A type of boron-doped molecular carbon compound with near-infrared absorption and its preparation method and application

Abstract

The present invention relates to a type of boron-hetero molecular carbon compound with near-infrared absorption and a preparation method and application thereof, and belongs to the technical field of near-infrared absorption materials. The problems of the difficulty in designing and synthesizing stable boron-containing organic materials with near-infrared absorption in the prior art are solved. The boron-hetero molecular carbon compound with near-infrared absorption of the present invention has a structural formula as shown in 1‑13. The present invention also provides the use of the above-mentioned boron-hetero molecular carbon compound with near-infrared absorption in the preparation of organic functional materials with near-infrared absorption, bipolar organic field-effect transistor materials, and organic spintronic device materials. The boron-hetero molecular carbon compound has good solubility in a variety of organic solvents and has near-infrared absorption properties. The light absorption range, light absorption capacity and energy level band gap can be regulated by a conjugated structure. The synthesis method is simple, the yield is high, the purification process is convenient, and it is conducive to large-scale synthesis.

Description

Technical Field

[0001] The present invention belongs to the technical field of near-infrared absorption materials, and specifically relates to a class of boron-mixed molecular carbon compounds with near-infrared absorption, and a preparation method and application thereof, and in particular to the application of the boron-mixed molecular carbon compounds with near-infrared absorption in the preparation of organic functional materials with near-infrared absorption, bipolar organic field effect transistor materials, and organic spintronic device materials. Background Art

[0002] Near infrared (NIR) is an electromagnetic wave between visible light (VIS) and mid-infrared light (MIR), defined as a wavelength range of 780 to 2526 nm. The near infrared region is the earliest non-visible light region discovered. In recent years, near infrared materials have shown broad application prospects in laser shielding, optoelectronic devices, medical treatment and other fields due to their excellent optical, electrical, and magnetic properties.

[0003] Near-infrared materials generally refer to a class of substances that can absorb or reflect near-infrared light, or emit near-infrared light under external stimulation such as light excitation or electric field. According to the mechanism of action, they can be divided into near-infrared absorbing materials and near-infrared luminescent materials. Among them, near-infrared absorbing materials can be divided into inorganic materials and organic materials according to their composition. Among near-infrared organic materials, cyanine dyes, metal complex dyes, quinone dyes and azo dyes are the main molecular systems. They have good biocompatibility and light absorption properties, and are expected to be commercially applied in biomedicine, photoelectric detectors and other fields. For these organic materials, the absorption wavelength of the molecules is mainly adjusted to the near-infrared region by changing the side chain substituents of phthalocyanine compounds, the central metal of metal complexes and the donor or acceptor groups on the skeleton of azo compounds, so as to optimize the near-infrared light absorption performance. At present, the types of organic molecular materials with strong near-infrared absorption ability are still relatively small, which limits the development and application of near-infrared organic materials.

[0004] Boron atoms have empty p orbitals. 2 Selectively introducing boron atoms into the skeleton of carbon atoms can obtain electron-deficient tri-coordinate boron structural units. By expanding the structure of the tri-coordinate boron unit and designing a large-sized boron-containing conjugated system, the hybrid orbital and p-π conjugation effect formed by the p orbital of the boron atom and the π conjugated system can narrow the band gap of the molecule and red-shift the absorption spectrum, which is expected to develop a new type of boron-containing near-infrared light absorbing material. However, due to the high activity of boron atoms and the stability deviation of boron-containing compounds, the molecular design of boron-containing near-infrared light absorbing materials is difficult and the synthesis strategy is limited, which hinders the preparation and development of such near-infrared absorbing materials. Summary of the invention

[0005] In view of this, in order to solve the problems of difficulty in designing and synthesizing stable boron-containing organic materials with near-infrared absorption, the present invention provides a class of boron-containing molecular carbon compounds with near-infrared absorption and a preparation method and application thereof. The boron-containing molecular carbon compounds with near-infrared absorption are large-sized organic boron condensed ring structure compounds containing tricoordinate boron structural units or constructed with tricoordinate boron structural units.

[0006] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows.

[0007] The present invention provides a class of boron heteromolecular carbon compounds with near-infrared absorption, the structural formula of which is one of the following structures:

[0008]

[0009] The present invention also provides a method for preparing a boron heteromolecular carbon compound having near-infrared absorption and having a structural formula of 1, comprising the following steps:

[0010] Step 1: reacting the reactant 1c with boron tribromide under an inert atmosphere. After the reaction is completed, removing the remaining boron tribromide under reduced pressure to obtain compound 1d;

[0011] The structural formula of the compound 1c is:

[0012]

[0013] Step 2: Under an inert atmosphere, 10-bromo-1,8-bis(mesitylphenyloxy)anthracene and n-butyllithium are reacted in a solvent. After the reaction, the solvent is removed under reduced pressure. The obtained yellow solid and compound 1d are reacted in a solvent. After the reaction, the solvent is removed under reduced pressure. The crude product is washed with water, methanol and n-hexane in sequence to obtain a brown-yellow solid. The brown-yellow solid and ferric chloride are reacted in a solvent. After the reaction, the solvent is removed and purified to obtain a purple solid powder.

[0014] Step 3: Under an inert atmosphere, react the purple solid powder and N-bromosuccinimide in a solvent. After the reaction is completed, extract, dry, remove the solvent, and purify to obtain a purple-black solid powder, that is, a boron heteromolecular carbon compound with near-infrared absorption having a structural formula of 1.

[0015] The present invention also provides a method for preparing a boron heteromolecular carbon compound with near-infrared absorption having a structural formula of 2, comprising the following steps:

[0016] Step 1: reacting the reactant 1c and boron tribromide in a solvent under an inert atmosphere. After the reaction is completed, removing the remaining boron tribromide under reduced pressure to obtain compound 1d;

[0017] The structural formula of the compound 1c is:

[0018]

[0019] Step 2: Under an inert atmosphere, compound 1d and 2,4,6-triisopropylbenzene magnesium bromide are reacted in a solvent. After the reaction is completed, the solvent is removed under reduced pressure and purified to obtain a yellow-green powder;

[0020] Step 3: Under an inert atmosphere, react the yellow-green powder and N-bromosuccinimide in a solvent. After the reaction is completed, extract, dry, remove the solvent, and purify to obtain a yellow-green powder, which is a boron heteromolecular carbon compound with near-infrared absorption having a structural formula of 2.

[0021] The present invention also provides a method for preparing a boron heteromolecular carbon compound having near-infrared absorption and having a structural formula of 3, comprising the following steps:

[0022] Step 1: reacting the reactant 3b and boron tribromide in a solvent under an inert atmosphere. After the reaction is completed, removing the remaining boron tribromide under reduced pressure to obtain compound 3c;

[0023] The structural formula of the compound 3b is as follows:

[0024]

[0025] Step 2. Under an inert atmosphere, 10-bromo-1,8-bis(mesitylene-trimethylphenoxy)anthracene and n-butyllithium are reacted in a solvent. After the reaction, the solvent is removed under reduced pressure. The obtained yellow solid and compound 3c are reacted in a solvent. After the reaction, the solvent is removed under reduced pressure. The crude product is washed with water, methanol and n-hexane in sequence to obtain a brown-yellow solid. The brown-yellow solid and ferric chloride are reacted in a solvent. After the reaction, the solvent is removed and purified to obtain a purple solid powder, which is a boron heteromolecular carbon compound with near-infrared absorption having a structural formula of 3.

[0026] The present invention also provides a method for preparing a boron heteromolecular carbon compound with a structural formula of 4-10 or 12 having near-infrared absorption, comprising the following steps:

[0027] Step 1: Under an inert atmosphere, a coupling reaction is carried out in a solvent containing a tricoordinate boron structural unit, a coupling monomer, tetrakistriphenylphosphine palladium, 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl and potassium phosphate. After the reaction is completed, extraction, drying, removal of solvent and purification are performed to obtain a first intermediate product;

[0028] The tri-coordinated boron structural unit is any one of the boron heteromolecular carbon compounds with near-infrared absorption having structural formulas 1-3;

[0029] The coupling monomer is one of the following structures:

[0030]

[0031] Step 2: reacting the first intermediate product with mesitylene trimethylphenyl magnesium bromide in a solvent under an inert atmosphere, extracting and drying after the reaction, reacting the obtained solid with boron trifluoride etherate in a solvent, removing the solvent after the reaction, and obtaining a second intermediate product; reacting the second intermediate product with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in a solvent, removing the solvent after the reaction, and purifying to obtain a boron heteromolecular carbon compound with near-infrared absorption;

[0032] Alternatively, under an inert atmosphere, the first intermediate product, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and trifluoromethanesulfonic acid are reacted in a solvent, and after the reaction is completed, the solvent is removed and purified to obtain a boron heteromolecular carbon compound with near-infrared absorption;

[0033] Alternatively, under an inert atmosphere, the first intermediate product and ferric chloride are reacted in a solvent. After the reaction is completed, the solvent is removed and purified to obtain a boron-hetero molecular carbon compound with near-infrared absorption.

