The anode can include a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into the hole injection layer (HIL) or hole transport layer (HTL) or light-emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the anode and the HOMO energy level or valence band energy level of the light-emitting material in the light-emitting layer or the p-type semiconductor material serving as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

[0117] The cathode can comprise a conductive metal or metal oxide. The cathode can readily inject electrons into the EIL or ETL or directly into the light-emitting layer. In a preferred embodiment, the absolute difference between the work function of the cathode and the LUMO energy level or conduction band energy level of the luminophore in the light-emitting layer or the n-type semiconductor material serving as the electron injection layer (EIL), electron transport layer (ETL), or hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials that can be used as cathodes in OLEDs are possible cathode materials for the devices of the present invention. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloys, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

[0118] OLEDs may also include other functional layers, such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Suitable materials for these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1. The entire contents of these three patent documents are hereby incorporated by reference.

[0119] In a preferred embodiment, in the light-emitting device according to the present invention, the light-emitting layer thereof is prepared by the composition according to the present invention.

[0120] The light emitting device according to the present invention, in particular the OLED, has a light emission wavelength between 300 nm and 1500 nm, preferably between 350 nm and 1200 nm, and more preferably between 400 nm and 800 nm.

[0121] The present invention also relates to applications of the organic electronic device according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

[0122] The present invention also relates to electronic devices incorporating organic electronic devices according to the present invention, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like. In certain embodiments, the electronic device comprises a housing and the aforementioned device disposed on the housing. The electronic device can be any terminal device equipped with an OLED display screen, including, but not limited to, smartphones, tablet computers, personal laptop computers, smart televisions, in-car displays, smart watches, and the like. In some embodiments, the electronic device is a smartphone.

[0123] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should realize that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0124] Example

[0125] 1. Synthesis of compounds

[0126] Synthesis of intermediate 1b:

[0127] 1a (100 g), 4-tert-butylaniline (100 g), tris(dibenzylideneacetone)dipalladium (16 g), and anhydrous sodium tert-butoxide (67 g) were dissolved in toluene (500 mL), heated to 90°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 126 g of intermediate 1b in a 77% yield. Product characterization: MS (ASAP) = 337.5.

[0128] Synthesis of intermediate 2c:

[0129] Under nitrogen, a three-necked flask was charged with 2a (100 g), deuterated phenylboronic acid (100 g), potassium carbonate (25 g), tetrakistriphenylphosphine palladium (3 g), and 1000 mL of toluene / 50 mL of ethanol / 50 mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was terminated by heating under reflux for 12 hours. The temperature was then lowered. The product was extracted with ethyl acetate and deionized water, and the organic phase was washed twice with water, dried, filtered, and the filtrate was evaporated to dryness to obtain 180 g of crude product 2b. The product 2b was collected by column chromatography (petroleum ether / ethyl acetate 15:1) to yield 175 g, a 95% yield.

[0130] 2b (100 g), intermediate 1b (100 g), tris(dibenzylideneacetone)dipalladium (16 g), and anhydrous sodium tert-butoxide (67 g) were dissolved in toluene (500 mL), heated to 90°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 105 g of intermediate 2c in a 78% yield. Product characterization: MS (ASAP) = 573.6.

[0131] Synthesis of intermediate 3c:

[0132] 1a (100 g), 3b (100 g), tris(dibenzylideneacetone)dipalladium (16 g), and anhydrous sodium tert-butoxide (67 g) were dissolved in toluene (500 mL), heated to 90°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 167 g of intermediate 3c in a 91% yield. Product characterization: MS (ASAP) = 391.6.

[0133] Synthesis of intermediate 4d:

[0134] Under nitrogen, a three-necked flask was charged with 4a (100 g), carbazole (100 g), potassium carbonate (25 g), tetrakistriphenylphosphine palladium (3 g), and 1000 mL of toluene / 50 mL of ethanol / 50 mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was terminated by heating under reflux for 12 hours. The temperature was then lowered. The product was extracted with ethyl acetate and deionized water, and the organic phase was washed twice, dried, filtered, and the filtrate was evaporated to dryness to obtain 150 g of crude product 4b. The product 4b was collected by column chromatography (petroleum ether / ethyl acetate 15:1) to yield 142 g, a yield of 71%.

