A double-boron fused ring organic compound, and a preparation method and application thereof

Abstract

The application discloses a kind of double boron fused ring organic compounds, the structural formula of the double boron fused ring organic compound is as shown in formula I.The application also discloses the preparation method of the double boron fused ring organic compound and application in organic electronic device, especially in organic light emitting diode.The application also relates to organic electronic device, especially organic light emitting diode comprising double boron fused ring organic compound according to the application, and its application in display and lighting technology.Through device structure optimization, change the concentration of the double boron fused ring organic compound in matrix, can reach the best device performance, facilitate the realization of high efficiency high brightness high stability OLED device, provide better material option for full-color display and lighting application.

Description

Technical Field

[0001] This invention belongs to the field of new materials technology, specifically relating to a diboron fused-ring organic compound, its preparation method, and its application. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to the diversity of organic semiconductor materials in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

[0003] To improve the luminous efficiency of purely organic light-emitting materials in organic light-emitting diodes (OLEDs), Professor Adachi of Kyushu University in Japan designed and synthesized a series of organic compound light-emitting materials in 2012. He introduced a series of electron donor and acceptor units, which reduced the band gap between the singlet (S1) and triplet (T1) energy levels of the compounds to a certain extent. This allows the triplet exciton (T1) to obtain thermal energy from the environment and achieve singlet exciton (S1) radiative emission through an anti-intersystem crossing process, also known as thermally activated delayed fluorescence. This luminescence process can significantly improve the luminous efficiency of purely organic materials. This has sparked great interest in purely organic thermally activated delayed fluorescence materials. To date, the internal quantum efficiency of purely organic thermally activated delayed fluorescence materials has approached 100%.

[0004] However, the luminescent properties and types of these materials still need further improvement. In particular, the currently reported TADF materials still suffer from problems such as low luminescent efficiency and broad emission spectra. Therefore, how to develop luminescent materials with both high luminescent efficiency and narrow half-peak and broad spectral characteristics through rational structural design is one of the urgent problems to be solved. Summary of the Invention

[0005] Purpose of the invention: In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is to provide a class of bisboron fused ring organic compounds that can improve the luminescence efficiency of compounds, reduce the half-width of the emission spectrum, and ultimately improve the performance of the corresponding devices.

[0006] Another technical problem that this invention aims to solve is to provide a method for preparing this type of diboron fused-ring organic compound.

[0007] The final technical problem to be solved by this invention is to provide the application of this class of diboron fused-ring organic compounds in the preparation of organic electronic devices.

[0008] Technical solution: To solve the above-mentioned technical problems, the present invention provides a diboron fused-ring organic compound as shown in general formula (I):

[0009]

[0010] In Formula I, Ar1 is an aromatic ring group, X is an oxygen or sulfur atom, and R is a hydrogen atom or a tert-butyl group.

[0011] The aromatic ring group is an aromatic cyclic hydrocarbon of an aromatic amine, carbazole or its derivatives that has a certain electron-donating ability.

[0012] Specifically, the aforementioned diboron-fused-ring organic compounds are preferably selected from the following general formulas:

[0013]

[0014]

[0015] Where X is an oxygen or sulfur atom, and R is a hydrogen atom or a tert-butyl group.

[0016] This invention also includes a method for preparing a diboron fused-ring organic compound, the method comprising the following steps:

[0017] 1) First, 2-bromo-1,3-difluoro-5-iodobenzene is used as a raw material and reacted with phenol or its derivative or thiophenol or its derivative at high temperature in an alkaline environment to obtain the corresponding diphenoxy ether or its derivative or diphenyl sulfide or its derivative. Then, under anhydrous, oxygen-free and low-temperature conditions, bromine atoms are removed by n-butyllithium (n-BuLi). Boron tribromide is then added and the reaction is stirred. Finally, under the alkaline environment of N,N-diisopropylethylamine, by controlling the reaction temperature and time, brominated dioxin-bridged triphenylboron or brominated disulfide-bridged triphenylboron compounds can be obtained. Then, they are prepared into corresponding boron ester compounds.

[0018] 2) Using 2-bromo-1,3-difluoro-5-iodobenzene as a raw material, it reacts with carbazole or its derivatives, 9,9-dimethyl-9,10-dihydroacridine, phenoxazine, phenothiazine or phenselenazine under alkaline conditions to generate the corresponding CN-coupled disubstituted intermediates. Then, under anhydrous, oxygen-free and low-temperature conditions, bromine atoms are removed by n-butyllithium (n-BuLi), and boron tribromide is added and stirred. Finally, under the alkaline environment of N,N-diisopropylethylamine, a series of brominated dinitrogen-bridged triarylboron derivatives can be obtained by controlling the reaction temperature and time.

[0019] 3) The boron ester compound prepared in step 1) and the brominated dinitrogen-bridged triarylboron derivative prepared in step 2) are coupled via Suzuki reaction to obtain a series of target diboron fused-ring organic compounds.

[0020] The present invention also includes the application of the aforementioned diboron fused-ring organic compound in the preparation of organic electronic devices.

[0021] The organic electronic devices mentioned above include organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light-emitting cells (OLEECs), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes.

[0022] The present invention also includes an organic electronic device comprising the aforementioned diboron fused-ring organic compound.

[0023] The mass concentration of the diboron fused-ring organic compound is 5-15 wt%.