[0034] The present invention also provides a method for preparing a boron heteromolecular carbon compound having a near-infrared absorption and a structural formula of 11 or 13, comprising the following steps:

[0035] Step 1: Under an inert atmosphere, a reaction monomer, a coupling monomer, tetrakistriphenylphosphine palladium, 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl and potassium phosphate are subjected to a coupling reaction in a solvent. After the reaction is completed, extraction, drying, removal of the solvent and purification are performed to obtain a first intermediate product;

[0036] The structural formula of the reaction monomer is as follows:

[0037]

[0038] The coupling monomer is one of the following structures:

[0039]

[0040] Step 2: Under an inert atmosphere, react the first intermediate product with ferric chloride in a solvent, remove the solvent, and purify to obtain a boron-heterocarbon molecular compound with near-infrared absorption.

[0041] The present invention also provides application of the boron heteromolecular carbon compound with near-infrared absorption in the preparation of organic functional materials with near-infrared absorption.

[0042] The present invention also provides the use of the boron-mixed molecular carbon compound with near-infrared absorption in the preparation of bipolar organic field effect transistor materials.

[0043] The present invention also provides application of the boron heteromolecular carbon compound with near-infrared absorption in preparing organic spin electronic device materials.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] 1. The boron-heterocarbon molecular compound (1-3) with near-infrared absorption of the present invention has good water-oxygen stability in the air and high tolerance to various organic reactions, which is helpful for the design and preparation of structure-expanded molecules.

[0046] 2. The boron-hetero molecular carbon compound (4-13) with near-infrared absorption of the present invention is expanded through the boron-hetero molecular carbon compound (1-3) with near-infrared absorption; the spin density of the molecule is mainly distributed on the molecular skeleton, and the mesitylene trimethylphenyl group can act as a steric hindrance to protect the carbon atoms with larger spin density, thereby increasing the stability of the open-shell compound; the large-sized carbon skeleton of the molecule can increase the degree of conjugation of the molecule, reduce the molecular band gap, and achieve the adjustment of the electronic structure and energy level band gap of the molecule; the introduction of boron atoms can not only stabilize free radicals, but also conjugate the electronic distribution and energy level structure of the skeleton; the boron atom is embedded in the molecular skeleton, or protected by triisopropylphenyl at the edge, which can improve the stability of the boron atom; the introduction of mesitylene trimethylphenyl group or triisopropylphenyl group or alkyl chain significantly improves the solubility of the molecule.

[0047] 3. The boron heteromolecule carbon compound (1-13) with near-infrared absorption of the present invention has good solubility in a variety of organic solvents, such as dichloromethane, tetrahydrofuran, and toluene solvents, and the solubility is greater than 2 mg mL -1 , facilitating solution processing of materials and device assembly.

[0048] 4. The boron heteromolecular carbon compound (1-13) with near-infrared absorption of the present invention has a simple synthesis method, a high yield, a convenient purification process, and is conducive to large-scale synthesis.

[0049] 5. The boron-heterocarbon molecular compound (1-13) with near-infrared absorption of the present invention has near-infrared absorption properties. The light absorption range, light absorption capacity and energy band gap can be regulated by the conjugated structure. It is expected to be customized to meet the application requirements of different near-infrared materials and has the potential to develop into a new type of near-infrared organic material. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0051] Figure 1 is the ultraviolet-visible-near-infrared absorption spectrum of the boron-hetero-molecular carbon compound with near-infrared absorption according to Example 4 of the present invention;

[0052] Figure 2 is the ultraviolet-visible-near-infrared absorption spectrum of the boron-hetero-molecular carbon compound with near-infrared absorption according to Example 10 of the present invention;

[0053] Figure 3 is the ultraviolet-visible-near-infrared absorption spectrum of the boron-hetero-molecular carbon compound with near-infrared absorption according to Example 11 of the present invention;

[0054] Figure 4 The electrochemical test cyclic voltammetry curve of the boron-doped molecular carbon compound with near-infrared absorption of Example 11 of the present invention;

[0055] Figure 5 This is the electron spin resonance test spectrum of the boron-hetero molecular carbon compound with near-infrared absorption according to Example 4 of the present invention. DETAILED DESCRIPTION

[0056] In order to further understand the present invention, preferred embodiments of the present invention are described below. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0057] The boron heteromolecular carbon compound with near-infrared absorption of the present invention has a structural formula of one of the following structures:

[0058]

[0059] In the above technical scheme, 1-3 is a tri-coordinated boron structural unit, and 4-13 is a large-sized organic boron condensed ring structure compound constructed by using the tri-coordinated boron structural unit (1-3). Among them, the spin density of the molecule is mainly distributed on the molecular skeleton, and the mesitylene trimethylphenyl group can be used as a steric hindrance to protect the carbon atoms with larger spin density, thereby increasing the stability of the open-shell compound; the large-sized carbon skeleton of the molecule can increase the degree of conjugation of the molecule, reduce the molecular band gap, and adjust the electronic structure and energy level band gap of the molecule; the introduction of boron atoms can not only stabilize free radicals, but also conjugate the electronic distribution and energy level structure of the skeleton; the boron atom is embedded in the molecular skeleton, or protected by triisopropylphenyl at the edge, which can improve the stability of the boron atom; the introduction of mesitylene trimethylphenyl group or triisopropylphenyl group or alkyl chain significantly improves the solubility of the molecule. Therefore, the boron-hetero molecular carbon compound with near-infrared absorption of the present invention can achieve the near-infrared light absorption ability of the material by adjusting the shell opening degree of the boron-hetero molecular carbon compound; the near-infrared light absorption ability of the material can also be achieved by adjusting the conjugated size and conjugated degree of the boron-hetero molecular carbon compound.

[0060] The boron heteromolecular carbon compound with near-infrared absorption of the present invention has the structural formula 1-3, that is, contains a tri-coordinated boron structural unit, and the synthesis route is as follows:

[0061]

[0062] The method for preparing the boron heteromolecule carbon compound with near-infrared absorption and structural formula 4-10 or 12 of the present invention comprises the following steps:

[0063] Step 1: Under an inert atmosphere, a coupling reaction is carried out in a solvent containing a tricoordinate boron structural unit, a coupling monomer, tetrakistriphenylphosphine palladium, 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl and potassium phosphate. After the reaction is completed, extraction, drying, removal of solvent and purification are performed to obtain a first intermediate product;

[0064] Wherein, the coupling monomer is one of the following structures:

[0065]

[0066] Step 2: reacting the first intermediate product with mesitylene trimethylphenyl magnesium bromide in a solvent under an inert atmosphere, extracting and drying after the reaction, reacting the obtained solid with boron trifluoride etherate in a solvent, removing the solvent after the reaction, and obtaining a second intermediate product; reacting the second intermediate product with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in a solvent, removing the solvent after the reaction, and purifying to obtain a boron heteromolecular carbon compound with near-infrared absorption;

[0067] Alternatively, under an inert atmosphere, the first intermediate product, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and trifluoromethanesulfonic acid are reacted in a solvent, and after the reaction is completed, the solvent is removed and purified to obtain a boron heteromolecular carbon compound with near-infrared absorption;

[0068] Alternatively, under an inert atmosphere, the first intermediate product and ferric chloride are reacted in a solvent. After the reaction is completed, the solvent is removed and purified to obtain a boron-hetero molecular carbon compound with near-infrared absorption.