[0135] 4b (100 g), intermediate 3c (100 g), tris(dibenzylideneacetone)dipalladium (16 g), and anhydrous sodium tert-butoxide (67 g) were dissolved in toluene (500 mL), heated to 90°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 152 g of intermediate 4d in an 85% yield. Product characterization: MS (ASAP) = 650.9.

[0136] Synthesis of intermediate 5b

[0137] 1a (100 g), 5a (100 g), tris(dibenzylideneacetone)dipalladium (16 g), and anhydrous sodium tert-butoxide (67 g) were dissolved in toluene (500 mL), heated to 90°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 131 g of intermediate 5b in a 78% yield. Product characterization: MS (ASAP) = 371.5.

[0138] Synthesis of intermediate 5c:

[0139] Intermediate 5b (100 g), m-fluorobromobenzene (100 g), tris(dibenzylideneacetone)dipalladium (16 g), and anhydrous sodium tert-butoxide (67 g) were dissolved in toluene (500 mL), heated to 90°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 82 g of intermediate 5c in a 70% yield. Product characterization: MS (ASAP) = 465.6.

[0140] Synthesis of intermediate 6a:

[0141] o-Diphenylamine (20 g), p-tert-butylbenzoic acid (30 g), and polyphosphoric acid (20 g) were added to a 250 mL two-necked flask and heated to 180°C with stirring for 24 hours. After cooling the reaction mixture to room temperature, aqueous ammonia (500 mL, 6% in H2O) was added, filtered, and rinsed with ammonia. Recrystallization yielded a 99% yield. (Reference: Host-Guest Interactions in a Metal-Organic Framework Isoreticular Series for Molecular Photocatalytic CO2 Reduction). Product characterization: MS (ASAP) = 250.

[0142] Synthesis of intermediate 8a:

[0143] Similar to the synthesis method of intermediate 6a, dibenzofuran-3-carboxylic acid was used to replace p-tert-butylbenzoic acid to obtain intermediate 8a. Product characterization: MS (ASAP) = 284.

[0144] Synthesis of intermediate 9a:

[0145] Similar to the synthesis method of intermediate 6a, 9,9'-spirobifluorene-2-carboxylic acid was used to replace p-tert-butylbenzoic acid to obtain intermediate 9a. Product characterization: MS (ASAP) = 432.

[0146] Synthesis of intermediate 10a:

[0147] Similar to the synthesis of intermediate 6a, intermediate 10a was obtained by replacing p-tert-butylbenzoic acid with 9,9-dimethyl-7-phenylfluorene-2-carboxylic acid. Product characterization: MS (ASAP) = 386.

[0148] Synthesis of intermediate 15c:

[0149] Under nitrogen, a three-necked flask was charged with 4a (100 g), 15a (100 g), potassium carbonate (25 g), tetrakistriphenylphosphine palladium (3 g), and 1000 mL of toluene / 50 mL of ethanol / 50 mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was terminated by heating under reflux for 12 hours. The temperature was then lowered. Extraction was performed with ethyl acetate and deionized water, and the organic phase was washed twice, dried, filtered, and the filtrate was evaporated to dryness to obtain 140 g of crude product 15b. The product was separated by column chromatography (petroleum ether / ethyl acetate 15:1) to yield 130 g, with a yield of 65%.

[0150] 15b (100 g), intermediate 3c (100 g), tris(dibenzylideneacetone)dipalladium (16 g), and anhydrous sodium tert-butoxide (67 g) were dissolved in toluene (500 mL), heated to 90°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 141 g of intermediate 15c in a 70% yield. Product characterization: MS (ASAP) = 803.

[0151] Synthesis of intermediate 16b:

[0152] 16a (100 g), 4-tert-butylaniline (100 g), tris(dibenzylideneacetone)dipalladium (16 g), and anhydrous sodium tert-butoxide (67 g) were dissolved in toluene (500 mL), heated to 90°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 60 g of intermediate 16b in a 60% yield. Product characterization: MS (ASAP) = 337.5.

