Polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bond and preparation method of polycyclic fusion molecule

Abstract

The invention discloses a polycyclic fusion molecule containing an oxygen-boron-nitrogen coordination bond and a preparation method of the polycyclic fusion molecule, and belongs to the field of organic photoelectric functional materials. The structural formula of the polycyclic fusion molecule is # imgabs0 #. According to the invention, oxygen, boron, nitrogen and other hetero-elements are introduced into an all-carbon two-dimensional large conjugate skeleton, and meanwhile, a side substituent of the boron element is cut, so that the photoelectric property and aggregation performance of molecules are effectively regulated and controlled, and the problem that in the prior art, conjugated molecules cannot simultaneously ensure relatively high mobility and luminescent quantum yield is solved. The prepared polycyclic fusion molecule has potential application value in organic photoelectric devices such as organic field effect transistors, organic light emitting diodes, organic solar cells, organic photoelectric detectors and organic electrochemical transistors.

Description

Technical Field

[0001] The invention belongs to the field of organic photoelectric functional materials, and in particular relates to a polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds and a preparation method thereof. Background Art

[0002] Organic conjugated molecules are widely used in organic photovoltaic devices, organic light-emitting devices, organic field-effect transistor devices, organic photodetection devices, and organic electrochemical transistors due to their good structural tailorability, solution processability, light weight, and flexibility. With the rapid development of information technology, higher requirements are placed on the integrated performance of organic optoelectronic devices. For example, traditional light-emitting devices and field-effect transistor devices only require materials to have high luminescence quantum yields or mobility, while the application of emerging devices requires a material to have both high mobility and quantum yield. Therefore, the design and preparation of high-mobility emission-type organic conjugated molecules that integrate efficient charge transfer and powerful emission functions is expected to achieve the preparation of organic optoelectronic devices with higher functional integration.

[0003] However, for organic conjugated molecules, mobility and luminescence quantum yield are two contradictory parameters that are difficult to coordinate. Mobility requires molecules to have good skeleton planarity and π-π interaction, while luminescence quantum yield requires weakening the π-π interaction between molecules. Therefore, it is currently a high technical challenge to achieve high mobility and high emission on the same molecule. Therefore, the development of new organic conjugated molecules through molecular structure tailoring is of great significance to the development of organic optoelectronic devices. Summary of the invention

[0004] In view of the above-mentioned technical defects in the art, the present invention provides a polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds and a preparation method thereof, which regulates the polarity and electronic properties of the conjugated molecule by introducing heteroatoms such as oxygen, boron, and nitrogen into an all-carbon conjugated skeleton; while ensuring the planarity of the skeleton, substituents located outside the plane are introduced into the boron atoms in a tetrahedral configuration, thereby weakening the π-π interaction between molecules, thereby ensuring that the molecules have a higher mobility and achieving a higher luminescence quantum efficiency.

[0005] In order to achieve the above purpose, the technical solution of the present invention is: One of the purposes of the present invention is to protect a polycyclic fusion molecule containing an oxygen-boron-nitrogen coordination bond, which has the following structural formula: , In the formula, π is any one of the following structural formulas: , Among them, R is a fatty chain, and its structural formula is , p is an integer from 0 to 5, m is an integer from 0 to 20, and n is an integer from 1 to 20; X is any one of the following structural formulas: , Among them, R' is a fatty chain, and its structural formula is , p is an integer from 0 to 5, m is an integer from 0 to 20, and n is an integer from 1 to 20.

[0006] The second object of the present invention is to protect the preparation method of the polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds, and the reaction flow diagram thereof is as follows: ; It includes the following steps: S1: Preparation of 3-hydroxy-6-bromo[2,2]bipyridine: 6-bromo-3-hydroxypyridine is dissolved in an organic solvent A, a base and iodophenyldiacetic acid are added, and the mixture is stirred at room temperature for a certain period of time, and the obtained crude product is recrystallized or separated by column chromatography to obtain 3-hydroxy-6-bromo[2,2]bipyridine; S2: Preparation of boronated precursor: dissolving the obtained 3-hydroxy-6-bromo[2,2]bipyridine and the methoxy-containing boric acid functionalized aromatic unit in a mixed solvent consisting of an organic solvent B and an inorganic base aqueous solution, and carrying out a coupling reaction using a palladium compound as a catalyst. After the reaction is completed, the crude product is extracted and concentrated, and recrystallized with a mixed solution of n-hexane and dichloromethane to obtain a boronated precursor; S3: dissolving the obtained borylated precursor in an organic solvent C, adding a borylation reagent to carry out a borylation ring-closing reaction, extracting and concentrating the obtained crude product after the reaction is completed, and separating the crude product by recrystallization or column chromatography to obtain the polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds.