[0069] The method for preparing the boron heteromolecular carbon compound with near-infrared absorption of structural formula 11 or 13 of the present invention comprises the following steps:

[0070] Step 1: Under an inert atmosphere, a reaction monomer, a coupling monomer, tetrakistriphenylphosphine palladium, 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl and potassium phosphate are subjected to a coupling reaction in a solvent. After the reaction is completed, extraction, drying, removal of the solvent and purification are performed to obtain a first intermediate product;

[0071] Among them, the structural formula of the reaction monomer is as follows:

[0072]

[0073] Wherein, the coupling monomer is one of the following structures:

[0074]

[0075] Step 2: Under an inert atmosphere, react the first intermediate product with ferric chloride in a solvent, remove the solvent, and purify to obtain a boron-heterocarbon molecular compound with near-infrared absorption.

[0076] In the above technical scheme, during the preparation of the boron hetero molecular carbon compound with near-infrared absorption of structural formula 1-13, the solvent is not particularly limited, and can be a solvent that can dissolve the corresponding reaction raw materials. The proportion of the reaction raw materials can be determined by those skilled in the art according to the structural formula of the boron hetero molecular carbon compound with near-infrared absorption to be prepared. The inert atmosphere is usually nitrogen, and it should be noted that other inert atmospheres known to those skilled in the art may also be used.

[0077] The present invention also provides application of the boron heteromolecular carbon compound with near-infrared absorption in the preparation of organic functional materials with near-infrared absorption.

[0078] The present invention also provides the use of the boron-mixed molecular carbon compound with near-infrared absorption in the preparation of bipolar organic field effect transistor materials.

[0079] The present invention also provides application of the boron heteromolecular carbon compound with near-infrared absorption in preparing organic spin electronic device materials.

[0080] The terms used in the present invention generally have the meanings commonly understood by those of ordinary skill in the art, unless otherwise specified. In order to enable those of ordinary skill in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below in conjunction with embodiments.

[0081] In the following examples, various processes and methods not described in detail are conventional methods known in the art. Unless otherwise specified, the materials, reagents, devices, instruments, equipment, etc. used in the following examples can be obtained from commercial sources.

[0082] The present invention is further described below with reference to the examples.

[0083] Example 1 Synthesis of Compound 1

[0084] Step 1: Compound 1a (1.0 g, 2.99 mmol), 1,8-dibromonaphthalene (941 mg, 3.29 mmol), tetrakis(triphenylphosphine)palladium (346 mg, 0.30 mmol), potassium carbonate (4.14 g, 29.91 mmol) were placed in a dry reaction bottle with a condenser tube, and after three vacuum and argon ventilation operations, aerated and deoxygenated tetrahydrofuran (20 mL) and aerated and deoxygenated water (4 mL) were injected in sequence. The sealed system was then heated to 90 ° C for 2 h. After the reaction was completed, the reaction mixture was placed in water, and the aqueous phase was extracted three times with dichloromethane. The obtained dichloromethane phase was washed with water once and then the organic phase was combined and dried over anhydrous sodium sulfate. After removing dichloromethane under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent to obtain a white solid, which was recorded as compound 1b. The yield was 831 mg and the yield was 56%.

[0085] The molecular ion (C 25 H 20 Br2O) mass: 495.9733 (calculated value: 495.9860). Theoretical element content (%) C 25 H 20 Br2O: C, 60.51; H, 4.06; Br, 32.20; O, 3.22; Measured element content (%): C, 60.52; H, 4.13. 1 H NMR (400MHz, CDCl3): δ (ppm) 7.92-7.87 (m, 2H), 7.79 (d, 1H), 7.53 (t, 1H), 7.39 (d, 1H), 7. 28(t,1H),7.15(d,1H),7.05(d,1H),6.93(s,2H),6.77(d,1H),2.32(s,3H),2.16(s,6H).

[0086]

[0087] Step 2: Compound 1b (445 mg, 0.90 mmol) was placed in a strictly baked reaction bottle, and after three vacuum and argon gas extraction operations, it was dissolved in 20 mL of dry ether. After the reaction system was cooled to 0 ° C and stabilized for a while, n-butyl lithium solution (1.6M, 1.1 ml, 1.80 mmol) was added dropwise. After reacting at 0 ° C for 2 hours, dichlorodimethylsilane (0.10 mL, 1.15 mmol) was added dropwise, and the reaction was gradually heated to 25 ° C for 6 hours. After the reaction was completed, 3 ml of saturated ammonium chloride solution was added and stirred for 30 minutes, and then the reaction mixture was put into water, and the aqueous phase was extracted with ethyl acetate three times. The obtained ethyl acetate phase was washed with water once and then the organic phase was combined and dried over anhydrous sodium sulfate. After removing ethyl acetate under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent to obtain a light yellow solid, which was recorded as compound 1c. The yield was 198 mg, and the yield was 56%.

[0088] The molecular ion (C 27 H 26 OSi) mass: 394.1662 (calculated value: 394.1573). Theoretical element content (%) C 27 H 26 OSi: C, 82.19; H, 6.64; O, 4.05; Si, 7.12; Measured element content (%): C, 82.20; H, 6.65. 1 H NMR (400MHz, CDCl3): δ (ppm) 8.16 (d, 2H), 8.02 (d, 1H), 7.91 (d, 1H), 7.82-7.77 (m, 2H), 7. 53(t,2H),7.17(d,1H),6.94(s,2H),6.78(d,1H),2.34(s,3H),2.14(s,6H),0.44(s,6H).

[0089]

[0090] Step 3. Compound 1c (106 mg, 0.27 mmol) was placed in a strictly baked reaction bottle with a condenser. After three vacuum and argon ventilation operations, boron tribromide (0.86 ml, 8.24 mmol) was added. The reaction was then carried out at 25°C for 8 hours, and the remaining boron tribromide was removed under reduced pressure to obtain compound 1d. The compound 1d was dissolved and dispersed in 5 ml of dry toluene solution and the system temperature was lowered to 0°C.

[0091] 10-Bromo-1,8-bis(mesitylphenyloxy)anthracene (159mg, 0.30mmol) was placed in a strictly baked reaction bottle, and after three vacuum and argon gas extraction operations, it was dissolved in 8mL of dry ether. After the reaction system was cooled to 0℃ and stabilized for a while, n-butyl lithium solution (1.6M, 0.18ml, 0.30mmol) was added dropwise, and the reaction was carried out at 25℃ for 30min. After the reaction was completed, the ether solvent was removed under reduced pressure to obtain a yellow solid, which was dissolved and dispersed in 5ml of dry toluene solution and added dropwise to 1d of 0℃ toluene solution. After the reaction was completed for 30min, the temperature was raised to 25℃ and the reaction was carried out for 12h. After the reaction was completed, the toluene solution was removed under reduced pressure, and the crude product was washed with water, methanol, and n-hexane in turn to obtain a brown-yellow solid (108mg).

[0092] The obtained brown-yellow solid was put into a strictly baked reaction bottle, and after three vacuum and argon gas extraction operations, it was dissolved in 35mL of dry dichloromethane. After the reaction system was cooled to 0°C and stabilized for a while, ferric chloride (176mg, 1.10mmol) was dissolved in 3ml of nitromethane and added dropwise to the reaction system, and the reaction was carried out at 0°C for 30min. Subsequently, 3ml of methanol was added to quench and terminate the reaction. The solvent was removed under reduced pressure, and the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase, and dichloromethane to petroleum ether = 1:5 (volume ratio) as the eluent to obtain a purple solid powder, which was recorded as compound 1e. The yield was 41mg, and the yield was 38%.

[0093] The molecular ion (C 57 H 45 BO3) mass: 788.3455 (calculated value: 788.3462). Theoretical element content (%) C 57 H 45 BO3: C, 86.79; H, 5.75; B, 1.37; O, 6.08; Measured element content (%): C, 86.78; H, 5.77. 1 H NMR (400MHz, CDCl3): δ (ppm) 10.69 (s, 1H), 10.13 (d, 1H), 9.07 (d, 1H), 8. 81(d,1H),8.76(d,1H),8.52(d,1H),8.35(d,1H),8.05(d,1H),7.78(t,1H ),7.14(d,1H),7.06(s,2H),7.02(s,2H),7.01(s,2H),6.86(d,1H),6.77( d,1H),2.41(s,3H),2.38(s,3H),2.37(s,3H),2.29(s,12H),2.19(s,6H).