[0153] Synthesis of intermediate 16c:

[0154] 2b (100 g), intermediate 16b (100 g), tris(dibenzylideneacetone)dipalladium (16 g), and anhydrous sodium tert-butoxide (67 g) were dissolved in toluene (500 mL), heated to 90°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 100 g of intermediate 16c in a 50% yield. Product characterization: MS (ASAP) = 573.6.

[0155] Synthesis of compound 1:

[0156] Dissolve m-difluorobenzene (50 g), intermediate 1b (110 g), and anhydrous cesium carbonate (285 g) in anhydrous N,N-dimethylformamide (500 mL), heat to 100°C, and stir for 8 hours. After cooling the reaction solution to room temperature, extract with a large amount of deionized water and dichloromethane, and retain the organic phase. After removing the organic solvent by vacuum distillation, the product was purified by silica gel column chromatography to obtain 105 g of intermediate 1c in a 92% yield.

[0157] Intermediate 1c (50 g), 1d (100 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 90 g of intermediate 1e in an 85% yield.

[0158] Intermediate 1e (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 3.3 g of compound 1 in a 34% yield. Product characterization: MS (ASAP) = 613.6.

[0159] Synthesis of compound 2:

[0160] 1d (50 g), intermediate 2c (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 112 g of intermediate 2d in a 95% yield.

[0161] Intermediate 2d (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 3.9 g of compound 2 in a 41% yield. Product characterization: MS (ASAP) = 694.7.

[0162] Synthesis of compound 3:

[0163] Dissolve m-difluorobenzene (50 g), intermediate 3c (110 g), and anhydrous cesium carbonate (285 g) in anhydrous N,N-dimethylformamide (500 mL), heat to 100°C, and stir for 8 hours. After cooling the reaction solution to room temperature, extract with a large amount of deionized water and dichloromethane, and retain the organic phase. After removing the organic solvent by vacuum distillation, the product was purified by silica gel column chromatography to obtain 101 g of intermediate 3d in a 95% yield.

[0164] 1d (30 g), intermediate 3d (50 g), and anhydrous cesium carbonate (100 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 101 g of intermediate 3e in a 35% yield.

[0165] Intermediate 3e (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 2.1 g of compound 3 in a 24% yield. Product characterization: MS (ASAP) = 667.7.

[0166] Synthesis of compound 4:

[0167] Intermediate 4d (50 g), 1d (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 43 g of intermediate 4e in a 53% yield.

[0168] Intermediate 4e (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 2.6 g of compound 4 in a 30% yield. Product characterization: MS (ASAP) = 832.9.

[0169] Synthesis of compound 5:

[0170] Intermediate 5c (50 g), 1d (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 52 g of intermediate 5d in a 64% yield.

[0171] Intermediate 5d (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 2.5 g of compound 5 in a 30% yield. Product characterization: MS (ASAP) = 647.6.

[0172] Synthesis of compound 6:

[0173] Intermediate 4d (50 g), 6a (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 43 g of intermediate 6b in a 53% yield.

[0174] Intermediate 6b (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 2.6 g of compound 6 in a 30% yield. Product characterization: MS (ASAP) = 889.

[0175] Synthesis of compound 7:

[0176] Intermediate 1c (50 g), 7a (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 105 g of intermediate 7b in a 92% yield.

[0177] Intermediate 7b (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 3.3 g of compound 7 in a 34% yield. Product characterization: MS (ASAP) = 679.7.

[0178] Synthesis of compound 8:

[0179] Intermediate 1c (50 g), 8a (100 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 73 g of intermediate 8b with a yield of 63%.

[0180] Intermediate 8b (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 2.3 g of compound 8 in a 23% yield. Product characterization: MS (ASAP) = 703.7.

[0181] Synthesis of compound 9:

[0182] Intermediate 1c (50 g), 9a (100 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 75 g of intermediate 9b in a 64% yield.

[0183] Intermediate 9b (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 3.0 g of compound 9 in a 30% yield. Product characterization: MS (ASAP) = 851.9.

[0184] Synthesis of compound 10:

[0185] Intermediate 1c (50 g), 10a (100 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 80 g of intermediate 10b in a 72% yield.