[0024] The following are specific examples of suitable diboron fused-ring organic compounds according to the present invention, but are not limited to:

[0025]

[0026]

[0027]

[0028]

[0029] Beneficial Effects: Compared with existing technologies, the present invention has the following advantages: The compound prepared by the present invention has two boron-containing fused-ring organic multiple resonant units and possesses good rigidity, chemical and thermal stability, thus effectively improving the luminous efficiency of the compound and the performance of corresponding devices. The present invention also relates to organic electronic devices, particularly organic light-emitting diodes (OLEDs), comprising the fused-ring organic compound prepared according to the present invention, and their applications in display and lighting technologies. By optimizing the device structure and changing the concentration of the fused-ring organic compound in the matrix, optimal device performance can be achieved, facilitating the realization of high-efficiency, high-brightness, and high-stability OLED devices, and providing better material options for full-color display and lighting applications. Detailed Implementation

[0030] Example 1: Synthesis of a diboron-fused-ring organic compound

[0031] The synthetic route for the diboron fused-ring organic compound BB-1 is as follows:

[0032]

[0033] 1. Synthetic intermediate 1-b:

[0034] 2,5-Dibromo-1,3-difluorobenzene (10.21 g, 37.8 mmol), potassium carbonate (15.3 g, 110.8 mmol), and phenol (10.41 g, 110.8 mmol) were placed in a dry two-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, 55 mL of N-methylpyrrolidone was added, and the mixture was stirred at 170 °C for 24 hours. After cooling to room temperature, water was added to precipitate the solid. The precipitate was filtered, washed with n-hexane, and dried to give 13.22 g of a white solid. The yield of intermediate 1-b was 84%. MALDI-TOF-MS (m / z): 421.1 ([M+1)) + ).

[0035] 2. Synthetic intermediate 1-c:

[0036] Intermediate 1-b (1.22 g, 2.92 mmol) was placed in a dry Schlenck flask, evacuated, and purged with nitrogen three times. Then, dry m-xylene (25 mL) was added under a nitrogen atmosphere. Butyllithium (1.28 mL, 3.21 mmol, 2.5 M) was added at 0 °C, and the reaction was maintained at 0 °C with stirring for 20 min. The mixture was then transferred to room temperature and stirred for 1 h. Boron tribromide (0.49 mL, 5.25 mmol) was added after cooling to 0 °C, and the mixture was maintained at 0 °C with stirring for 20 min. The mixture was then transferred to room temperature and stirred for 30 min. Next, the mixture was heated to 45 °C and stirred for 50 min. It was then cooled again to 0 °C, N,N-diisopropylethylamine (1.03 mL, 6 mmol) was added, and finally the mixture was heated to 140 °C and stirred for 12 h. After the reaction was complete, the mixture was cooled to room temperature, quenched with water, and extracted several times with dichloromethane. The combined organic phases were concentrated and dried to give 0.78 g of the target product as a white solid, with a yield of 76% for intermediate 1-c. MALDI-TOF-MS (m / z): 350.3 ([M+1]). + ).

[0037] 3. Synthetic intermediate B-1:

[0038] Weigh out intermediate 1-c (200 mg, 0.57 mmol), pinacol diboronate (230 mg, 0.91 mmol), and potassium acetate (600 mg, 6.11 mmol) into a dry double-necked flask. Vacuum the flask and purge with nitrogen. Add 1,4-dioxane (25 ml) and tetra-(triphenylphosphine)palladium (32 mg, 0.028 mmol) under nitrogen flow. Stir at room temperature for 10 minutes, then heat to 90 °C and react for 5 hours. Cool to room temperature, remove solvent by vacuum distillation, and purify by column chromatography with ethyl acetate:petroleum ether = 1:3 to give 151 mg of a pale yellow solid. The yield of intermediate B-1 was 67%. MALDI-TOF-MS (m / z): 396.2 ([M]). +).

[0039] 4. Synthetic intermediate 2-b:

[0040] Carbazole (0.84 g, 5 mmol) and cesium carbonate (3.9 g, 12 mmol) were placed in a dry double-necked flask and circulated under vacuum three times. Dry DMF (15 ml) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 30 minutes. Then, 2,5-dibromo-1,3-difluorobenzene (0.54 g, 2 mmol) was added under a nitrogen atmosphere, and the mixture was heated to 155 °C and reacted for 12 hours until the reactants were completely reacted. After the reaction was complete, a large amount of water was added to form a precipitate. The precipitate was filtered, collected, and purified by column chromatography using dichloromethane:petroleum ether = 1:8 to give 676 mg of a white solid. The yield of intermediate 2-b was approximately 60%. MALDI-TOF-MS (m / z): 566.3 ([M]) + ).

[0041] 5. Synthetic intermediate 2-c:

[0042] Take a dry Schlenck tube, place intermediate 2-b (0.282 g, 0.5 mmol) inside, and then evacuate and purge with nitrogen 3-5 times. Under nitrogen, add 10 mL of dry m-xylene, cool to 0°C, and then add n-butyllithium (0.22 mL, 0.55 mmol, 2.5 M) under nitrogen. Transfer to room temperature and stir for 1 hour. Next, add boron tribromide (0.06 mL, 0.6 mmol) at 0°C, transfer to room temperature and stir for 50 minutes. Then, add N,N-diisopropylethylamine (0.17 mL, 1 mmol) at 0°C, transfer to room temperature and stir for 30 minutes, and then heat to 140°C and react for 12 hours. After the reaction is complete, concentrate and then purify by column chromatography with dichloromethane:petroleum ether = 1:10 to give 148 mg of yellow solid, with a yield of intermediate 2-c of 60%. MALDI-TOF-MS (m / z): 495.1 ([M] + ).