[0094]

[0095] Step 4: Compound 1e (156 mg, 0.20 mmol) and N-bromosuccinimide (42 mg, 0.24 mmol) were placed in a reaction bottle with a condenser tube. After three vacuum and argon gas extraction operations, dichloromethane (25 mL) and glacial acetic acid (5 mL) were injected in sequence. The sealed system was then heated to 50 ° C for 2 h. After the reaction was completed, the reaction mixture was put into water, and the aqueous phase was extracted three times with dichloromethane. The obtained dichloromethane phase was washed once and then the organic phase was combined and dried over anhydrous sodium sulfate. After removing dichloromethane under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and dichloromethane to petroleum ether = 1:5 (volume ratio) as the eluent to obtain a purple-black solid powder, which was compound 1. The yield was 122 mg, and the yield was 70%.

[0096] The molecular ion (C 57 H 44 BBrO3) mass: 886.2566 (calculated value: 886.2567). Theoretical element content (%) C 57 H 44 BBrO3: C, 78.90; H, 5.11; B, 1.25; Br, 9.21; O, 5.53; Measured element content (%): C, 78.89; H, 5.12. 1 H NMR (400MHz, CDCl3): δ (ppm) 10.72 (s, 1H), 10.16 (d, 1H), 9.10 (d, 1H), 8.87 (d, 1H), 8.69 (d, 1H), 8.54 (d, 1H), 8.46 (d, 1H), 7.99 (d, 1H), 7.13 (d,1H),7.07(s,2H),7.02(s,2H),7.01(s,2H),6.89(d,1H),6.79(d,1 H),2.41(s,3H),2.38(s,3H),2.36(s,3H),2.28(s,12H),2.19(s,6H).

[0097]

[0098] Example 2 Synthesis of Compound 2

[0099] Step 1: Compound 1c (106 mg, 0.27 mmol) in Example 1 was placed in a strictly baked reaction bottle with a condenser. After three vacuum and argon gas extraction operations, boron tribromide (0.86 ml, 8.24 mmol) was added, and then the reaction was carried out at 25°C for 8 hours, and the remaining boron tribromide was removed under reduced pressure to obtain compound 1d, which was dissolved and dispersed in 5 ml of dry toluene solution. After the reaction system was reduced to 0°C and stabilized for a while, 2,4,6-triisopropylbenzene magnesium bromide (0.4M, 1.37 ml, 0.55 mmol) was added dropwise, and the temperature was raised to 25°C for 2 hours after the reaction for 30 minutes. After the reaction was completed, the toluene solvent was removed under reduced pressure, and the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent to obtain a yellow-green powder, which was recorded as compound 2a. The yield was 68 mg, and the yield was 45%.

[0100] The molecular ion (C 40 H 43 BO) mass: 550.3524 (calculated value: 550.3407). Theoretical element content (%) C 40 H 43 BO: C, 87.26; H, 7.87; B, 1.96; O, 2.91; Measured element content (%): C, 87.25; H, 7.87. 1 H NMR (400MHz, CDCl3): δ (ppm) 8.62 (d, 1H), 8.45 (d, 2H), 8.23 ​​(d, 2H), 8.00 (d, 1H), 7.73 (t, 1H), 7.65 (t, 1H), 7.16-7. 13(m,2H),6.99(s,2H),6.81(s,2H),2.99-2.92(m,1H),2.32-2.25(m,5H),2.02(s,6H),1.34(d,6H),0.93(t,12H).

[0101]

[0102] Step 2: Compound 2a (300 mg, 0.55 mmol) and N-bromosuccinimide (116 mg, 0.65 mmol) were placed in a reaction bottle with a condenser tube. After three vacuum and argon gas extraction operations, dichloromethane (30 mL) and glacial acetic acid (5 mL) were injected in sequence. The sealed system was then heated to 50 ° C for 12 h. After the reaction was completed, the reaction mixture was put into water, and the aqueous phase was extracted three times with dichloromethane. The obtained dichloromethane phase was washed once and then the organic phase was combined and dried over anhydrous sodium sulfate. After removing dichloromethane under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent to obtain a yellow-green powder, which was compound 2. The yield was 192 mg and the yield was 56%.

[0103] The molecular ion (C 40 H 42 BBrO) mass: 628.2338 (calculated value: 628.2512). Theoretical element content (%) C 40 H 42 BBrO: C, 76.32; H, 6.73; B, 1.72; Br, 12.69; O, 2.54; measured element content (%): C, 76.31; H, 6.75. 1 H NMR (400MHz, CDCl3): δ (ppm) 8.68 (d, 1H), 8.38 (t, 2H), 8.24 (d, 1H), 7.99 (d, 1H), 7.73 (t, 1H), 7.14-7.09 (m, 2H),6.98(s,2H),6.81(s,2H),2.99-2.92(m,1H),2.27-2.22(m,5H),2.02(s,6H),1.33(d,6H),0.93(t,12H).

[0104]

[0105] Example 3 Synthesis of Compound 3

[0106] Step 1: Compound 3a (1.0 g, 3.47 mmol), 2,6-di-tert-butyl-4-methylpyridine (1.1 g, 5.21 mmol), and 1,3,5-trichlorobenzene (5 ml) were placed in a dry reaction bottle with a condenser. After three vacuum and argon gas extraction operations, boron tribromide (0.67 ml, 6.94 mmol) was injected, and the system was sealed and heated to 200 ° C for 12 hours. After the reaction was completed, 3 ml of methanol was added dropwise to the system, and then 200-300 mesh silica gel was used as the stationary phase, and ethyl acetate was used as the eluent for column chromatography separation, and the organic solvent was removed under reduced pressure. The crude product was washed once with n-hexane to obtain a light brown solid, which was recorded as compound 3b. The yield was 490 mg, and the yield was 45%.

[0107] The molecular ion (C 20 H 12 BClO) mass: 314.0796 (calculated value: 314.0670). Theoretical element content (%) C 20 H 12 BClO: C, 76.36; H, 3.85; B, 3.44; Cl, ​​11.27; O, 5.09; Measured element content (%): C, 76.37; H, 3.86. 1 H NMR (400MHz, CDCl3): δ (ppm) 9.53 (s, 1H), 9.03 (d, 1H), 8.73 (d, 1H), 8.28 (d, 1H), 8.11 (d,1H),8.03(d,1H),7.84(t,1H),7.79(d,1H),7.72(d,1H),7.67(d,1H),7.41(t,1H).

[0108]

[0109] Step 2: Compound 3b (100 mg, 0.32 mmol) was placed in a strictly baked reaction bottle with a condenser. After three vacuum and argon ventilation operations, boron tribromide (0.92 ml, 9.55 mmol) was added. The mixture was reacted at 25°C for 8 h and then the remaining boron tribromide was removed under reduced pressure to obtain compound 3c. The compound 3c was dissolved and dispersed in 5 ml of dry toluene solution and the system temperature was lowered to 0°C.

[0110] 10-Bromo-1,8-bis(mesitylphenyloxy)anthracene (183mg, 0.35mmol) was put into a strictly baked reaction bottle, and after three vacuum and argon gas extraction operations, it was dissolved in 8mL of dry ether. After the reaction system was cooled to 0℃ and stabilized for a while, n-butyl lithium solution (1.6M, 0.22ml, 0.35mmol) was added dropwise, and the reaction was carried out at 25℃ for 30min. The ether solvent was then removed under reduced pressure to obtain a yellow solid, which was dissolved and dispersed in 5ml of dry toluene solution and added dropwise to the 0℃ toluene solution of 3c. After reacting for 30mins, the temperature was raised to 25℃ and reacted for 12h. After the reaction was completed, the toluene solution was removed under reduced pressure, and the crude product was washed with water, methanol, and n-hexane in turn to obtain a brown-yellow solid (118mg).

[0111] Step 3: Put the obtained brown-yellow solid into a strictly baked reaction bottle, vacuumize and ventilate it with argon three times, and then dissolve it in 35mL of dry dichloromethane. After the reaction system is cooled to 0°C and stabilized for a while, ferric chloride (203mg, 1.27mmol) is dissolved in 3ml of nitromethane and added dropwise to the reaction system, and reacted at 0°C for 30min. Then 3ml of methanol is added to quench and the reaction is terminated. The solvent is removed under reduced pressure, and the crude product is separated by column chromatography using 200-300 mesh silica gel as the stationary phase, and dichloromethane to petroleum ether = 1:5 (volume ratio) as the eluent to obtain a purple solid powder, which is compound 3. The yield is 43mg, and the yield is 37%.