[0007] Furthermore, in step S1, the organic solvent A is dichloromethane, toluene, chloroform or tetrahydrofuran.

[0008] Furthermore, in step S1, the base is potassium carbonate, sodium carbonate or cesium carbonate.

[0009] Furthermore, in step S1, the molar ratio of 6-bromo-3-hydroxypyridine to the base and iodophenyldiacetic acid is 8:1:2 to 6:1:2.

[0010] Furthermore, in step S1, the reaction time is 1 to 12 hours.

[0011] Further, in step S2, the methoxy-containing boronic acid functionalized aromatic unit is any one of 2-hydroxyphenylboronic acid, 4-tert-butyl-2-hydroxyphenylboronic acid, 3-hydroxy-5-alkyl-2-boric acid furan, 3-hydroxy-5-alkyl-2-boric acid thiophene, 3-hydroxy-5-alkyl-2-boric acid selenophene, 3-hydroxy-2-boric acid naphthalene, 3-hydroxy-7-tert-butyl-2-boric acid naphthalene, 2-alkyl-6-hydroxy-5-boric acid benzofuran, 2-alkyl-6-hydroxy-5-boric acid benzothiophene, 2-alkyl-6-hydroxy-5-boric acid benzoselenophene, 3-hydroxy-5-alkyl-2-boric acid dithiophene, 3-hydroxy-5-alkyl-2-boric acid terthiophene, and 3-methoxythiophene-2-boric acid pinacol ester.

[0012] Furthermore, in step S2, the molar ratio of 3-hydroxy-6-bromo[2,2]bipyridine to the methoxy-containing boronic acid functionalized aromatic unit is 1:2 to 1:3.

[0013] Furthermore, in step S2, the organic solvent B is at least one of anhydrous ethanol, toluene, chloroform, tetrahydrofuran, 1,4-dioxane or ethylene glycol dimethyl ether.

[0014] Furthermore, in step S2, the inorganic base aqueous solution is an aqueous solution of sodium carbonate, potassium carbonate or cesium carbonate, and its concentration is 1 M.

[0015] Furthermore, the volume ratio of the organic solvent B to the inorganic alkali aqueous solution in the mixed solvent of step S2 is 2:1~1:1.

[0016] Furthermore, in step S2, the palladium compound is tetrakistriphenylphosphine palladium or palladium dichloride, and the molar ratio of the palladium compound to 3-hydroxy-6-bromo[2,2]bipyridine is 3:100 to 5:100.

[0017] Furthermore, in step S2, the coupling reaction is carried out at a temperature of 40 to 120 °C and for a time of 4 to 24 hours.

[0018] Furthermore, during the recrystallization in step S2, the volume ratio of n-hexane to dichloromethane used is 4:1.

[0019] Further, in step S2, the π in the structural formula of the obtained boronated precursor can be benzene, 4-tert-butylbenzene, 2-alkylfuran, 2-alkylthiophene, 2-alkylselenophene, naphthalene, 7-tert-butylnaphthalene, 2-alkylbenzofuran, 2-alkylbenzothiophene, 2-alkylphenylpropionylselenophene, 2-alkyldithiophene, 2-alkylterthiophene, and the methoxy and boric acid functionalized aromatic units are 2-hydroxyphenylboronic acid, 4-tert-butyl-2-hydroxyphenylboronic acid, 3-hydroxy-5-alkyl- 2-Boric acid furan, 3-hydroxy-5-alkyl-2-boric acid thiophene, 3-hydroxy-5-alkyl-2-boric acid selenophene, 3-hydroxy-2-boric acid naphthalene, 3-hydroxy-7-tert-butyl-2-boric acid naphthalene, 2-alkyl-6-hydroxy-5-boric acid benzofuran, 2-alkyl-6-hydroxy-5-boric acid benzothiophene, 2-alkyl-6-hydroxy-5-boric acid benzoselenophene, 3-hydroxy-5-alkyl-2-boric acid dithiophene, 3-hydroxy-5-alkyl-2-boric acid terthiophene.

[0020] Furthermore, in step S3, the organic solvent C is dichloromethane, toluene, chloroform, tetrahydrofuran or 1,4-dioxane.