[0043] 5. Synthesis of the diboron-fused-ring organic compound BB-1:

[0044] Intermediate 2-C (0.25 g, 0.5 mmol), B-1 (0.22 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 89 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-1 was 26%. MALDI-TOF-MS (m / z): 684.3 ([M]) + ).

[0045] Example 2: Synthesis of the diboron-fused-ring organic compound BB-2

[0046] Synthetic route of BB-2, a diboron-fused-ring organic compound:

[0047]

[0048] 1. Synthetic intermediate 3-b:

[0049] 2,5-Dibromo-1,3-difluorobenzene (10.21 g, 37.8 mmol), potassium carbonate (15.3 g, 110.8 mmol), and 4-tert-butylphenol (16.62 g, 110.8 mmol) were placed in a dry two-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, 55 mL of N-methylpyrrolidone was added, and the mixture was stirred at 170 °C for 24 hours. After cooling to room temperature, water was added to precipitate the precipitate. The precipitate was filtered, washed with n-hexane, and dried to give 16.03 g of a white solid, with an 80% yield of intermediate 3-b. MALDI-TOF-MS (m / z): 332.2 ([M]). + ).

[0050] 2. Synthetic intermediate 3-c:

[0051] Intermediate 3-b (1.55 g, 2.92 mmol) was placed in a dry Schlenck flask, evacuated, and purged with nitrogen three times. Then, dry m-xylene (25 mL) was added under a nitrogen atmosphere. Butyllithium (1.28 mL, 3.21 mmol, 2.5 M) was added at 0 °C, and the reaction was maintained at 0 °C with stirring for 20 min. The mixture was then transferred to room temperature and stirred for 1 h. After cooling to 0 °C, boron tribromide (0.49 mL, 5.25 mmol) was added, and the mixture was maintained at 0 °C with stirring for 20 min. The mixture was then transferred to room temperature and stirred for 30 min. Next, the mixture was heated to 45 °C and stirred for 50 min. It was then cooled again to 0 °C, N,N-diisopropylethylamine (1.03 mL, 6 mmol) was added, and finally, the mixture was heated to 140 °C and stirred for 12 h. After the reaction was complete, the mixture was cooled to room temperature, quenched with water, and extracted several times with dichloromethane. The combined organic phases were concentrated and dried to give 0.94 g of the target product as a white solid, with a yield of 70% for intermediate 3-c. MALDI-TOF-MS (m / z): 462.3 ([M+1]). + ).

[0052] 3. Synthetic intermediate B-2:

[0053] Weigh out intermediate 3-c (262 mg, 0.57 mmol), pinacol diboronate (230 mg, 0.91 mmol), and potassium acetate (600 mg, 6.11 mmol) into a dry double-necked flask. Vacuum the flask and purge with nitrogen. Add 1,4-dioxane (25 ml) and tetra-(triphenylphosphine)palladium (32 mg, 0.028 mmol) under nitrogen flow. Stir at room temperature for 10 minutes, then heat to 90 °C and react for 5 hours. Cool to room temperature, remove solvent by vacuum distillation, and purify by column chromatography with ethyl acetate:petroleum ether = 1:3 to obtain 174 mg of a pale yellow solid. The yield of intermediate B-2 is 60%. MALDI-TOF-MS (m / z): 508.3 ([M] + ).

[0054] 4. Synthesis of the diboron-fused-ring organic compound BB-2:

[0055] Intermediate 2-C (0.36 g, 0.5 mmol), BB-2 (0.28 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 119 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-2 was 30%. MALDI-TOF-MS (m / z): 796.6 ([M]) + ).

[0056] Example 3: Synthesis of the diboron-fused-ring organic compound BB-3

[0057] Synthetic route of BB-3, a diboron-fused-ring organic compound:

[0058]

[0059] 1. Synthetic intermediate 4-b:

[0060] 3,6-Di-tert-butylcarbazole (1.39 g, 5 mmol) and cesium carbonate (3.9 g, 12 mmol) were placed in a dry double-necked flask and circulated under vacuum three times. Dry DMF (15 ml) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 30 minutes. Then, 2,5-dibromo-1,3-difluorobenzene (0.54 g, 2 mmol) was added under a nitrogen atmosphere, and the mixture was heated to 155 °C and reacted for 12 hours until the reactants were completely reacted. After the reaction was complete, a large amount of water was added to form a precipitate. The precipitate was filtered, collected, and purified by column chromatography using dichloromethane:petroleum ether = 1:8 to give 850 mg of a white solid. The yield of intermediate 4-b was approximately 54%. MALDI-TOF-MS (m / z): 790.4 ([M]) + ).

[0061] 2. Synthetic intermediate 4-c:

[0062] Take a dry Schlenck tube, place intermediate 4-b (0.394 g, 0.5 mmol) inside, and then evacuate and purge with nitrogen 3-5 times. Under nitrogen, add 10 mL of dry m-xylene, cool to 0°C, and then add n-butyllithium (0.22 mL, 0.55 mmol, 2.5 M) under nitrogen. Transfer to room temperature and stir for 1 hour. Next, add boron tribromide (0.06 mL, 0.6 mmol) at 0°C, transfer to room temperature and stir for 50 minutes. Then, add N,N-diisopropylethylamine (0.17 mL, 1 mmol) at 0°C, transfer to room temperature and stir for 30 minutes, and then heat to 140°C and react for 12 hours. After the reaction is complete, concentrate and then purify by column chromatography with dichloromethane:petroleum ether = 1:10 to give 197 mg of yellow solid, with a yield of intermediate 4-c of 55%. MALDI-TOF-MS (m / z): 719.3 ([M]) + ).