[0112] The molecular ion (C 52 H 36 BClO2) mass: 738.2355 (calculated value: 738.2497). Theoretical element content (%) C 52 H 36 BClO2: C, 84.50; H, 4.91; B, 1.46; Cl, ​​4.80; O, 4.33; Measured element content (%): C, 84.52; H, 4.89. 1 H NMR (400MHz, CDCl3): δ (ppm) 10.59 (s, 1H), 10.20 (s, 1H), 9.18 (d, 1H), 9.01 (d, 1H), 8.85 (t, 2H), 8.76 (d, 1H), 8.44 (d, 1H) ),8.19(d,1H),7.98(d,1H),7.80(t,1H),7.71(t,1H),7.06(s,4H),6.84(d,1H),6.77(d,1H),2.41(s,6H),2.38(s,12H).

[0113]

[0114] Example 4 Synthesis of Compound 4

[0115] Step 1: Compound 1 (66 mg, 0.08 mmol), compound 4a (59 mg, 0.24 mmol), tetrakistriphenylphosphine palladium (4.4 mg, 0.004 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl (3 mg, 0.008 mmol), potassium phosphate (37 mg, 0.38 mmol) were put into a reaction bottle with a condenser, and after three vacuum and argon gas extraction operations, aerated deoxygenated toluene (12 mL), aerated deoxygenated ethanol (3 mL), and aerated deoxygenated water (3 mL) were injected in sequence. Then the temperature was raised to 90 ° C for 2 hours. After the reaction was completed, the reaction mixture was put into water, and the aqueous phase was extracted three times with ethyl acetate. The obtained ethyl acetate phase was washed with water once and then the organic phase was combined and dried over anhydrous sodium sulfate. After removing ethyl acetate under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and ethyl acetate: petroleum ether = 1:12 (volume ratio) as the eluent to obtain a purple-red solid, which was recorded as compound 4b. The yield was 45 mg and the yield was 65%.

[0116] The molecular ion (C 65 H 49 BO5) mass: 920.3558 (calculated value: 920.3673). Theoretical element content (%) C 65 H 49 BO5: C, 84.78; H, 5.36; B, 1.17; O, 8.69; Measured element content (%): C, 84.78; H, 5.35. 1 HNMR (400MHz, CDCl3): δ (ppm) 10.75 (s, 1H), 10.20 (d, 1H), 9.73 (s, 2H), 9.05 (d,1H),8.88(d,1H),8.78(d,1H),8.60(d,1H),8.42(d,2H),7.84(t,2H),7.7 8(d,1H),7.20(d,1H),7.05(s,2H),7.03(s,4H),6.87(d,1H),6.82(d,1H),2 .40(s,3H),2.39(s,3H),2.37(s,3H),2.29(s,6H),2.27(s,6H),2.21(s,6H).

[0117]

[0118] Step 2: Disperse compound 4b (56 mg, 0.06 mmol) in 25 mL of dry tetrahydrofuran under strictly anhydrous and oxygen-free conditions. Add mesitylene trimethylphenylmagnesium bromide (1.0 M, 0.6 mL, 0.60 mmol) dropwise at 25 °C and react for 30 min. After the reaction, the reaction mixture was put into water and the aqueous phase was extracted with ethyl acetate. The ethyl acetate layer was dried and spin-dried, and the obtained solid was placed in a dry reaction bottle, dissolved in 25 mL of dry dichloromethane, and boron trifluoride ether (0.07 mL, 0.6 mmol) was added dropwise at 25 °C. After reacting for 30 min, quench with 2 ml of methanol to terminate the reaction. The reaction solvent was removed under reduced pressure to obtain a purple-black solid, recorded as compound 4c. The yield was 41 mg, and the yield was 60%.

[0119] The molecular ion (C 83 H 69 BO3) mass: 1124.5364 (calculated value: 1124.5340). Theoretical element content (%) C 83 H 69 BO3: C, 88.59; H, 6.18; B, 0.96; O, 4.27; Measured element content (%): C, 88.60; H, 6.18.

[0120]

[0121] Step 3. Under strict anhydrous conditions, compound 4c (20 mg, 0.02 mmol) was dissolved in 8 mL of dry toluene. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (8 mg, 0.04 mmol) was dissolved in 2 mL of dry toluene. The toluene solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was transferred dropwise to the reaction system, and then reacted at 25°C for 30 min. After the reaction, the system was chromatographed on a neutral alumina column (eluent was toluene). After toluene was removed under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and toluene: petroleum ether = 1:3 (volume ratio) as the eluent to obtain a black purple solid, recorded as compound 4. The yield was 10 mg, and the yield was 50%.

[0122] The molecular ion (C 83 H 67 BO3) mass: 1122.5162 (calculated value: 1122.5183). Theoretical element content (%) C 83 H 67 BO3: C, 88.75; H, 6.01; B, 0.96; O, 4.27; Measured element content (%): C, 88.75; H, 6.02.

[0123]

[0124] Example 5 Synthesis of Compound 5

[0125] Step 1: Compound 1 (66 mg, 0.08 mmol), compound 5a (53 mg, 0.23 mmol), tetrakistriphenylphosphine palladium (5 mg, 0.004 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl (3 mg, 0.008 mmol), potassium phosphate (37 mg, 0.38 mmol) were put into a reaction bottle with a condenser, and after three vacuum and argon gas extraction operations, aerated and deoxygenated toluene (12 mL), aerated and deoxygenated ethanol (3 mL), and aerated and deoxygenated water (3 mL) were injected in sequence. Then the temperature was raised to 90 ° C for 2 hours. After the reaction was completed, the reaction mixture was put into water, and the aqueous phase was extracted three times with ethyl acetate. The obtained ethyl acetate phase was washed with water once and then the organic phase was combined and dried over anhydrous sodium sulfate. After removing ethyl acetate under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and ethyl acetate: petroleum ether = 1:15 (volume ratio) as the eluent to obtain a purple-red solid, which was recorded as compound 5b. The yield was 39 mg and the yield was 58%.

[0126] The molecular ion (C 64 H 49 BO4) mass: 892.3364 (calculated value: 892.3724). Theoretical element content (%) C 64 H 49 BO4: C, 86.09; H, 5.53; B, 1.21; O, 7.17; Measured element content (%): C, 86.10; H, 5.52. 1 HNMR (400MHz, CDCl3): δ (ppm) 10.73 (s, 1H), 10.17 (d, 1H), 9.83 (s, 1H), 9.04 (d, 1H), 8 .84(d,1H),8.76(d,1H),8.58(d,1H),8.20(d,1H),8.07(d,1H),7.78(t,1H),7.73(d,1 H),7.65(d,2H),7.18(d,1H),7.05(s,2H),7.02(s,4H),6.86(d,1H),6.80(d,1H),2.40 (s,3H),2.38(s,3H),2.37(s,3H),2.29(s,6H),2.28(s,6H),2.21(s,3H),2.19(s,3H).

[0127]

[0128] Step 2: Disperse compound 5b (35 mg, 0.04 mmol) in 25 mL of dry tetrahydrofuran under anhydrous and oxygen-free conditions. Add mesitylene trimethylphenylmagnesium bromide (1.0 M, 0.4 mL, 0.40 mmol) dropwise at 25 °C and react for 30 min. After the reaction, the reaction mixture was put into water and the aqueous phase was extracted with ethyl acetate. The ethyl acetate layer was dried and spin-dried, and the obtained solid was placed in a dry reaction bottle, dissolved in 25 mL of dry dichloromethane, and boron trifluoride ether (0.05 mL, 0.40 mmol) was added dropwise at 25 °C. After reacting for 30 min, quench with 2 ml of methanol to terminate the reaction. The reaction system was spin-dried to obtain a purple-black solid, recorded as compound 5c. The yield was 23 mg, and the yield was 60%.