[0186] Intermediate 10b (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 3.1 g of compound 10 in a 31% yield. Product characterization: MS (ASAP) = 805.9.

[0187] Synthesis of compound 11:

[0188] Compound 5 can be prepared into intermediate 11a under the action of catalyst [Ir(COD)(OCH3)]2, reference: DOI:10.31635 / ccschem.021.202101033.

[0189] Intermediate 11a (10 g) was added to a 100 mL two-necked flask, followed by toluene (50 mL), ethanol (10 mL), and water (10 mL). Then, 11b (10 g), tetrakistriphenylphosphine palladium (0.5 g), and potassium carbonate (2 g) were added. The reaction solution was heated to 100°C and refluxed, stirring for 24 hours. Subsequently, the reaction solution was cooled to room temperature, extracted with a large amount of deionized water and dichloromethane, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 5 g of compound 11 with a yield of 50%. Product characterization: MS (ASAP) = 733.7.

[0190] Synthesis of compound 12:

[0191] Similar to the synthesis method of compound 11, intermediate 12a was prepared in the presence of catalyst [Ir(COD)(OCH3)]2, and then compound 12 was obtained by Suzuki reaction, MS (ASAP) = 903.8.

[0192] Synthesis of compound 13:

[0193] Similar to the synthesis method of compound 11, intermediate 11a was prepared in the presence of catalyst [Ir(COD)(OCH3)]2, and then compound 13 was obtained by Suzuki reaction, MS (ASAP) = 952.

[0194] Synthesis of compound 14:

[0195] Similar to the synthesis method of compound 11, intermediate 14a was prepared in the presence of catalyst [Ir(COD)(OCH3)]2, and then compound 14 was obtained by Suzuki reaction, MS (ASAP) = 918.

[0196] Synthesis of compound 15:

[0197] Intermediate 15c (50 g), 1d (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 50 g of intermediate 15d in a 75% yield.

[0198] Intermediate 15d (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 2 g of compound 15 in a 20% yield. Product characterization: MS (ASAP) = 985.

[0199] Synthesis of compound 16:

[0200] Intermediate 16c (50 g), 1d (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 40 g of intermediate 16d in a 50% yield.

[0201] Intermediate 16d (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 2.1 g of compound 6 in a 21% yield. Product characterization: MS (ASAP) = 889.

[0202] Synthesis of compound 17:

[0203] 17a (50 g), intermediate 6a (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 31 g of intermediate 17b in a 30% yield.

[0204] Intermediate 17b (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 1.9 g of compound 17 in a 19% yield. Product characterization: MS (ASAP) = 873.

[0205] Synthesis of compound 18:

[0206] 18a (50 g), carbazole (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 12 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 40 g of intermediate 18b in a 40% yield.

[0207] 18b (50 g) and sodium hydroxide (10 g) were dissolved in 75% ethanol, heated to 60°C, and stirred for 12 hours. After cooling the reaction to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation to obtain intermediate 18c, which was used directly in the next reaction without further treatment.

[0208] Intermediate 18c (100 g), 3-bromo-5-(tert-butyl)benzothiophene (110 g), and sodium hydroxide (20 g) were dissolved in acetonitrile (500 mL), heated to 60°C, and stirred for 12 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation to obtain Intermediate 18d, which was used directly in the next reaction without further treatment.

[0209] Intermediate 18d (50 g), intermediate 6a (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 101 g of intermediate 18e in a 90% yield.

[0210] Intermediate 18e (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 1 g of compound 18 in a 10% yield. Product characterization: MS (ASAP) = 703.

[0211] Synthesis of compound 19:

[0212] Intermediate 16c (50 g), 7a (110 g), and anhydrous cesium carbonate (285 g) were dissolved in anhydrous N,N-dimethylformamide (500 mL), heated to 100°C, and stirred for 8 hours. After cooling the reaction solution to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 30 g of intermediate 19a in a 60% yield.