[0063] 3. Synthesis of the diboron-fused-ring organic compound BB-3:

[0064] Intermediate 4-C (0.36 g, 0.5 mmol), B-1 (0.22 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 118 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-3 was 26%. MALDI-TOF-MS (m / z): 908.8 ([M]) + ).

[0065] Example 4: Synthesis of the diboron fused-ring organic compound BB-4

[0066] Synthetic route of BB-4, a diboron-fused-ring organic compound:

[0067]

[0068] Synthesis of the diboron fused-ring organic compound BB-4:

[0069] Intermediate 4-C (0.36 g, 0.5 mmol), B-2 (0.28 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 153 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-4 was 30%. MALDI-TOF-MS (m / z): 1021.1 ([M] + ).

[0070] Example 5: Synthesis of the diboron-fused-ring organic compound BB-5

[0071] Synthetic route of BB-5, a diboron-fused-ring organic compound:

[0072]

[0073] 1. Synthetic intermediate 5-b:

[0074] 9,9-Dimethyl-9,10-dihydroacrylidine (1.38 g, 6.6 mmol) and potassium tert-butoxide (0.84 g, 8.1 mmol) were placed in a dry double-necked flask and circulated under vacuum three times. Dry DMF (20 ml) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 30 minutes. Then, 2,5-dibromo-1,3-difluorobenzene (0.84 g, 3 mmol) was added under a nitrogen atmosphere, and the mixture was heated to 140 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was collected. The filtrate was concentrated and purified by column chromatography using dichloromethane:petroleum ether = 1:5 to give 1.07 g of a pale yellow solid, with a yield of 55% for intermediate 5-b. MALDI-TOF-MS (m / z): 651.2 ([M+1)). + ).

[0075] 2. Synthetic intermediate 5-c:

[0076] Take a dry Schlenck tube, place intermediate 5-b (0.324 g, 0.5 mmol) inside, and then evacuate and circulate nitrogen gas 3-5 times. Under nitrogen atmosphere, add 10 mL of dry m-xylene, cool to 0°C, and then add n-butyllithium (0.22 mL, 0.55 mmol, 2.5 M) under nitrogen atmosphere. Transfer to room temperature and stir for 1 hour. Next, add boron tribromide (0.06 mL, 0.6 mmol) at 0°C, transfer to room temperature and stir for 50 minutes. Then, add N,N-diisopropylethylamine (0.17 mL, 1 mmol) at 0°C, transfer to room temperature and stir for 30 minutes, and then heat to 140°C and react for 12 hours. After the reaction is complete, concentrate and then purify by column chromatography with dichloromethane:petroleum ether = 1:10 to give 173 mg of yellow solid, with a yield of intermediate 5-c of 60%. MALDI-TOF-MS (m / z): 579.3 ([M]) + ).

[0077] 3. Synthesis of the diboron fused-ring organic compound BB-5:

[0078] Intermediate 5-C (0.29 g, 0.5 mmol), B-1 (0.22 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 154 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-5 was 40%. MALDI-TOF-MS (m / z): 768.3 ([M]) + ).

[0079] Example 6: Synthesis of the diboron-fused-ring organic compound BB-6

[0080] Synthetic route of BB-6, a diboron-fused-ring organic compound:

[0081]

[0082] Synthesis of the diboron fused-ring organic compound BB-6:

[0083] In a dry double-necked flask, intermediates 5-C (0.29 g, 0.5 mmol), BB-2 (0.28 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography with dichloromethane:petroleum ether = 1:25 to give 185 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-6 was 42%. MALDI-TOF-MS (m / z): 881.3 ([M+1)). + ).

[0084] Example 7 Synthesis of the diboron-fused-ring organic compound BB-7

[0085] Synthetic route of BB-7, a diboron-fused-ring organic compound:

[0086]

[0087] 1. Synthetic intermediate 6-b:

[0088] A dry double-necked flask was filled with phenoxazine (1.21 g, 6.6 mmol) and potassium tert-butoxide (0.84 g, 8.1 mmol). The mixture was circulated under vacuum three times. Dry DMF (20 ml) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 30 minutes. Then, 2,5-dibromo-1,3-difluorobenzene (0.84 g, 3 mmol) was added under a nitrogen atmosphere, and the mixture was heated to 140 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane and water. The organic phase was collected, the filtrate was concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:5 to give 875 mg of a pale yellow solid. The yield of intermediate 6-b was 49%. MALDI-TOF-MS (m / z): 598.1 ([M]). + ).

[0089] 2. Synthetic intermediate 6-c:

[0090] Take a dry Schlenck tube, place intermediate 6-b (0.298 g, 0.5 mmol) inside, and then evacuate and circulate nitrogen gas 3-5 times. Under nitrogen atmosphere, add 10 mL of dry m-xylene, cool to 0°C, and then add n-butyllithium (0.22 mL, 0.55 mmol, 2.5 M) under nitrogen atmosphere. Transfer to room temperature and stir for 1 hour. Next, add boron tribromide (0.06 mL, 0.6 mmol) at 0°C, transfer to room temperature and stir for 50 minutes. Then, add N,N-diisopropylethylamine (0.17 mL, 1 mmol) at 0°C, transfer to room temperature and stir for 30 minutes, and then heat to 140°C and react for 12 hours. After the reaction is complete, concentrate and then purify by column chromatography with dichloromethane:petroleum ether = 1:10 to give 171 mg of brownish-yellow solid, with a yield of intermediate 6-c of 65%. MALDI-TOF-MS(m / z): 528.1([M+1] + ).