[0129] The molecular ion (C 73 H 59 BO3) mass: 994.4368 (calculated value: 994.4557). Theoretical element content (%) C 73 H 59 BO3: C, 88.11; H, 5.98; B, 1.09; O, 4.82; Measured element content (%): C, 88.10; H, 5.97.

[0130]

[0131] Step 3. Under anhydrous conditions, compound 5c (30 mg, 0.03 mmol) was dissolved in 9 mL of dry toluene. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (13 mg, 0.06 mmol) was dissolved in 2 mL of dry toluene. The toluene solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was transferred dropwise to the reaction system, and then the temperature was raised to 80°C for reaction for 5 hours. After the reaction was completed, the system returned to room temperature and was chromatographed on a neutral alumina column (eluent was toluene). After toluene was removed under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and carbon disulfide as the eluent to obtain a black purple solid, recorded as compound 5. The yield was 9 mg, and the yield was 30%.

[0132] The molecular ion (C 73 H 58 BO3·) mass: 993.4315 (calculated value: 993.4479). Theoretical element content (%) C 73 H 58 BO3·: C, 88.20; H, 5.88; B, 1.09; O, 4.83; Measured element content (%): C, 88.21; H, 5.87.

[0133]

[0134] Example 6 Synthesis of Compound 6

[0135] Step 1: Compound 2 (90 mg, 0.14 mmol), compound 4a (111 mg, 0.42 mmol), tetrakistriphenylphosphine palladium (8 mg, 0.007 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl (10 mg, 0.014 mmol), potassium phosphate (99 mg, 0.72 mmol) were put into a reaction bottle with a condenser, and after three vacuum and argon gas extraction operations, aerated and deoxygenated toluene (15 mL), aerated and deoxygenated ethanol (5 mL), and aerated and deoxygenated water (5 mL) were injected in sequence. Then the temperature was raised to 90 ° C for 3 hours. After the reaction was completed, the reaction mixture was put into water, and the aqueous phase was extracted three times with ethyl acetate. The obtained ethyl acetate phase was washed with water once and then the organic phase was combined and dried over anhydrous sodium sulfate. After removing ethyl acetate under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and ethyl acetate: petroleum ether = 1:12 (volume ratio) as the eluent to obtain an apricot yellow solid, which was recorded as compound 6a. The yield was 52 mg and the yield was 53%.

[0136] The molecular ion (C 48 H 47 BO3) mass: 682.3379 (calculated value: 682.3618). Theoretical element content (%) C 48 H 47 BO3: C, 84.45; H, 6.94; B, 1.58; O, 7.03; Measured element content (%): C, 84.45; H, 6.92. 1 HNMR (400MHz, CDCl3): δ (ppm) 9.66 (s, 2H), 8.68 (d, 1H), 8.49 (d, 1H), 8.38 (d, 2H), 8.25 (d, 1H), 7.80 (t, 1H), 7.71 (t, 2H), 7.58 (t ,1H),7.20-7.18(m,2H),7.00(s,2H),6.83(s,2H),2.99-2.93(m,1H),2.33-2.26(m,5H),2.04(s,6H),1.34(d,6H),0.98(t,12H).

[0137]

[0138] Step 2: Disperse compound 6a (42 mg, 0.06 mmol) in 25 mL of dry tetrahydrofuran under anhydrous and oxygen-free conditions. Add trimethylphenylmagnesium bromide (1.0 M, 0.6 mL, 0.60 mmol) dropwise at 25 ° C and react for 30 min. After the reaction is completed, the reaction mixture is put into water and the aqueous phase is extracted with ethyl acetate. The ethyl acetate layer is dried and spin-dried, and the obtained solid is placed in a dry reaction bottle, dissolved in 25 mL of dry dichloromethane, and boron trifluoride ether (0.07 mL, 0.6 mmol) is added dropwise at 25 ° C. After reacting for 30 min, quench with 2 ml of methanol to terminate the reaction. The reaction system is spin-dried to obtain a brown solid, recorded as compound 6b. The yield is 36 mg, and the yield is 66%.

[0139] The molecular ion (C 66 H 67 BO) mass: 886.5274 (calculated value: 886.5285). Theoretical element content (%) C 66 H 67 BO: C, 89.36; H, 7.61; B, 1.22; O, 1.80; Measured element content (%): C, 89.35; H, 7.59.

[0140]

[0141] Step 3. Under anhydrous conditions, compound 6b (25 mg, 0.03 mmol) was dissolved in 8 mL of dry toluene. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (13 mg, 0.06 mmol) was dissolved in 2 mL of dry toluene. The toluene solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was transferred dropwise to the reaction system, and then the temperature was raised to 80°C for reaction for 3 hours. After the reaction was completed and the system returned to room temperature, it was chromatographed on a neutral alumina column (the eluent was toluene). After toluene was removed under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and carbon disulfide as the eluent to obtain a blue-black solid, recorded as compound 6. The yield was 12 mg, and the yield was 46%.

[0142] The molecular ion (C 66 H 65 BO) mass: 884.5139 (calculated value: 884.5128). Theoretical element content (%) C 66 H 65 BO: C, 89.57; H, 7.40; B, 1.22; O, 1.81; Measured element content (%): C, 89.57; H, 7.39.

[0143]

[0144] Example 7 Synthesis of Compound 7

[0145] Step 1: Compound 2 (50 mg, 0.08 mmol), compound 5a (53 mg, 0.23 mmol), tetrakistriphenylphosphine palladium (5 mg, 0.004 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl (3 mg, 0.008 mmol), potassium phosphate (37 mg, 0.38 mmol) were put into a dry reaction bottle with a condenser, and after three vacuum and argon gas extraction operations, dry toluene (12 mL), aerated deoxygenated ethanol (3 mL), and aerated deoxygenated water (3 mL) were injected in sequence. Then the temperature was raised to 90 ° C for 2 hours. After the reaction was completed, the reaction mixture was put into water, and the aqueous phase was extracted three times with ethyl acetate. The obtained ethyl acetate phase was washed with water once and then the organic phase was combined and dried over anhydrous sodium sulfate. After removing ethyl acetate under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and ethyl acetate: petroleum ether = 1:15 (volume ratio) as the eluent to obtain an apricot yellow solid, which was recorded as compound 7a. The yield was 33 mg and the yield was 63%.

[0146] The molecular ion (C 47 H 47 BO2) mass: 654.3518 (calculated value: 654.3669). Theoretical element content (%) C 47 H 47 BO2: C, 86.23; H, 7.24; B, 1.65; O, 4.89; Measured element content (%): C, 86.20; H, 7.31. 1 H NMR (400MHz, CDCl3): δ (ppm) 9.75 (s, 1H), 8.66 (d, 1H), 8.49 (d, 1H), 8.24 (d, 1H), 8.15 (d, 1H), 7.92 (d, 1H), 7.74 (t, 1H), 7.65 (t, 2H), 7 .55(t,1H),7.18-7.16(m,2H),7.00(s,2H),6.82(s,2H),2.99-2.92(m,1H),2.33-2.26(m,5H),2.04(s,6H),1.34(d,6H),0.98(t,12H).

[0147]

[0148] Step 2: Disperse compound 7a (26 mg, 0.04 mmol) in 25 mL of dry tetrahydrofuran under anhydrous and oxygen-free conditions. Add mesitylene trimethylphenylmagnesium bromide (1.0 M, 0.4 mL, 0.40 mmol) dropwise at 25 ° C and react for 30 min. After the reaction is completed, the reaction mixture is put into water and the aqueous phase is extracted with ethyl acetate. The ethyl acetate layer is dried and spin-dried, and the obtained solid is placed in a dry reaction bottle, dissolved in 25 mL of dry dichloromethane, and boron trifluoride ether (0.05 mL, 0.40 mmol) is added dropwise at 25 ° C. After reacting for 30 min, quench with 2 ml of methanol to terminate the reaction. The reaction system is spin-dried to obtain a light brown solid, recorded as compound 7b. The yield is 18 mg, and the yield is 58%.

[0149] The molecular ion (C 56 H 57 BO) mass: 756.4175 (calculated value: 756.4502). Theoretical element content (%) C 56 H 57 BO: C, 88.87; H, 7.59; B, 1.43; O, 2.11; Measured element content (%): C, 88.85; H, 7.62.

