An aryl boron nitrogen compound, its preparation method, and its application in organic electroluminescent devices.
By introducing aryl boron nitrogen compounds into MR-TADF molecules as the light-emitting layer material, the problem of spectral broadening caused by the easy aggregation of MR-TADF molecules was solved, and the performance of organic electroluminescent devices was improved and the structure was simplified.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- TIANJIN UNIVERSITY OF TECHNOLOGY
- Filing Date
- 2026-02-13
- Publication Date
- 2026-06-30
AI Technical Summary
Existing MR-TADF molecules are prone to molecular aggregation due to their planar structure, resulting in drastic spectral broadening and decreased luminescence efficiency.
Aryl boron nitrogen compounds are used as the light-emitting layer material. By introducing different electron-donating groups, organic light-emitting materials with space charge transfer characteristics are formed. Novel organic light-emitting materials are constructed using BN covalent bonds, maintaining the MR effect and optimizing the material structure.
It achieves simplification of device structure and improvement of performance, and has narrow-band emission, high luminous intensity, good thermal stability and solubility, making it suitable for organic electroluminescent devices.
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Figure CN122301922A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic synthesis technology, and in particular to an arylboron nitrogen compound, its preparation method, and its application in organic electroluminescent devices. Background Technology
[0002] Organic light-emitting diodes (OLEDs) are a type of device with a sandwich-like structure, consisting of positive and negative electrode layers and an organic functional material layer sandwiched between them. Due to their advantages such as high brightness, fast response, wide viewing angle, simple manufacturing process, and flexibility, OLED devices have attracted significant attention in the fields of new display technology and new lighting technology. Currently, this technology is widely used in display panels for new lighting fixtures, smartphones, and tablets, and its application is further expanding to large-size display products such as televisions. It is a rapidly developing and technologically demanding new display technology.
[0003] Since the first report of multiple resonance thermal activation delayed fluorescence (MR-TADF) molecules, their narrow-band emission and high luminescence quantum efficiency have sparked sustained research interest in organic electronics, especially in organic light-emitting diodes (OLEDs), rapidly becoming a key research focus and leading to the emergence of numerous high-performance molecules and devices. Devices using MR-TADF molecules as the emitting layer are constantly redefining our understanding of OLEDs, with some devices fabricated using superfluorescence technology representing the highest performance values for OLEDs in certain color fields.
[0004] However, due to the relatively planar structure of MR dyes, they are prone to molecular aggregation, which leads to drastic spectral broadening and a sharp decrease in luminescence efficiency. Summary of the Invention
[0005] The purpose of this invention is to address the technical deficiencies in the prior art by providing an aryl boron nitrogen compound.
[0006] Another object of the present invention is to provide a method for preparing the aryl boron nitrogen compounds.
[0007] Another object of the present invention is to provide the application of the arylborium nitrogen compounds in organic electroluminescent devices.
[0008] The technical solution adopted to achieve the purpose of this invention is: An aryl boron nitrogen compound has the following general structural formula:
[0009] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 The halogen atom X is substituted or unsubstituted aryl or heteroaryl, alkyl, alkenyl, alkynyl, hydrogen, or a single substituted halogen atom; X1, X2, X3, X4, X5, X6, X7, and X8 are each independently represented as B, N, or C.
[0010] In the above technical solution, the aryl boron nitrogen compound has the structural formula shown in formulas (1) to (252):
[0011] Another aspect of the present invention includes a method for preparing the aforementioned aryl boron nitrogen compound, comprising the following steps: Step 1: Add raw material I and raw material II to a solvent with a base to carry out a nucleophilic substitution reaction, and separate and purify to obtain intermediate I; Step 2: Intermediate I, raw material III, and Suzuki reagent are added to a solvent for coupling reaction, and intermediate II is obtained by separation and purification. Step 3: Intermediate II and n-butyllithium are added to a solvent for halolithium exchange, followed by the addition of boron tribromide to generate a boron-containing intermediate. Finally, N,N-diisopropylethylamine is added and the temperature is raised to obtain the aryl boron nitrogen compound, i.e., product I.
[0012] The synthesis route is shown below:
[0013] In the above technical solution, in step 1, the alkali is cesium carbonate. 1.0 equivalent of raw material I, 1.0~1.5 equivalents of raw material II, and 4.0~6.0 equivalents of cesium carbonate are mixed in a solvent and reacted at 150~160℃ for 7~12 hours. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, and the organic layer is collected, dried, and purified to obtain intermediate I. The solvent is preferably DMF, and the solvent is preferably dichloromethane.