[0213] Intermediate 19a (10 g) was dissolved in tert-butylbenzene (300 mL), and tert-butyllithium (16 mL, 1.3 M solution in n-hexane) was added dropwise under an ice bath. After the addition was complete, the reaction solution was heated to 100°C and stirred for 2 hours. Subsequently, the reaction solution was cooled to an ice bath, and boron tribromide (5.2 mL) was added dropwise. After the addition was complete, the solution was heated to 180°C and stirred for 8 hours. Subsequently, N,N-diisopropylethylamine (24 mL) was added dropwise under an ice bath. After the addition was complete, the solution was heated to 180°C and stirred overnight. After the reaction solution was cooled to room temperature, a large amount of deionized water and dichloromethane were added for extraction, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 0.3 g of compound 19 in a 3% yield. Product characterization: MS (ASAP) = 679.7.

[0214] Synthesis of compound 20:

[0215] The synthesis of intermediate 20a is similar to that of intermediate 18d, except that 2-bromo-5-(tert-butyl)benzothiophene is substituted for 3-bromo-5-(tert-butyl)benzothiophene in the reaction for synthesizing intermediate 18d. Subsequent synthesis is similar to that of compound 18, except that intermediate 18d is replaced with intermediate 20a to obtain compound 20. Product characterization: MS (ASAP) = 703.

[0216] Comparative Compound 1

[0217] The existing boron-nitrogen material structure is as follows:

[0218] The specific synthesis method of the existing boron-nitrogen material can adopt the existing synthesis method, and the present invention will not go into details.

[0219] 2. Energy level structure of the compound

[0220] The energy levels of organic compounds can be calculated through quantum calculations, such as using TD-DFT (time-dependent density functional theory) with Gaussian 09W (Gaussian Inc.). For detailed simulation methods, see WO2011141110. The molecular geometry is first optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet). The energy structure of the organic molecule is then calculated using TD-DFT (time-dependent density functional theory) using the "TD-SCF / DFT / Default Spin / B3PW91" basis set "6-31G(d)" (Charge 0 / Spin Singlet). The HOMO and LUMO energy levels are calculated using the following calibration formulas, using S1 and T1 as is.

[0221] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206

[0222] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0223] The HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree. The results are shown in Table 1:

[0224] Table 1

[0225] 3. Preparation and Characterization of OLED Devices

[0226] Example 1 (Preparation of OLED Device 1)

[0227] Step S1: Use transparent glass as a substrate, clean the anode (ITO (15nm) / Ag (150nm) / ITO (15nm)) on it, and use stripping liquid, pure water, and isopropyl alcohol ultrasonic cleaning respectively, and then dry and then perform Ar2 ozone treatment.

[0228] Step S2: The cleaned substrate is moved into a vacuum vapor deposition device and placed in a high vacuum (1×10 -6 mbar), the ratio of PD to HT-1 was controlled to be 3:100, and a 10 nm hole injection layer (HIL) was formed.

[0229] Step S3: On the hole injection layer, 125 nm of hole transport layer material HT-1 is evaporated by vacuum evaporation.

[0230] Step S4: On the hole injection layer, 10 nm of electron blocking layer material HT-2 is deposited by vacuum evaporation.

[0231] Step S5: On the electron blocking layer, a light-emitting layer is deposited by vacuum evaporation, wherein the host material is BH and the guest material is the compound 1 of the present invention, with a mass ratio of 98:2 and a thickness of 25 nm.

[0232] Step S6: depositing 2 nm of hole blocking layer material ET-1 on the light-emitting layer by vacuum evaporation.

[0233] Step S7: On the hole blocking layer, ET-2 and Liq are vacuum evaporated as an electron transport layer with a mass ratio of 50:50 and a thickness of 35 nm.

[0234] Step S8: 1.5 nm of Yb is evaporated on the electron transport layer by vacuum evaporation as an electron injection layer.

[0235] Step S9: 17 nm of Mg:Ag (1:9) alloy was evaporated on the electron injection layer as a cathode.

[0236] Step S10: evaporating 55 nm of CPL material on the cathode layer.

[0237] The following are the structural formulas of the materials used in each functional layer:

[0238] Example 2 (Preparation of OLED Device 2)

[0239] Example 2 differs from Example 1 in that, in step S3, a 120 nm thick layer of hole transport layer material HT-1 is vacuum-deposited on the hole injection layer, and in step S5, the aforementioned compound 2 is used as the guest material. The remaining steps are identical to those in Example 1; please refer to Example 1 for details.