[0150]

[0151] Step 3. Under anhydrous conditions, compound 7b (22 mg, 0.03 mmol) was dissolved in 9 mL of dry toluene. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (14 mg, 0.06 mmol) was dissolved in 2 mL of dry toluene. The toluene solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was transferred dropwise to the reaction system, and then the temperature was raised to 80°C for reaction for 2 hours. After the reaction was completed, the system returned to room temperature and was chromatographed on a neutral alumina column (eluent was toluene). After toluene was removed under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and carbon disulfide as the eluent to obtain a brown solid, recorded as compound 7. The yield was 3 mg, and the yield was 13%.

[0152] The molecular ion (C 56 H 56 The mass of BO· is: 755.4126 (calculated value: 755.4424). Theoretical element content (%) C 56 H 56 BO·: C, 88.99; H, 7.47; B, 1.43; O, 2.12; Measured element content (%): C, 88.91; H, 7.47.

[0153]

[0154] Example 8 Synthesis of Compound 8

[0155] Compound 1 (95 mg, 0.11 mmol), 4,9-dipinacol boroester-2,7-di-tert-butylpyrene (30 mg, 0.05 mmol), tetrakistriphenylphosphine palladium (3 mg, 0.003 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl (2 mg, 0.006 mmol), potassium phosphate (56 mg, 0.26 mmol) were put into a reaction bottle with a condenser, and after three vacuum and argon gas extraction operations, aerated deoxygenated toluene (12 mL), aerated deoxygenated ethanol (3 mL), and aerated deoxygenated water (3 mL) were injected in sequence. Then the temperature was raised to 90 ° C for 5 hours. After the reaction was completed, the reaction mixture was put into water, and the aqueous phase was extracted three times with ethyl acetate. The obtained ethyl acetate phase was washed with water once and then the organic phase was combined and dried over anhydrous sodium sulfate. After removing ethyl acetate under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and dichloromethane: petroleum ether = 1:5 (volume ratio) as the eluent to obtain a purple solid (56 mg).

[0156] The obtained purple solid and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (20 mg, 0.09 mmol) were put into a strictly baked reaction bottle, and after three vacuum and argon gas extraction operations, they were dissolved in 30 mL of dry dichloromethane. After the reaction system was cooled to 0 ° C and stabilized for a while, trifluoromethanesulfonic acid (0.08 ml) was added dropwise, and then the temperature was raised to 25 ° C for 1 h. Subsequently, 3 ml of methanol solution was added, and after the solvent was removed under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and dichloromethane to petroleum ether = 1:1 (volume ratio) as the eluent to obtain a purple-black solid powder, namely compound 8. The yield was 15 mg, and the yield was 31%.

[0157] The molecular ion (C 138 H 108 B2O6) mass: 1883.8351 (calculated value: 1883.8366). Theoretical element content (%) C 138 H 108 B2O6: C, 87.98; H, 5.78; B, 1.15; O, 5.10; Measured element content (%): C, 87.97; H, 5.75.

[0158]

[0159] Example 9 Synthesis of Compound 9

[0160] According to the reaction conditions and process of Example 8, compound 1 and (2,6-bis(hexyloxy)naphthalene-1,5-diyl)diboric acid were used as raw materials to obtain a purple-black powder, namely compound 9.

[0161] The molecular ion (C 136 H 114 B2O8) mass: 1897.8765 (calculated value: 1897.8733). Theoretical element content (%) C 136 H 114 B2O8: C, 86.06; H, 6.05; B, 1.14; O, 6.74; Measured element content (%): C, 86.05; H, 6.06.

[0162]

[0163] Example 10 Synthesis of Compound 10

[0164] Compound 3 (78 mg, 0.11 mmol), 4,9-dipinacol boroester-2,7-di-tert-butylpyrene (30 mg, 0.05 mmol), tetrakistriphenylphosphine palladium (3 mg, 0.003 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl (3 mg, 0.006 mmol), potassium phosphate (56 mg, 0.26 mmol) were put into a dry reaction bottle with a condenser, and after three vacuum and argon gas extraction operations, dry toluene (8 mL), aerated deoxygenated ethanol (2 mL), and aerated deoxygenated water (2 mL) were injected in sequence. Then the temperature was raised to 100 ° C for 8 hours. After the reaction was completed, the reaction mixture was put into water, and the aqueous phase was extracted three times with ethyl acetate. The obtained ethyl acetate phase was washed with water once and the organic phase was combined and dried over anhydrous sodium sulfate. After removing ethyl acetate under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and dichloromethane:petroleum ether=1:6 (volume ratio) as the eluent to obtain a purple solid (51 mg).

[0165] The obtained purple-black solid was put into a strictly baked reaction bottle with a condenser tube, and after three vacuum and argon gas extraction operations, it was dissolved in 30mL of dry dichloromethane. After the reaction system was cooled to 0°C and stabilized for a while, ferric chloride (78mg, 0.48mmol) was dissolved in 3ml of nitromethane and added dropwise to the reaction system, and reacted at 0°C for 30min. Subsequently, 3ml of methanol was added to quench and terminate the reaction. After removing the solvent under reduced pressure, the crude product was separated by column chromatography using 200-300 mesh silica gel as the stationary phase and dichloromethane to petroleum ether = 1:5 (volume ratio) as the eluent to obtain a purple-black solid powder, which is compound 10. The yield is 2mg, and the yield is 5%.

[0166] The molecular ion (C 128 H 88 B2O4) mass: 1711.6935 (calculated value: 1711.6902). Theoretical element content (%) C 128 H 88 B2O4: C, 89.82; H, 5.18; B, 1.26; O, 3.74; Measured element content (%): C, 89.83; H, 5.20. 1 H NMR (400MHz, C2D2Cl4): δ (ppm) 10.83 (s, 2H), 10.23 (d, 2H), 10.00 (s, 2H), 9.69 (d, 2H), 9.51 (t, 4H), 9.40 (d, 2H), 9.33 (d, 4H), 8.9 2(d,2H),8.33(d,2H),7.15(s,4H),7.13(s,4H),7.10(d,2H),7.04(d,2H),2.47(s,6H),2.46(s,6H),2.37(s,24H),1.57(s,18H).

[0167]

[0168] Example 11 Synthesis of Compound 11

[0169] According to the reaction conditions and process of Example 10, the reaction monomer and 4,9-dipinacol boroester-2,7-di-tert-butylpyrene were used as raw materials to obtain a purple powder, namely Compound 11. The structural formula of the reaction monomer is as follows:

[0170]

[0171] The molecular ion (C 94 H 84 B2) Mass: 1235.6755 (calculated value: 1235.6793). Theoretical element content (%) C 94 H 84 B2: C, 91.40; H, 6.85; B, 1.75; Measured element content (%): C, 91.38; H, 6.86. 1HNMR (400MHz, CDCl3): δ (ppm) 9.86 (d, 2H), 9.63 (d, 2H), 9.46 (d, 2H), 9.21 (d, 2H), 8.74 (d, 4H), 8.54 (t, 2H), 8.23-8.20 ( m,4H),7.99(d,2H),7.24(s,4H),3.16-3.09(m,2H),2.79-2.65(m,4H),1.70(s,18H),1.49(d,12H),1.14-1.10(m,24H).

[0172]

[0173] Example 12 Synthesis of Compound 12

[0174] According to the reaction conditions and process of Example 10, compound 3 and 2',5'-dibromo-4,4'-di-tert-butyl-1,1':4',1"-terphenyl were used as raw materials to obtain a purple-black powder, namely compound 12.

[0175] The molecular ion (C 130 H 92 B2O4) mass: 1739.7258 (calculated value: 1739.7215). Theoretical element content (%) C 130 H 92 B2O4: C, 89.75; H, 5.33; B, 1.24; O, 3.68; Measured element content (%): C, 89.75; H, 5.31.