[0021] Further, in step S3, when X is a fluorine atom, a chlorine atom, or a bromine atom, the boronating agent is boron trifluoride, boron trichloride, or boron tribromide; when X is an aliphatic chain, a phenyl group, p-tert-butylbenzene, p-alkylbenzene, p-fluorobenzene, trifluorobenzene, trimethylbenzene, p-trifluoromethylbenzene, trifluoromethylbenzene, or 2-alkylthiophene, the boronating agent is a composition of boron tribromide and a corresponding one of alkylmagnesium bromide, phenylmagnesium bromide, p-tert-butylphenylmagnesium bromide, p-alkylphenylmagnesium bromide, p-fluorophenylmagnesium bromide, trifluorophenylmagnesium bromide, trimethylphenylmagnesium bromide, p-trifluoromethylphenylmagnesium bromide, trifluoromethylphenylmagnesium bromide, or 2-alkylthiophenemagnesium bromide.

[0022] Furthermore, in step S3, the molar ratio of the boronation precursor to the boronation reagent is 1:4 to 1:16.

[0023] Furthermore, in step S3, the temperature of the borylation ring-closing reaction is 40-120 °C, and the time is 4-24 hours.

[0024] The third purpose of the present invention is to protect the application of the polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds in the preparation of organic photoelectric devices.

[0025] Compared with the prior art, the present invention has the following beneficial effects: 1. The polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds provided by the present invention is a novel polycyclic fusion molecule prepared by introducing heteroelements such as oxygen, boron, and nitrogen into a full carbon skeleton. Its structure and properties are adjustable, which expands the types of organic conjugated molecules and has broad application prospects in the field of organic optoelectronic devices. 2. The preparation method of the polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds provided by the present invention has a simple route, and only three steps are required from the initial raw materials to the final product, which is economical and efficient and is conducive to commercialization; 3. The skeleton of the polycyclic fusion unit containing oxygen-boron-nitrogen coordination bonds of the present invention has good planarity, which can ensure good mobility. The substituents on the tetracoordinated boron and the skeleton are not in the same plane, which can effectively prevent the π-π stacking between molecules and achieve a higher luminescence quantum yield. Therefore, it has important application prospects in emissive organic field effect transistors. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the H NMR spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 1d prepared in Example 1.

[0027] Figure 2 This is the UV-visible absorption spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 1d prepared in Example 1.

[0028] Figure 3 This is the fluorescence emission spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 1d prepared in Example 1.

[0029] Figure 4 This is the H-NMR spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 2a prepared in Example 2.

[0030] Figure 5 This is the UV-visible absorption spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 2a prepared in Example 2.

[0031] Figure 6 This is the fluorescence emission spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 2a prepared in Example 2.

[0032] Figure 7 This is the H NMR spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 3a prepared in Example 3.

[0033] Figure 8 This is the UV-visible absorption spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 3a prepared in Example 3.

[0034] Fig. 9 This is the fluorescence emission spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 3a prepared in Example 3.

[0035] Fig.10 This is the H NMR spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 4b prepared in Example 4.

[0036] Fig.11 This is the UV-visible absorption spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 4b prepared in Example 4.

[0037] Fig.12 This is the fluorescence emission spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 4b prepared in Example 4.

[0038] Fig.13 This is the H-NMR spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 5b prepared in Example 5.

[0039] Fig.14 This is the UV-visible absorption spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 5b prepared in Example 5.

[0040] Fig.15 This is the fluorescence emission spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 5b prepared in Example 5.

[0041] Fig.16 This is the H-NMR spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 6b prepared in Example 6.

[0042] Fig.17 This is the UV-visible absorption spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 6b prepared in Example 6.

[0043] Fig.18 This is the fluorescence emission spectrum of the oxygen-containing boron-nitrogen coordination bond polycyclic fusion molecule 6b prepared in Example 6. DETAILED DESCRIPTION