[0014] In the above technical solution, in step 2, under the protection of a protective gas, 1.0 equivalent of intermediate I, 1.0~1.5 equivalent of raw material III, 0.1~0.5 equivalent of tetraphenylphosphine palladium and 5.0~10.0 equivalent of potassium carbonate are added to a solvent and mixed. The mixture is reacted at 80~90℃ for 8~14h. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, the organic layer is collected, dried and purified to obtain intermediate II. The solvent is preferably ethylene glycol dimethyl ether and water, with ethylene glycol dimethyl ether:water = 2:1~6:1, and the solvent is preferably dichloromethane.
[0015] In the above technical solution, in step 3, under the protection of a protective gas, 1.0 equivalent of intermediate II is added to a solvent, 3.0 to 5.0 equivalents of n-butyllithium are added at -30℃ to 40℃, and then the mixture is reacted at room temperature for 2 to 4 hours. Then, 3.0 to 5.0 equivalents of boron tribromide are added at -30℃ to 40℃, and the mixture is reacted at room temperature for 1 to 2 hours. Then, 5.0 to 10.0 equivalents of N,N-diisopropylethylamine are added at 0℃ to 10℃, and the mixture is heated to 150℃ to 160℃ and reacted for 24 to 48 hours. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, the organic layer is collected, dried, and purified to obtain product I. The solvent is preferably tert-butylbenzene, and the solvent is preferably dichloromethane.
[0016] Another aspect of the present invention includes the application of the aforementioned aryl boron nitrogen compounds in organic light-emitting materials.
[0017] In the above technical solution, the aryl boron nitrogen compound is used as a light-emitting layer material in organic electroluminescent devices.
[0018] Another aspect of the present invention includes an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers inserted between the first electrode and the second electrode, wherein the organic layers comprise at least one of the aryl boron nitrogen compounds described above.
[0019] Another aspect of the present invention includes an electronic product comprising the aforementioned organic electroluminescent device, wherein preferably, the electronic product is a lighting fixture, a mobile phone, or a computer.
[0020] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention introduces different electron-donating groups around the aryl boron nitrogen to form organic light-emitting materials with space charge transfer characteristics, thereby simplifying the device structure and improving its performance and lifetime.
[0021] 2. The aryl boron nitrogen compounds of the present invention can be used as narrow-emission fluorescent materials, possessing unique narrow-band emission, high luminescence intensity and delayed fluorescence, good thermal stability and good solubility, and have significant economic value in applications such as the preparation of luminescent materials, luminescent devices or smart materials.
[0022] 3. The aryl boron nitrogen skeleton of the present invention is the basic skeleton of TADF. Derivatization of it will not affect the short-range separation of HOMO-LUMO, so they all have narrow-band emission. At the same time, due to the presence of BN in the carbazole, the light color (emission wavelength) can be effectively controlled. Attached Figure Description
[0023] Figure 1 The following is a description of the compound of formula (1). 1 H NMR spectrum (400 MHz, CD2Cl2).
[0024] Figure 2 The following is a description of the compound of formula (65). 1 H NMR spectrum (400 MHz, CD2Cl2).
[0025] Figure 3 The following is a description of the compound of formula (128). 1 H NMR spectrum (400 MHz, CD2Cl2).
[0026] Figure 4 The following is a description of the compound of formula (192). 1 H NMR spectrum (400 MHz, CD2Cl2).
[0027] Figure 5 The fluorescence emission spectrum of the compound of formula (1) is shown.
[0028] Figure 6 The fluorescence emission spectrum of compound (65) is shown.
[0029] Figure 7 The fluorescence emission spectrum of compound (128) is shown.
[0030] Figure 8The fluorescence emission spectrum of compound (192) is shown. Detailed Implementation
[0031] The present invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0032] Example 1 The compound of formula (1) has the following structural formula:
[0033] The synthesis method includes the following steps: Step 1, synthesize compound formula (1)-1:
[0034] Carbazole (1.0 equiv, 12.00 mmol, 2.0 g), 2,3-dibromofluorobenzene (1.0 equiv, 12.00 mmol, 3.0 g), and cesium carbonate (4.0 equiv, 48.00 mmol, 15.6 g) were placed in a 100 mL round-bottom flask, purged three times, and protected with nitrogen. 24 mL of N,N-dimethylformamide solvent was added, and the mixture was stirred at 150 °C for 6 h. After the reaction was complete, water was added to quench the reaction. The mixture was extracted with dichloromethane and water, and the organic phase was collected, dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (1)-1.
[0035] Step 2, synthesize compounds of formula (1)-3:
[0036] Formula (1)-1 (1.0 equiv, 1.13 mmol, 454.8 mg), Formula (1)-2 (1.2 equiv, 1.36 mmol, 400.00 mg), tetraphenylphosphine palladium (0.1 equiv, 0.11 mmol, 131.03 mg), and potassium carbonate (5.0 equiv, 5.67 mmol, 783.6 mg) were placed in a 50 mL Schlenk tube, purged three times, and protected with nitrogen. 10.8 mL of ethylene glycol dimethyl ether and 2.7 mL of water were added, and the mixture was stirred at 80 °C for 12 h. After the reaction was complete, the mixture was extracted with dichloromethane and water, and the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain Formula (1)-3.