[0176]

[0177] Example 13 Synthesis of Compound 13

[0178] According to the reaction conditions and process of Example 10, the reaction monomer and 6,13-dipinacol boroester-2-(tert-butyl)-9b boronaphtho[1,8-ab]perylene were used as raw materials to obtain a purple powder, namely Compound 13. The structural formula of the reaction monomer is as follows:

[0179]

[0180] The molecular ion (C 100 H 85 B3) Mass: 1318.6975 (calculated value: 1318.6930). Theoretical element content (%) C 100 H 85 B3: C, 91.05; H, 6.49; B, 2.46; Measured element content (%): C, 91.06; H, 6.48.1 H NMR (400MHz, CDCl3): δ (ppm) 10.13 (d, 2H), 9.47 (t, 2H), 9.22 (d, 2H), 9.06 (d, 2 H),8.93(t,4H),8.83(t,2H),8.60(t,2H),8.44(d,4H),8.30-8.25(m,2H),8.07 -8.04(m,2H),7.96(t,2H),7.81-7.77(m,2H),7.35(d,2H),7.18(d,4H),3.08- 3.05(m,2H),2.53-2.46(m,4H),1.75(s,9H),1.43(d,12H),1.16-0.99(t,24H).

[0181]

[0182] The boron hetero molecular carbon compound 4 synthesized in Example 4, the boron hetero molecular carbon compound 10 synthesized in Example 10, and the boron hetero molecular carbon compound 11 synthesized in Example 11 were subjected to UV-visible absorption spectral analysis. The results are as follows: Figure 1 , Figure 2 , Figure 3 As shown, it can be seen from the figure that the main absorption peaks of boron heteromolecule carbon compound 4 are at 953nm, 858nm, 783nm, and 606nm, showing visible and near-infrared absorption properties; the main absorption peaks of boron heteromolecule carbon compound 10 are at 685nm, 575nm, and 513nm, showing near-infrared absorption properties; the main absorption peaks of boron heteromolecule carbon compound 11 are at 585nm, 546nm, and 490nm, and compared with boron heteromolecule carbon compound 10, its maximum absorption blue shift is 100nm, indicating that the conjugated π skeleton expansion and increase can significantly red-shift the absorption spectrum of the compound to the near-infrared. The boron heteromolecule carbon compound of the present invention has obvious near-infrared absorption properties, and these compounds can be separated and purified by column chromatography through a silica gel column, indicating that it has good stability and has the application potential for preparing near-infrared materials.

[0183] Electrochemical analysis was performed on the boron heteromolecular carbon compound 11 synthesized in Example 11. The results are as follows: Figure 4 As shown, the calculated HOMO and LUMO energy levels of the boron heteromolecular carbon compound 11 are -5.20 eV and -3.03 eV respectively, and the band gap is 2.17 eV. This shows that the energy level structure and narrow band gap properties of the boron heteromolecular carbon compound of the present invention indicate that it has the potential to be used as a bipolar organic field effect transistor material.

[0184] Electron paramagnetic resonance (ESR) analysis was performed on the boron heteromolecular carbon compound 4 synthesized in Example 4. The results are as follows: Figure 5As shown in the figure, it can be seen that the boron-doped carbon compound 4 has an ESR signal response at 25°C, g e The value is 2.0032, indicating the existence of a single electron in a free radical. Its paramagnetic property indicates that the boron heteromolecular carbon compound of the present invention has the potential to be used as a material for organic spin electronic devices.

[0185] Obviously, the above-mentioned embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the embodiments. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. The obvious changes or modifications derived therefrom are still within the protection scope of the invention.

Claims

1. An intermediate for synthesizing a boron heteromolecular carbon compound, characterized in that: The structural formula is one or more of the following structures:

2. Boron-hetero molecular carbon compound, characterized in that: The structural formula is one or more of the following structures:

3. The method for preparing the boron heteromolecular carbon compound of structural formula 1 according to claim 1, characterized in that: The following steps are involved: Step 1: reacting the reactant 1c with boron tribromide under an inert atmosphere. After the reaction is completed, removing the remaining boron tribromide under reduced pressure to obtain compound 1d; The structural formulas of compounds 1c and 1d are: Step 2: Under an inert atmosphere, 10-bromo-1,8-bis(mesitylphenyloxy)anthracene and n-butyllithium are reacted in a solvent. After the reaction, the solvent is removed under reduced pressure. The obtained yellow solid and compound 1d are reacted in a solvent. After the reaction, the solvent is removed under reduced pressure. The crude product is washed with water, methanol and n-hexane in sequence to obtain a brown-yellow solid. The brown-yellow solid and ferric chloride are reacted in a solvent. After the reaction, the solvent is removed and purified to obtain a purple solid powder. Step 3: Under an inert atmosphere, react the purple solid powder and N-bromosuccinimide in a solvent. After the reaction is completed, extract, dry, remove the solvent, and purify to obtain a purple-black solid powder, i.e., a boron heteromolecular carbon compound with a structural formula of 1.

4. The method for preparing the boron heteromolecular carbon compound of structural formula 2 according to claim 1, characterized in that: The following steps are involved: Step 1: reacting the reactant 1c and boron tribromide in a solvent under an inert atmosphere. After the reaction is completed, removing the remaining boron tribromide under reduced pressure to obtain compound 1d; The structural formulas of compounds 1c and 1d are: Step 2: Under an inert atmosphere, compound 1d and 2,4,6-triisopropylbenzene magnesium bromide are reacted in a solvent. After the reaction is completed, the solvent is removed under reduced pressure and purified to obtain a yellow-green powder; Step 3: Under an inert atmosphere, react the yellow-green powder and N-bromosuccinimide in a solvent. After the reaction is completed, extract, dry, remove the solvent, and purify to obtain a yellow-green powder, which is a boron heteromolecular carbon compound with a structural formula of 2.

5. The method for preparing the boron heteromolecular carbon compound of structural formula 3 according to claim 1, characterized in that: The following steps are involved: Step 1: reacting the reactant 3b and boron tribromide in a solvent under an inert atmosphere. After the reaction is completed, removing the remaining boron tribromide under reduced pressure to obtain compound 3c; The structural formulas of the compounds 3b and 3c are as follows: Step 2. Under an inert atmosphere, 10-bromo-1,8-bis(mesitylene-trimethylphenoxy)anthracene and n-butyllithium are reacted in a solvent. After the reaction, the solvent is removed under reduced pressure. The obtained yellow solid and compound 3c are reacted in a solvent. After the reaction, the solvent is removed under reduced pressure. The crude product is washed with water, methanol and n-hexane in sequence to obtain a brown-yellow solid. The brown-yellow solid and ferric chloride are reacted in a solvent. After the reaction, the solvent is removed and purified to obtain a purple solid powder, which is a boron heteromolecular carbon compound with structural formula 3.

6. The method for preparing the boron heteromolecular carbon compound of structural formula 4, 6, 8, 9, 10, 11 or 12 according to claim 2, characterized in that: The following steps are involved: Step 1: Under an inert atmosphere, a coupling reaction is carried out in a solvent containing a tricoordinate boron structural unit, a coupling monomer, tetrakistriphenylphosphine palladium, 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl and potassium phosphate. After the reaction is completed, extraction, drying, removal of solvent and purification are performed to obtain a first intermediate product; The tri-coordinate boron structural unit is any one of the intermediates 1-3 for synthesizing the boron heteromolecular carbon compound according to claim 1; The coupling monomer is one of the following structures: Step 2: reacting the first intermediate product with mesitylene trimethylphenyl magnesium bromide in a solvent under an inert atmosphere, extracting and drying after the reaction, reacting the obtained solid with boron trifluoride etherate in a solvent, removing the solvent after the reaction, and obtaining a second intermediate product; reacting the second intermediate product with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in a solvent, removing the solvent after the reaction, and purifying to obtain a boron heteromolecular carbon compound; Alternatively, under an inert atmosphere, the first intermediate product, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and trifluoromethanesulfonic acid are reacted in a solvent, and after the reaction is completed, the solvent is removed and purified to obtain a boron heteromolecular carbon compound; Alternatively, under an inert atmosphere, the first intermediate product and ferric chloride are reacted in a solvent, and after the reaction is completed, the solvent is removed and purified to obtain a boron heteromolecular carbon compound.

7. Use of the boron heteromolecular carbon compound with structural formula 4, 6, 8, 9, 10 or 12 as claimed in claim 2 in the preparation of organic functional materials with near-infrared absorption.

8. Use of the boron heteromolecular carbon compound of structural formula 11 as claimed in claim 2 in the preparation of bipolar organic field effect transistor materials.

9. Use of the boron heteromolecular carbon compound with structural formula 4 or 6 as claimed in claim 2 in the preparation of organic spin electronic device materials.

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