[0044] A polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds, the preparation of which comprises the following steps: S1: dissolving 6-bromo-3-hydroxypyridine in organic solvent A to a concentration of 0.36 M, then adding a base and iodophenyldiacetic acid, stirring and reacting at room temperature for 1 to 12 hours, and separating the obtained crude product by recrystallization or column chromatography to obtain 3-hydroxy-6-bromo[2,2]bipyridine; the molar ratio of 6-bromo-3-hydroxypyridine to the base and iodophenyldiacetic acid is 8:1:2 to 6:1:2; S2: Preparation of borylation precursor: 3-hydroxy-6-bromo[2,2]bipyridine and methoxy-containing boric acid functionalized aromatic unit in a molar ratio of 1:2~1:3 are dissolved in a mixed solvent consisting of an organic solvent B and a 1 M aqueous solution of an inorganic base (2:1~1:1, v / v), wherein the concentration of 3-hydroxy-6-bromo[2,2]bipyridine is 0.07~0.08 M, and then a palladium compound is used as a catalyst (cuprous chloride can be added as a co-catalyst if necessary), and stirred at 40~120 °C for 4~24 hours to allow a coupling reaction to occur. After the reaction is completed, the crude product is extracted and concentrated, and recrystallized with n-hexane and dichloromethane (4:1, v / v) to obtain a borylation precursor; the molar ratio of the palladium compound to 3-hydroxy-6-bromo[2,2]bipyridine is 3:100~5:100; S3: dissolving the obtained boronated precursor in an organic solvent C to a concentration of 0.005 M to 0.006 M, then adding a boronating reagent at a molar ratio of 1:4 to 1:16, stirring at 40 to 120 °C for 4 to 24 hours to allow a boronating ring-closing reaction to occur, extracting and concentrating the obtained crude product after completion of the reaction, and separating it by recrystallization or column chromatography to obtain the polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds.

[0045] Wherein, in step S1, the organic solvent A is dichloromethane, toluene, chloroform or tetrahydrofuran, and the base is potassium carbonate, sodium carbonate or cesium carbonate.

[0046] In step S2, the methoxy-containing boric acid functionalized aromatic unit is any one of 2-hydroxyphenylboronic acid, 4-tert-butyl-2-hydroxyphenylboronic acid, 3-hydroxy-5-alkyl-2-boric acid furan, 3-hydroxy-5-alkyl-2-boric acid thiophene, 3-hydroxy-5-alkyl-2-boric acid selenophene, 3-hydroxy-2-boric acid naphthalene, 3-hydroxy-7-tert-butyl-2-boric acid naphthalene, 2-alkyl-6-hydroxy-5-boric acid benzofuran, 2-alkyl-6-hydroxy-5-boric acid benzothiophene, 2-alkyl-6-hydroxy-5-boric acid benzoselenophene, 3-hydroxy-5-alkyl-2-boric acid dithiophene, 3-hydroxy-5-alkyl-2-boric acid terthiophene, and 3-methoxythiophene-2-boric acid pinacol ester. The organic solvent B is at least one of anhydrous ethanol, toluene, chloroform, tetrahydrofuran, 1,4-dioxane or ethylene glycol dimethyl ether. The inorganic alkali aqueous solution is an aqueous solution of sodium carbonate, potassium carbonate or cesium carbonate. The palladium compound is tetrakistriphenylphosphine palladium or palladium dichloride.

[0047] In step S3, the organic solvent C is dichloromethane, toluene, chloroform, tetrahydrofuran or 1,4-dioxane. When X is a fluorine atom, a chlorine atom or a bromine atom, the boronating agent is boron trifluoride, boron trichloride or boron tribromide; when X is an aliphatic chain, a phenyl group, p-tert-butylbenzene, p-alkylbenzene, p-fluorobenzene, trifluorobenzene, trimethylbenzene, p-trifluoromethylbenzene, trifluoromethylbenzene or 2-alkylthiophene, the boronating agent is a composition of boron tribromide and a corresponding one of alkylmagnesium bromide, p-tert-butylphenylmagnesium bromide, p-alkylphenylmagnesium bromide, p-fluorophenylmagnesium bromide, trifluorophenylmagnesium bromide, trimethylphenylmagnesium bromide, p-trifluoromethylphenylmagnesium bromide, trifluoromethylphenylmagnesium bromide or 2-alkylthiophenemagnesium bromide.

[0048] In order to make the contents of the present invention easier to understand, the technical solution of the present invention is further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0049] Example 1 The synthesis route of a polycyclic fusion molecule 1d containing an oxygen-boron-nitrogen coordination bond provided in this embodiment is as follows: , 1) Preparation of compound 1b: In an anhydrous and oxygen-free environment under the protection of inert gas, 6-bromo-3-hydroxypyridine (1a, 500 mg, 2.87 mmol) was dissolved in 8 ml of dichloromethane, and cesium carbonate (156 mg, 0.48 mmol) and iodophenyldiacetic acid (PIDA) (309 mg, 0.96 mmol) were added in sequence. The mixture was stirred at room temperature for 2 hours. The crude product was chromatographed on a silica gel column (200-300 mesh) using a mixture of petroleum ether / ethyl acetate (10:1, v / v) as an eluent. The product was recrystallized with n-hexane and dichloromethane (4:1, v / v) to obtain 98 mg of compound 1b with a yield of 19.71%. The theoretical calculated values ​​of elemental analysis are C, 34.72%, H, 1.75%, O, 9.25%, N, 8.10%. The actual experimental values ​​are C, 34.56%, H, 1.72%, O, 9.35%, N, 8.06%.