[0091] 3. Synthesis of the diboron-fused-ring organic compound BB-7:

[0092] Intermediate 6-C (0.26 g, 0.5 mmol), B-1 (0.22 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 215 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-7 was 60%. MALDI-TOF-MS (m / z): 716.4 ([M]) + ).

[0093] Example 8: Synthesis of the diboron-fused-ring organic compound BB-8

[0094] Synthetic route of BB-8, a diboron-fused-ring organic compound:

[0095]

[0096] Synthesis of BB-8, a diboron-fused-ring organic compound:

[0097] Intermediate 6-C (0.26 g, 0.5 mmol), B-2 (0.28 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 224 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-8 was 54%. MALDI-TOF-MS (m / z): 828.3 ([M]) + ).

[0098] Example 9: Synthesis of the diboron-fused-ring organic compound BB-9

[0099] Synthetic route of BB-9, a diboron-fused-ring organic compound:

[0100]

[0101] 1. Synthetic intermediate 7-b:

[0102] Phenothiazine (1.31 g, 6.6 mmol) and potassium tert-butoxide (0.84 g, 8.1 mmol) were placed in a dry double-necked flask and circulated under vacuum three times. Dry DMF (20 ml) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 30 minutes. Then, 2,5-dibromo-1,3-difluorobenzene (0.84 g, 3 mmol) was added under a nitrogen atmosphere, and the mixture was heated to 140 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was collected. The filtrate was concentrated and purified by column chromatography using dichloromethane:petroleum ether = 1:5 to give 1.03 g of a pale yellow solid, with a 55% yield of intermediate 7-b. MALDI-TOF-MS (m / z): 631.2 ([M+1)). + ).

[0103] 2. Synthetic intermediate 7-c:

[0104] Take a dry Schlenck tube, place intermediate 7-b (0.314 g, 0.5 mmol) inside, and then evacuate and circulate nitrogen gas 3-5 times. Under nitrogen atmosphere, add 10 mL of dry m-xylene, cool to 0°C, and then add n-butyllithium (0.22 mL, 0.55 mmol, 2.5 M) under nitrogen atmosphere. Transfer to room temperature and stir for 1 hour. Next, add boron tribromide (0.06 mL, 0.6 mmol) at 0°C, transfer to room temperature and stir for 50 minutes. Then, add N,N-diisopropylethylamine (0.17 mL, 1 mmol) at 0°C, transfer to room temperature and stir for 30 minutes, and then heat to 140°C and react for 12 hours. After the reaction is complete, concentrate and then purify by column chromatography with dichloromethane:petroleum ether = 1:10 to give 167 mg of yellow solid, with a yield of intermediate 7-c of 60%. MALDI-TOF-MS (m / z): 559.3 ([M]) + ).

[0105] 3. Synthesis of the diboron fused-ring organic compound BB-9:

[0106] Intermediate 7-C (0.28 g, 0.5 mmol), B-1 (0.22 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 187 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-9 was 50%. MALDI-TOF-MS (m / z): 749.2 ([M+1)). + ).

[0107] Example 10 Synthesis of the diboron fused-ring organic compound BB-10

[0108] Synthetic route of BB-10, a diboron-fused-ring organic compound:

[0109]

[0110] Synthesis of the diboron-fused-ring organic compound BB-10:

[0111] Intermediate 7-C (0.28 g, 0.5 mmol), B-2 (0.28 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 194 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-10 was 45%. MALDI-TOF-MS (m / z): 860.3 ([M]) + ).

[0112] Example 11 Synthesis of the diboron fused-ring organic compound BB-11

[0113] Synthetic route of BB-11, a diboron fused-ring organic compound:

[0114]

[0115] 1. Synthetic intermediate 8-b:

[0116] Place phenselenazine (1.62 g, 6.6 mmol) and potassium tert-butoxide (0.84 g, 8.1 mmol) in a dry double-necked flask, circulate under vacuum three times, add dry DMF (20 ml) under a nitrogen stream, stir at room temperature for 30 minutes, then add 2,5-dibromo-1,3-difluorobenzene (0.84 g, 3 mmol) under a nitrogen stream, and heat to 140 °C for 12 hours. After the reaction is complete, cool to room temperature, extract with dichloromethane and water, collect the organic phase, concentrate the filtrate, and purify by column chromatography with dichloromethane:petroleum ether = 1:5 to give 1.08 g of yellow solid, with a 50% yield of intermediate 8-b. MALDI-TOF-MS (m / z): 725.3 ([M]) + ).