[0240] Example 3 (Preparation of OLED Device 3)

[0241] Example 3 differs from Example 1 in that, in step S3, a 122 nm thick layer of hole transport layer material HT-1 is vacuum-deposited on the hole injection layer, and the aforementioned compound 3 is used as the guest material in step S5. The remaining steps are the same as in Example 1. For details, please refer to Example 1.

[0242] Example 4 (Preparation of OLED Device 4)

[0243] Example 4 differs from Example 1 in that, in step S3, a 122 nm thick layer of hole transport layer material HT-1 is vacuum-deposited on the hole injection layer, and in step S5, the guest material is compound 4. The remaining steps are the same as in Example 1; please refer to Example 1 for details.

[0244] Example 5 (Preparation of OLED Device 5)

[0245] Example 5 differs from Example 1 in that, in step S3, a 122 nm thick layer of hole transport layer material HT-1 is vacuum-deposited on the hole injection layer, and the guest material in step S5 is compound 8. The remaining steps are the same as in Example 1. For details, please refer to Example 1.

[0246] Example 6 (Preparation of OLED Device 6)

[0247] Example 6 differs from Example 1 in that, in step S3, a 122 nm thick layer of hole transport layer material HT-1 is vacuum-deposited on the hole injection layer, and in step S5, the guest material is compound 11. The remaining steps are the same as in Example 1; please refer to Example 1 for details.

[0248] Example 7 (Preparation of OLED Device 7)

[0249] Example 7 differs from Example 1 in that, in step S3, a 122 nm thick layer of hole transport layer material HT-1 is vacuum-deposited on the hole injection layer, and the aforementioned compound 14 is used as the guest material in step S5. The remaining steps are the same as in Example 1. For details, please refer to Example 1.

[0250] Example 8 (Preparation of OLED Device 8)

[0251] Example 8 differs from Example 1 in that, in step S3, a 122 nm thick layer of hole transport layer material HT-1 is vacuum-deposited on the hole injection layer, and the aforementioned compound 17 is used as the guest material in step S5. The remaining steps are the same as in Example 1. For details, please refer to Example 1.

[0252] Comparative Example 1 (Preparation of OLED Device 4)

[0253] Comparative Example 1 differs from Example 1 in that, in step S3, a 121 nm thick layer of hole transport layer material HT-1 is vacuum-evaporated onto the hole injection layer, and in step S5, the guest material is the existing boron-nitrogen material of Comparative Compound 1. The remaining steps are identical to those of Example 1; please refer to Example 1 for details.

[0254] The performance of the devices prepared in Examples 1 to 8 and Comparative Example 1 is shown in Table 2. The current efficiency, EQE and LT95 are all based on the comparative example.

[0255] Table 2

[0256] Note: EQE: External Quantum Efficiency; LT95@1000nit: The operating time when the device experiences 5% brightness loss at 1000 nits brightness.

[0257] From the external quantum efficiency (EQE), luminescence spectrum FWHM and device operating life at 1000 brightness (operating time when 5% maximum brightness loss occurs) of the devices of Examples 1 to 8 and Comparative Example 1 in Table 2, it can be seen that compared with Comparative Example 1, the OLED devices of Examples 1 to 8 using the boron and nitrogen-containing organic compounds synthesized by the present invention exhibit higher luminescence efficiency and narrower FWHM, and have a longer operating life and higher device stability.

[0258] From the comparison of the device results of device embodiments 1 and 7, it can be seen that the substituents on the B atom in the boron nitrogen compound described in this patent can adjust the light color, improve the molecular stacking effect, and reduce the quenching effect of the luminescent molecule in the device, which plays an important role that cannot be ignored. On the other hand, from the device results of device embodiments 1 and 8, it can be seen that the change of the substituents on the imidazole ring has a certain effect on the device improvement, but the effect is not significant. From the comparison of the device results of device embodiments 1 and 6, it can be seen that the substituents on the N atom have little effect on the device. Therefore, in terms of molecular design, under the condition that it does not affect the overall performance of the molecule, from the perspective of cost-effectiveness, the substituents on the N atom should be as small as possible under the condition of having a conjugated molecule.