[0050] 2) Preparation of compound 1c: In an anhydrous and oxygen-free environment under inert gas protection, 1b (125 mg, 0.36 mmol) was dissolved in 10 ml of tetrahydrofuran, and 2 ml of anhydrous ethanol, 10 ml of water, potassium carbonate (1497.9 mg, 10.84 mmol) were added, followed by tetrakis(triphenylphosphine)palladium (12.5 mg, 0.011 mmol) and 2-methoxyphenylboronic acid (132 mg, 0.86 mmol), and refluxed at 80°C for 12 hours under nitrogen atmosphere. After the reaction was completed, the mixture was extracted 3-4 times with a mixture of 80 ml of water and 50 ml of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was recrystallized with a mixture of dichloromethane and n-hexane (1:4, v / v) to obtain 136 mg of compound 1c with a yield of 85.78%. The theoretical calculated values ​​of elemental analysis are C, 71.99%, H, 5.03%, O, 15.98%, N, 7.00%. The actual experimental values ​​are C, 71.86%, H, 5.08%, O, 15.89%, N, 7.12%.

[0051] 3) Preparation of compound 1d: In an anhydrous and oxygen-free environment under the protection of inert gas, 1c (100 mg, 0.23 mmol) was dissolved in 50 ml of anhydrous toluene, and then a solution of boron trifluoride in ether (1 mol / L, 1.37 mL) was added and refluxed at 80°C for 24 hours. After the reaction was completed, it was extracted 3-4 times with a mixture of 80 ml of water and 50 ml of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was recrystallized with a mixture of dichloromethane and petroleum ether (1:4, v / v) to obtain 69 mg of a polycyclic fusion molecule 1d containing an oxygen-boron-nitrogen coordination bond, with a yield of 71.01%. The theoretical calculated values ​​of elemental analysis were C, 61.74%, H, 2.83%, O, 14.95%, N, 6.55%, and the actual experimental values ​​were C, 61.64%, H, 2.80%, O, 14.97%, N, 6.48%. The quantum yield of 1d was determined to be 71.67% and the hole mobility was 1.29 cm 2 / V•s.

[0052] Example 2 The synthesis route of a polycyclic fusion molecule 2a containing an oxygen-boron-nitrogen coordination bond provided in this embodiment is as follows:

[0053] In an anhydrous and oxygen-free environment under the protection of inert gas, 1c (100.0 mg, 0.23 mmol) obtained in Example 1 was dissolved in 50 ml of anhydrous toluene, and then boron tribromide (131 μL, 1.36 mmol) was added, and refluxed and stirred at 80°C for 12 hours, and then phenylmagnesium bromide (1 mol / L, 4.1 mL) was added, and the reaction was continued at 80°C for 12 hours. After the reaction was completed, it was extracted 3-4 times with a mixed solution of 80 ml water and 50 ml dichloromethane, and the obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was recrystallized with a mixed solution of dichloromethane and n-hexane (1:4, v / v) to obtain 92 mg of a polycyclic fusion molecule 2a containing an oxygen-boron-nitrogen coordination bond, and the yield was 74.46%. Theoretical calculation values ​​of elemental analysis are C, 75.04%, H, 4.08%, O, 11.76%, N, 5.15%, and actual experimental values ​​are C, 74.97%, H, 4.11%, O, 11.59%, N, 5.17%. The quantum yield of 2a is 29.94% and the hole mobility is 1.12 cm 2 / V•s.