[0117] 2. Synthetic intermediate 8-c:

[0118] Take a dry Schlenck tube, place intermediate 8-b (0.362 g, 0.5 mmol) inside, and then evacuate and circulate nitrogen gas 3-5 times. Under nitrogen atmosphere, add 10 mL of dry m-xylene, cool to 0°C, and then add n-butyllithium (0.22 mL, 0.55 mmol, 2.5 M) under nitrogen atmosphere. Transfer to room temperature and stir for 1 hour. Next, add boron tribromide (0.06 mL, 0.6 mmol) at 0°C, transfer to room temperature and stir for 50 minutes. Then, add N,N-diisopropylethylamine (0.17 mL, 1 mmol) at 0°C, transfer to room temperature and stir for 30 minutes, and then heat to 140°C and react for 12 hours. After the reaction is complete, concentrate and then purify by column chromatography with dichloromethane:petroleum ether = 1:10 to give 163 mg of yellow solid, with a yield of 50% for intermediate 8-c. MALDI-TOF-MS (m / z): 653.2 ([M] + ).

[0119] 3. Synthesis of the diboron fused-ring organic compound BB-11:

[0120] Intermediate 8-C (0.33 g, 0.5 mmol), B-1 (0.22 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 169 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-11 was 40%. MALDI-TOF-MS (m / z): 844.1 ([M]) + ).

[0121] Example 12 Synthesis of the diboron fused-ring organic compound BB-12

[0122] Synthetic route of the diboron fused-ring organic compound BB-12:

[0123]

[0124] Synthesis of the diboron-fused-ring organic compound BB-12:

[0125] Intermediate 8-C (0.33 g, 0.5 mmol), B-2 (0.28 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 239 mg of a yellow-green solid. The yield of the diboron fused-ring organic compound BB-12 was 50%. MALDI-TOF-MS (m / z): 956.2 ([M]). + ).

[0126] Example 13 Synthesis of the diboron fused-ring organic compound BB-13

[0127] Synthetic route of the diboron fused-ring organic compound BB-13:

[0128]

[0129] 1. Synthetic intermediate 9-b:

[0130] 10.41 g (110.8 mmol) of thiophenol was placed in a dry two-necked flask. 50 mL of dry DMF solution was added under nitrogen atmosphere, followed by the addition of NaH (68.9 mg, 132.9 mmol). The mixture was stirred at room temperature for 30 minutes, then 10.21 g (37.8 mmol) of 2,5-dibromo-1,3-difluorobenzene was added. The mixture was stirred at 120 °C for 10 hours. After cooling to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic phase was concentrated, washed with n-hexane, and dried to give 11.88 g of a pale yellow solid. The yield of intermediate 9-b was 70%. MALDI-TOF-MS (m / z): 452.3 ([M+1)). + ).

[0131] 2. Synthetic intermediate 9-c:

[0132] Intermediate 9-b (1.31 g, 2.92 mmol) was placed in a dry Schlenck flask, evacuated, and purged with nitrogen three times. Then, dry m-xylene (25 mL) was added under a nitrogen atmosphere. Butyllithium (1.28 mL, 3.21 mmol, 2.5 M) was added at 0 °C, and the reaction was maintained at 0 °C with stirring for 20 min. The mixture was then transferred to room temperature and stirred for 1 h. Boron tribromide (0.49 mL, 5.25 mmol) was added after cooling to 0 °C, and the mixture was maintained at 0 °C with stirring for 20 min. The mixture was then transferred to room temperature and stirred for 30 min. Next, the mixture was heated to 45 °C and stirred for 50 min. It was then cooled again to 0 °C, N,N-diisopropylethylamine (1.03 mL, 6 mmol) was added, and finally, the mixture was heated to 140 °C and stirred for 12 h. After the reaction was complete, the mixture was cooled to room temperature, quenched with water, and extracted several times with dichloromethane. The combined organic phases were concentrated and dried to give 0.67 g of the target product, a yellow solid, with a yield of 60% for intermediate 9-c. MALDI-TOF-MS (m / z): 381.2 ([M+1]). + ).

[0133] 3. Synthetic intermediate B-3:

[0134] Take a dry double-necked flask and weigh intermediate 9-c (217 mg, 0.57 mmol), pinacol diboronate (288 mg, 1.14 mmol), Pd₂(dppf)Cl₂ (42 mg, 0.057 mmol), and potassium acetate (224 mg, 2.28 mmol). Evacuate the flask under nitrogen atmosphere and add DMF (10 ml) under nitrogen flow. React at 90 °C for 12 hours. Cool to room temperature, remove the solvent by vacuum distillation, add water, extract with dichloromethane, concentrate the organic phase, and purify by column chromatography with ethyl acetate:petroleum ether = 1:3 to give 159 mg of a pale yellow solid. The yield of intermediate B-3 was 65%. MALDI-TOF-MS (m / z): 428.1 ([M] + ).

[0135] 4. Synthesis of the diboron-fused-ring organic compound BB-13:

[0136] Intermediate 2-C (0.25 g, 0.5 mmol), BB-3 (0.24 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:20 to give 107 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-13 was 30%. MALDI-TOF-MS (m / z): 716.2 ([M]) + ).

[0137] Example 14 Synthesis of the diboron fused-ring organic compound BB-14

[0138] Synthetic route of the diboron fused-ring organic compound BB-14:

[0139]

[0140] 1. Synthetic intermediate 10-b:

[0141] 4-tert-butylthiophenol (18.39 g, 110.8 mmol) was placed in a dry two-necked flask. 50 mL of dry DMF solution was added under nitrogen atmosphere, followed by the addition of NaH (68.9 mg, 132.9 mmol). The mixture was stirred at room temperature for 30 minutes, then 2,5-dibromo-1,3-difluorobenzene (10.21 g, 37.8 mmol) was added. The mixture was stirred at 120 °C for 10 hours. After cooling to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic phase was concentrated, washed with n-hexane, and dried to give 13.81 g of a pale yellow solid, yield 65%. MALDI-TOF-MS (m / z): 563.9 ([M]). + ).