[0259] It should be noted that the above are only specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. The embodiments of the present invention and the features within the embodiments can be combined with each other unless there is a conflict. Therefore, the scope of protection of the present invention shall be based on the scope of protection of the claims.

Claims

1. A boron-nitrogen-containing organic compound, characterized in that: The boron-nitrogen-containing organic compound has a structure as shown in one of the chemical formulas (I) to (IV): in: Q1 ring and Q2 ring, when they appear each time, are independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted fused ring structure; X is selected from B, N, P, P═O or Al; Y1 and Y2, at each occurrence, are independently selected from C=O, N-R1, O, S, Se, P, P=O or P=S; V0, at each occurrence, is independently selected from C-R2 or N; V1, V2, and V3, at each occurrence, are independently selected from C-R3 or N; R, R1, R2, R3, at each occurrence, are selected, identically or differently, from H or D, or straight-chain alkyl, alkoxy or thioalkoxy having 1 to 20 C atoms, or branched or cyclic alkyl, alkoxy, thioalkoxy or silyl having 3 to 20 C atoms, or keto having 1 to 20 C atoms, or alkoxycarbonyl having 2 to 20 C atoms, or aryloxycarbonyl having 7 to 20 C atoms, or cyano, carbamoyl, halogen formyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups, and one or more groups of R3 can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which the groups are bonded.

2. The boron-nitrogen-containing organic compound according to claim 1, characterized in that The boron-nitrogen-containing organic compound has a structure as shown in one of the chemical formulas (I-1) to (IV-1): Wherein, Y1, Y2, R, V0, V1, V2, V3, Q1 ring and Q2 ring are defined as in claim 1.

3. The boron-nitrogen-containing organic compound according to claim 1 or 2, characterized in that: The boron-nitrogen-containing organic compound has a structure as shown in one of the chemical formulas (I-2) to (IV-2): The definitions of Y1, Y2, R, V0, V1, V2, V3, and Q1 ring are the same as those in claim 1, and the definition of V4 is the same as that of V1.

4. The boron-nitrogen-containing organic compound according to any one of claims 1 to 3, characterized in that: The Q1 ring, at each occurrence, is independently selected from one or more combinations of the following structures: wherein each occurrence of V is independently selected from C-R4 or N; W, at each occurrence, is independently selected from B-R5, C(=O), N-R6, O, S, P, P=O or P=S; R4-R6 are selected, at each occurrence, identically or differently, from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl radical having 3 to 20 C atoms, or a keto radical having 1 to 20 C atoms, or an alkoxycarbonyl radical having 2 to 20 C atoms, or an aryloxycarbonyl radical having 7 to 20 C atoms, or a cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic radical having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy radical having 5 to 40 ring atoms, or a combination of these radicals, wherein one or more of the radicals can form a ring system with each other and / or with the radical to which they are bonded.

5. A polymer comprising at least one first repeating unit, characterized in that The first repeating unit comprises at least one structure corresponding to the boron-nitrogen-containing organic compound according to any one of claims 1 to 4.

6. A composition comprising at least one organic solvent and at least one boron-nitrogen-containing organic compound as claimed in any one of claims 1 to 4 or at least one polymer as claimed in claim 5.

7. A mixture comprising an organic compound containing boron and nitrogen as described in any one of claims 1 to 4 or a polymer as described in claim 5, and at least one organic functional material, wherein the organic functional material is selected from at least one of a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminophore and a host material.

8. An organic electronic device comprising at least one boron-nitrogen-containing organic compound according to any one of claims 1 to 4 or a polymer according to claim 5 or a mixture according to claim 7.

9. The organic electronic device according to claim 8, characterized in that: The organic electronic device is selected from a color converter, an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spin electronic device, an organic sensor or an organic plasmon emission diode.

10. The organic electronic device according to claim 8, characterized in that: The organic electronic device is an organic light-emitting device, which comprises a light-emitting layer, wherein the guest material of the light-emitting layer comprises at least one boron-nitrogen-containing organic compound as described in any one of claims 1 to 4 or a polymer as described in claim 5 or a mixture as described in claim 7.

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