[0054] Example 3 The synthesis route of a polycyclic fusion molecule 3a containing an oxygen-boron-nitrogen coordination bond provided in this example is as follows:

[0055] In an anhydrous and oxygen-free environment under the protection of inert gas, 1c (100 mg, 0.23 mmol) obtained in Example 1 was dissolved in 50 ml of anhydrous toluene, and then boron tribromide (131 μL, 1.36 mmol) was added, and the mixture was refluxed and stirred at 80°C for 12 hours, and then 2-ethylhexylmagnesium bromide (1 mol / L, 4.1 mL) was added, and the reaction was continued at 80°C for 12 hours. After the reaction was completed, it was extracted 3-4 times with a mixed solution of 80 ml water and 50 ml dichloromethane, and the obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was subjected to silica gel column chromatography (200-300 mesh) using a mixed solution of petroleum ether / dichloromethane (10:1, v / v) as an eluent to obtain 45 mg of a polycyclic fusion molecule 3a containing an oxygen-boron-nitrogen coordination bond, with a yield of 32.15%. Theoretical calculation values ​​of elemental analysis are C, 74.04%, H, 7.52%, O, 10.38%, N, 4.54%, and actual experimental values ​​are C, 74.12%, H, 7.54%, O, 10.23%, N, 4.62%. The quantum yield of 3a is 71.38% and the hole mobility is 0.89 cm 2 / V•s.

[0056] Example 4 The synthesis route of a polycyclic fusion molecule 4b containing an oxygen-boron-nitrogen coordination bond provided in this example is as follows:

[0057] 1) Synthesis of compound 4a: In an anhydrous and oxygen-free environment under the protection of inert gas, 1b (250 mg, 0.72 mmol) prepared in Example 1 was dissolved in 10 ml of tetrahydrofuran, and 2 ml of anhydrous ethanol, 10 ml of water, potassium carbonate (1497.9 mg, 10.84 mmol) were added, followed by tetrakis(triphenylphosphine)palladium (25.1 mg, 0.022 mmol) and 3-methoxynaphthalene-2-boric acid (350.3 mg, 1.73 mmol). The mixture was refluxed at 80°C for 12 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted 3-4 times with a mixture of 80 ml of water and 50 ml of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was recrystallized with a mixture of dichloromethane and n-hexane (1:4, v / v) to obtain 285 mg of a yellow solid product 4a with a yield of 78.80%. Theoretical calculated values ​​of elemental analysis are C, 76.79%, H, 4.83%, O, 12.79%, N, 5.60%, and actual experimental values ​​are C, 76.67%, H, 4.93%, O, 12.91%, N, 5.41%. 2) Synthesis of compound 4b: In an anhydrous and oxygen-free environment under the protection of inert gas, 4a (150.0 mg, 0.30 mmol) was dissolved in 60 mL of anhydrous toluene, and then boron tribromide (173.2 μL, 1.80 mmol) was added, and the mixture was refluxed and stirred at 80°C for 12 hours. Then 4-tert-butylphenylmagnesium bromide (0.5 mol / L, 10.5 mL) was added, and the reaction was continued at 80°C for 12 hours. After the reaction was completed, it was extracted 3-4 times with a mixture of 80 ml of water and 50 ml of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was subjected to silica gel column chromatography (200-300 mesh) using a mixture of petroleum ether / dichloromethane (1:2, v / v) as an eluent to obtain 107 mg of a polycyclic fusion molecule 4b containing an oxygen-boron-nitrogen coordination bond, with a yield of 47.20%. Theoretical calculation values ​​of elemental analysis are C, 79.38%, H, 5.60%, O, 8.46%, N, 3.70%, and actual experimental values ​​are C, 79.53%, H, 5.55%, O, 8.39%, N, 3.75%. The quantum yield of 4b is 3.38% and the hole mobility is 3.58 cm 2 / V•s.

[0058] Example 5 The synthetic route of a polycyclic fusion molecule 5b containing oxygen-boron-nitrogen coordination bonds provided in this example is as follows:

[0059] 1) Synthesis of compound 5a: In an anhydrous and oxygen-free environment under the protection of inert gas, 1b (500 mg, 1.45 mmol) prepared in Example 1 was dissolved in 10 ml of ethylene glycol dimethyl ether (DME), and 10 ml of water and potassium carbonate (2995.8 mg, 21.68 mmol) were added, followed by tetrakis(triphenylphosphine)palladium (50.1 mg, 0.043 mmol), cuprous chloride (143.1 mg, 2.9 mmol) and 3-methoxythiophene-2-boronic acid pinacol ester (832.8 mg, 3.47 mmol). The mixture was stirred at 110 °C for 12 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted 3-4 times with a mixed solution of 80 ml of water and 50 ml of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was recrystallized from a mixture of dichloromethane and n-hexane (1:4, v / v) to obtain 322 mg of yellow solid product 5a with a yield of 55.70%. The theoretical calculated values ​​of elemental analysis were C, 58.24%, H, 3.91%, O, 15.52%, N, 6.79%, and the actual experimental values ​​were C, 58.36%, H, 3.79%, O, 15.57%, N, 6.57%.