[0142] 2. Synthetic intermediate 10-c:

[0143] Intermediate 10-b (1.64 g, 2.92 mmol) was placed in a dry Schlenck flask, evacuated, and purged with nitrogen three times. Then, dry m-xylene (25 mL) was added under a nitrogen atmosphere. Butyllithium (1.28 mL, 3.21 mmol, 2.5 M) was added at 0 °C, and the reaction was maintained at 0 °C with stirring for 20 min. The mixture was then transferred to room temperature and stirred for 1 h. Boron tribromide (0.49 mL, 5.25 mmol) was added after cooling to 0 °C, and the mixture was maintained at 0 °C with stirring for 20 min. The mixture was then transferred to room temperature and stirred for 30 min. Next, the mixture was heated to 45 °C and stirred for 50 min. It was then cooled again to 0 °C, N,N-diisopropylethylamine (1.03 mL, 6 mmol) was added, and finally, the mixture was heated to 140 °C and stirred for 12 h. After the reaction was complete, the mixture was cooled to room temperature, quenched with water, and extracted several times with dichloromethane. The combined organic phases were concentrated and dried to give 0.79 g of the target product, a yellow solid, with a 10-c intermediate yield of 55%. MALDI-TOF-MS (m / z): 492.1 ([M]). + ).

[0144] 3. Synthetic intermediate B-4:

[0145] Take a dry double-necked flask and weigh intermediate 10-c (280 mg, 0.57 mmol), pinacol diboronate (288 mg, 1.14 mmol), Pd₂(dppf)Cl₂ (42 mg, 0.057 mmol), and potassium acetate (224 mg, 2.28 mmol). Evacuate the flask under nitrogen atmosphere and add DMF (10 ml) under nitrogen flow. React at 90 °C for 12 hours. Cool to room temperature, remove solvent by vacuum distillation, add water, extract with dichloromethane, concentrate the organic phase, and purify by column chromatography with ethyl acetate:petroleum ether = 1:3 to give 185 mg of a pale yellow solid. The yield of intermediate B-4 was 60%. MALDI-TOF-MS (m / z): 440.3 ([M]) + ).

[0146] 4. Synthesis of the diboron-fused-ring organic compound BB-14:

[0147] In a dry double-necked flask, 2-C (0.25 g, 0.5 mmol), intermediate B-4 (0.30 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:20 to give 145 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-14 was 35%. MALDI-TOF-MS (m / z): 828.3 ([M]). + ).

[0148] Example 15 Synthesis of the diboron fused-ring organic compound BB-15

[0149] Synthetic route of the diboron fused-ring organic compound BB-15:

[0150]

[0151] Synthesis of the diboron-fused-ring organic compound BB-15:

[0152] Intermediate 4-C (0.36 g, 0.5 mmol), BB-3 (0.24 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:20 to give 141 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-15 was 30%. MALDI-TOF-MS (m / z): 940.9 ([M]) + ).

[0153] Example 16 Synthesis of the diboron-fused-ring organic compound BB-16

[0154] Synthetic route of BB-16, a diboron-fused-ring organic compound:

[0155]

[0156] Synthesis of the diboron-fused-ring organic compound BB-16:

[0157] Intermediate 4-C (0.36 g, 0.5 mmol), intermediate B-4 (0.30 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:20 to give 184 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-16 was 35%. MALDI-TOF-MS (m / z): 1052.6 ([M]). + ).

[0158] Example 17 Synthesis of the diboron fused-ring organic compound BB-17

[0159] Synthetic route of BB-17, a diboron-fused-ring organic compound:

[0160]

[0161] Synthesis of BB-17, a diboron-fused-ring organic compound:

[0162] In a dry double-necked flask, intermediates 5-C (0.29 g, 0.5 mmol), B-3 (0.24 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography with dichloromethane:petroleum ether = 1:25 to give 182 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-17 was 40%. MALDI-TOF-MS (m / z): 912.4 ([M]) + ).

[0163] Example 18 Synthesis of the diboron fused-ring organic compound BB-18

[0164] Synthetic route of the diboron-fused-ring organic compound BB-18:

[0165]

[0166] Synthesis of the diboron fused-ring organic compound BB-18:

[0167] Intermediate 5-C (0.29 g, 0.5 mmol), BB-4 (0.30 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 160 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-18 was 35%. MALDI-TOF-MS (m / z): 912.2 ([M] + ).

[0168] Example 19 Synthesis of the diboron fused-ring organic compound BB-19

[0169] Synthetic route of BB-19, a diboron-fused-ring organic compound:

[0170]

[0171] Synthesis of the diboron-fused-ring organic compound BB-19:

[0172] Intermediate 6-C (0.26 g, 0.5 mmol), intermediate B-3 (0.24 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 243 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-19 was 65%. MALDI-TOF-MS (m / z): 748.1 ([M]) + ).

[0173] Example 20 Synthesis of the diboron-fused-ring organic compound BB-20

[0174] Synthetic route of BB-20, a diboron-fused-ring organic compound:

[0175]

[0176] Synthesis of BB-20, a diboron-fused-ring organic compound:

[0177] Intermediate 6-C (0.26 g, 0.5 mmol), intermediate B-4 (0.30 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 215 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-20 was 50%. MALDI-TOF-MS (m / z): 860.2 ([M]) + ).