[0060] 2) Synthesis of compound 5b: In an anhydrous and oxygen-free environment under the protection of inert gas, 5a (200.00 mg, 0.48 mmol) was dissolved in 40 mL of anhydrous toluene, and then boron tribromide (280.3 μL, 2.91 mmol) was added, and the mixture was refluxed at 80°C for 12 h. Then 4-tert-butylphenylmagnesium bromide (0.5 mol / L, 17.5 mL) was added, and the reaction was continued at 80°C for 12 hours. After the reaction was completed, it was extracted 3-4 times with a mixture of 80 ml of water and 50 ml of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was subjected to silica gel column chromatography (200-300 mesh) using a mixture of petroleum ether / dichloromethane (1:1, v / v) as an eluent to obtain 144 mg of a polycyclic fusion molecule 5b containing an oxygen-boron-nitrogen coordination bond, with a yield of 44.43%. Theoretical calculation values ​​of elemental analysis are C, 68.28%, H, 5.13%, O, 9.57%, N, 4.19%, and actual experimental values ​​are C, 68.46%, H, 5.02%, O, 9.45%, N, 4.23%. The quantum yield of 5b is 13.57% and the hole mobility is 2.32 cm 2 / V•s.

[0061] Example 6 The synthesis route of a polycyclic fusion molecule 6b containing an oxygen-boron-nitrogen coordination bond provided in this example is as follows:

[0062] 1) Synthesis of compound 6a: In an anhydrous and oxygen-free environment under the protection of inert gas, 1b (250 mg, 0.72 mmol) prepared in Example 1 was dissolved in 10 ml of tetrahydrofuran, and 2 ml of anhydrous ethanol, 10 ml of water, potassium carbonate (1497.9 mg, 10.84 mmol) were added, followed by tetrakis(triphenylphosphine)palladium (25.1 mg, 0.022 mmol) and 5-tert-butyl-2-methoxyphenylboronic acid (390.9 mg, 1.88 mmol). The mixture was refluxed at 80°C for 12 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted 3-4 times with a mixture of 80 ml of water and 50 ml of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was recrystallized with a mixture of dichloromethane and n-hexane (1:4, v / v) to obtain 310 mg of a yellow solid product 6a with a yield of 83.69%. The theoretical calculated values ​​of elemental analysis are C, 74.97%, H, 7.08%, O, 12.48%, N, 5.46%. The actual experimental values ​​are C, 74.85%, H, 7.14%, O, 12.26%, N, 5.53%.

[0063] 2) Synthesis of compound 6b: In an anhydrous and oxygen-free environment under the protection of inert gas, 6a (100.0 mg, 0.20 mmol) was dissolved in 20 mL of anhydrous toluene, and then boron tribromide (112.8 μl, 1.17 mmol) was added, and the mixture was refluxed at 80°C with stirring for 12 hours. Then 4-tert-butylphenylmagnesium bromide (0.5 mol / L, 7.0 mL) was added, and the reaction was continued at 80°C for 12 hours. After the reaction was completed, it was extracted 3-4 times with a mixture of 80 ml of water and 50 ml of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and spin-dried to obtain a crude product. The crude product was subjected to silica gel column chromatography (200-300 mesh) using a mixture of petroleum ether / dichloromethane (1:1, v / v) as an eluent to obtain 88 mg of a polycyclic fusion molecule 6b containing an oxygen-boron-nitrogen coordination bond, with a yield of 58.69%. Theoretical calculation values ​​of elemental analysis are C, 78.13%, H, 7.08%, O, 8.33%, N, 3.64%, and actual experimental values ​​are C, 78.27%, H, 7.15%, O, 8.29%, N, 3.58%. The quantum yield of 6b is 21.18% and the hole mobility is 0.52 cm 2 / V•s.

[0064] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds, characterized in that: It has the following structural formula: ， In the formula, π is any one of the following structural formulas: ， Among them, R is a fatty chain, and its structural formula is , p is an integer from 0 to 5, m is an integer from 0 to 20, and n is an integer from 1 to 20; X is any one of the following structural formulas: ， Among them, R' is a fatty chain, and its structural formula is , p is an integer from 0 to 5, m is an integer from 0 to 20, and n is an integer from 1 to 20.

2. A method for preparing a polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds as claimed in claim 1, characterized in that: The steps include: S1: dissolving 6-bromo-3-hydroxypyridine in an organic solvent A, adding a base and iodophenyldiacetic acid, stirring and reacting at room temperature, and then recrystallizing or separating the obtained crude product by column chromatography to obtain 3-hydroxy-6-bromo[2,2]bipyridine; S2: dissolving the obtained 3-hydroxy-6-bromo[2,2]bipyridine and the methoxy-containing boric acid functionalized aromatic unit in a mixed solvent consisting of an organic solvent B and an inorganic base aqueous solution, and performing a coupling reaction using a palladium compound as a catalyst. After the reaction is completed, the crude product is extracted and concentrated, and recrystallized with n-hexane and dichloromethane to obtain a boronated precursor; S3: dissolving the obtained borylated precursor in an organic solvent C, adding a borylation reagent to carry out a borylation ring-closing reaction, extracting and concentrating the obtained crude product after the reaction is completed, and separating the crude product by recrystallization or column chromatography to obtain the polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds.

3. The method for preparing a polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds according to claim 2, characterized in that: In step S1, the organic solvent A is dichloromethane, toluene, chloroform or tetrahydrofuran; the base is potassium carbonate, sodium carbonate or cesium carbonate; the molar ratio of 6-bromo-3-hydroxypyridine to the base and iodophenyldiacetic acid is 8:1:2 to 6:1:2; and the reaction time is 1 to 12 hours.

4. The method for preparing a polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds according to claim 2, characterized in that: In step S2, the methoxy-containing boric acid functionalized aromatic unit is 2-hydroxyphenylboronic acid, 4-tert-butyl-2-hydroxyphenylboronic acid, 3-hydroxy-5-alkyl-2-boric acid furan, 3-hydroxy-5-alkyl-2-boric acid thiophene, 3-hydroxy-5-alkyl-2-boric acid selenophene, 3-hydroxy-2-boric acid naphthalene, 3-hydroxy-7-tert-butyl-2-boric acid naphthalene, 2-alkyl-6-hydroxy-5-boric acid benzofuran, 2-alkyl-6-hydroxy-5-boric acid benzothiophene, 2-alkyl-6-hydroxy-5-boric acid benzoselenophene, 3-hydroxy- The present invention relates to any one of 5-alkyl-2-boronic acid dithiophene, 3-hydroxy-5-alkyl-2-boronic acid trithiophene, and 3-methoxythiophene-2-boronic acid pinacol ester; the molar ratio of 3-hydroxy-6-bromo[2,2]bipyridine to the methoxy-containing boric acid functionalized aromatic unit is 1:2 to 1:3; the organic solvent B is at least one of anhydrous ethanol, toluene, chloroform, tetrahydrofuran, 1,4-dioxane, and ethylene glycol dimethyl ether; the inorganic alkali aqueous solution is an aqueous solution of sodium carbonate, potassium carbonate, or cesium carbonate, and its concentration is 1 M; the volume ratio of the organic solvent B to the inorganic base aqueous solution in the mixed solvent is 2:1~1:1; the palladium compound is tetrakistriphenylphosphine palladium or palladium dichloride, and the molar ratio of its usage to 3-hydroxy-6-bromo[2,2]bipyridine is 3:100~5:100; the temperature of the coupling reaction is 40~120 °C, and the time is 4~24 hours; during recrystallization, the volume ratio of n-hexane and dichloromethane used is 4:

1.

5. The method for preparing a polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds according to claim 2, characterized in that: In step S3, the organic solvent C is dichloromethane, toluene, chloroform, tetrahydrofuran or 1,4-dioxane; the boronating agent is boron trifluoride, boron trichloride, boron tribromide, or a combination of boron tribromide and any one of alkylmagnesium bromide, phenylmagnesium bromide, p-tert-butylphenylmagnesium bromide, p-alkylphenylmagnesium bromide, p-fluorophenylmagnesium bromide, isotrifluorophenylmagnesium bromide, isotrimethylphenylmagnesium bromide, p-trifluoromethylphenylmagnesium bromide, and 2-alkylthiophenemagnesium bromide; the molar ratio of the boronating precursor to the boronating agent is 1:4 to 1:16; the temperature of the boronating ring-closing reaction is 40 to 120 ° C, and the time is 4 to 24 hours.

6. Use of the polycyclic fusion molecule containing oxygen-boron-nitrogen coordination bonds as claimed in claim 1 in the preparation of organic optoelectronic devices.

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