[0178] Example 21 Synthesis of the diboron fused-ring organic compound BB-21

[0179] Synthetic route of BB-21, a diboron-fused-ring organic compound:

[0180]

[0181] Synthesis of BB-21, a diboron-fused-ring organic compound:

[0182] Intermediate 7-C (0.28 g, 0.5 mmol), intermediate B-3 (0.24 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:20 to give 137 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-21 was 35%. MALDI-TOF-MS (m / z): 780.1 ([M]) + ).

[0183] Example 22 Synthesis of the diboron fused-ring organic compound BB-22

[0184] Synthetic route of BB-22, a diboron-fused-ring organic compound:

[0185]

[0186] Synthesis of the diboron-fused-ring organic compound BB-22:

[0187] Intermediate 7-C (0.28 g, 0.5 mmol), intermediate B-4 (0.30 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 178 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-22 was 40%. MALDI-TOF-MS (m / z): 892.3 ([M]). + ).

[0188] Example 23 Synthesis of the diboron fused-ring organic compound BB-23

[0189] Synthetic route of BB-23, a diboron-fused-ring organic compound:

[0190]

[0191] Synthesis of the diboron-fused-ring organic compound BB-23:

[0192] Intermediate 8-C (0.33 g, 0.5 mmol), intermediate B-3 (0.24 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed in a dry double-necked flask. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 197 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-23 was 45%. MALDI-TOF-MS (m / z): 876.1 ([M]) + ).

[0193] Example 24 Synthesis of the diboron fused-ring organic compound BB-24

[0194] Synthetic route of BB-24, a diboron-fused-ring organic compound:

[0195]

[0196] Synthesis of the diboron-fused-ring organic compound BB-24:

[0197] In a dry double-necked flask, intermediates 8-c (0.33 g, 0.5 mmol), B-4 (0.30 g, 0.55 mmol), tetra-(triphenylphosphine)palladium (0.011 g, 0.01 mmol), and K₂CO₃ (0.14 g, 1 mmol) were placed. The mixture was evacuated and purged with nitrogen three times. Then, a mixed solution of toluene (4 ml), methanol (4 ml), and water (2 ml) was added under nitrogen flow. The mixture was heated to 110 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added. The mixture was extracted multiple times with dichloromethane, and the organic phase was collected, concentrated, and purified by column chromatography using dichloromethane:petroleum ether = 1:25 to give 272 mg of a yellow solid. The yield of the diboron fused-ring organic compound BB-24 was 55%. MALDI-TOF-MS (m / z): 988.2 ([M]). + ).

[0198] 2. Fabrication and characterization of OLED devices:

[0199] The fabrication steps for an OLED device with ITO / NPD (60nm) / BB-1~BB-24 (10wt%):DMIC-TRZ (90wt%) (15nm) / TPBi (65nm) / LiF (1nm) / Al (150nm) / cathode are as follows:

[0200] a. Cleaning of anodic conductive glass substrate ITO (indium tin oxide): For first-time use, various solvents can be used for cleaning, such as chloroform, ketone, and isopropanol, followed by ultraviolet ozone plasma treatment.

[0201] b. NPD (N,N′-di-1-naphthyl-N,N′-diphenylbenzidine) serves as the hole transport layer (HTL) (60 nm), BB-1 to BB-24 and DMIC-TRZ (5-(3′-(4,6-diphenyl-1,3,5-triazin-2-yl)[1,1′-biphenyl]-3-yl)-7,7-dimethyl-5,7-dihydroindole[2,1-B]carbazole) together serve as the luminescent layer (EML) (25 nm), in which the diboron fused-ring organic compounds BB-1 to B-24 are doped into the host material DMIC-TRZ at a weight ratio of 10 wt%, and TPBi (1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene) serves as the electron transport layer (ETL) (65 nm): under high vacuum (1×10 -6 It is formed by thermal evaporation in millibar (mbar).

[0202] c. Cathode: LiF / Al (1nm / 150nm) in high vacuum (1×10⁻⁶) -6 It is produced by thermal evaporation in millibars;

[0203] d. Packaging: The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0204] The current-voltage-luminance (JVL) characteristics of this OLED device were characterized using characterization equipment, while important parameters such as efficiency and external quantum efficiency were recorded. The maximum external quantum efficiency (EQE) of the OLED was measured to be 26%, as detailed below:

[0205] EQE 20％ 21％ 19％ 16％ 23％ 22％ 24％ 22％ Complex BB-9 BB-10 BB-11 BB-12 BB-13 BB-14 BB-15 BB-16 EQE 20％ 18％ 26％ 23％ 17％ 16％ 15％ 14％ Complex BB-17 BB-18 BB-19 BB-20 BB-21 BB-22 BB-23 BB-24 EQE 22％ 20％ 24％ 23％ 21％ 19％ 24％ 22％

[0206] Further optimizations, such as improvements to the device structure and the combination of HTM, ETM, and body materials, will further improve device performance, particularly efficiency, drive voltage, and lifespan.

Claims

1. A diboron-fused-ring organic compound, characterized in that, The diboron-fused-ring organic compound is selected from the following structures: 。 2. The application of the diboron fused-ring organic compound of claim 1 in the preparation of organic electronic devices, wherein the organic electronic device is an organic light-emitting diode.

3. An organic light-emitting diode, characterized in that, The organic light-emitting diode comprises the bis-boron fused-ring organic compound of claim 1.

Images