[0037] Step 3, synthesize compound formula (1):
[0038] Formula (1)-3 (1.0 equiv, 0.41 mmol, 200.00 mg) was placed in a 20 mL Schlenk tube, purged three times, and protected with nitrogen. 3.2 mL of tert-butylbenzene solvent was added, followed by n-butyllithium (2.0 equiv, 0.82 mmol, 0.51 mL) at -30 °C. The mixture was heated to room temperature and reacted for 2 h. The temperature was then lowered to -30 °C, and boron tribromide (1.2 equiv, 0.49 mmol, 46.50 μL) was added. The mixture was heated to room temperature and reacted for 1.5 h. The temperature was then lowered to 0 °C, and N,N-diisopropylethylamine (2.0 equiv, 0.82 mmol, 135.8 μL) was added. The mixture was heated to 150 °C and reacted for 24 h. After the reaction was complete, the mixture was quenched with water, extracted with dichloromethane and water, and the organic phase was collected. The phase was dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (1), and the 1H NMR spectrum is shown below. Figure 1 As shown.
[0039] Example 2 The synthetic compound (24) has the following structural formula:
[0040] The synthesis principle is the same as in Example 1, except that in step 1, the 2,3-dibromofluorobenzene in Example 1 is replaced with an equal amount of formula (24)-1 to synthesize compound formula (24)-2:
[0041] Then, replace compound formula (1)-1 with compound formula (24)-2, and proceed with steps 2 and 3 to obtain compound formula (24).
[0042] Example 3 The synthetic compound (35) has the following structural formula:
[0043] The synthesis principle is the same as in Example 1, except that in step 1, the 2,3-dibromofluorobenzene in Example 1 is replaced with an equal amount of formula (35)-1 to synthesize compound formula (35)-2:
[0044] Then, replace compound formula (1)-1 with compound formula (34)-2, and proceed with steps 2 and 3 to obtain compound formula (34).
[0045] Example 4 The synthetic compound (44) has the following structural formula:
[0046] The synthesis principle is the same as in Example 1, except that in step 1, the 2,3-dibromofluorobenzene in Example 1 is replaced with an equal amount of formula (44)-1 to synthesize compound formula (44)-2:
[0047] Then, replace compound formula (1)-1 with compound formula (44)-2, and proceed with steps 2 and 3 to obtain compound formula (44).
[0048] Example 5 The synthetic compound (54) has the following structural formula:
[0049] The synthesis principle is the same as in Example 1, except that in step 1, the 2,3-dibromofluorobenzene in Example 1 is replaced with an equal amount of formula (54)-1 to synthesize compound formula (54)-2:
[0050] Then, replace compound formula (1)-1 with compound formula (54)-2, and proceed with steps 2 and 3 to obtain compound formula (54).
[0051] Example 6 The compound of formula (65) is synthesized, and its structural formula is as follows:
[0052] The synthesis method includes the following steps: Step 1, synthesize compound formula (65)-1:
[0053] Carbazole (1.0 equiv, 12.00 mmol, 2.0 g), 2,3-dibromofluorobenzene (1.0 equiv, 12.00 mmol, 3.0 g), and cesium carbonate (4.0 equiv, 48.00 mmol, 15.6 g) were placed in a 100 mL round-bottom flask, purged three times, and protected with nitrogen. 24 mL of N,N-dimethylformamide solvent was added, and the mixture was stirred at 150 °C for 6 h. After the reaction was complete, water was added to quench the reaction. The mixture was extracted with dichloromethane and water, and the organic phase was collected, dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (65)-1.
[0054] Step 2, synthesize compound formula (65)-3:
[0055] Formula (65)-1 (1.0 equiv, 1.13 mmol, 454.8 mg), Formula (65)-2 (1.2 equiv, 1.36 mmol, 400.00 mg), tetraphenylphosphine palladium (0.1 equiv, 0.11 mmol, 131.03 mg), and potassium carbonate (5.0 equiv, 5.67 mmol, 783.6 mg) were placed in a 50 mL Schlenk tube, purged three times, and protected with nitrogen. 10.8 mL of ethylene glycol dimethyl ether and 2.7 mL of water were added, and the mixture was stirred at 80 °C for 12 h. After the reaction was complete, the mixture was extracted with dichloromethane and water, and the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain Formula (65)-3.
[0056] Step 3, synthesize compound formula (65):
[0057] Formula (65)-3 (1.0 equiv, 0.41 mmol, 200.00 mg) was placed in a 20 mL Schlenk tube, purged three times, and protected with nitrogen. 3.2 mL of tert-butylbenzene solvent was added, followed by n-butyllithium (2.0 equiv, 0.82 mmol, 0.51 mL) at -30 °C. The mixture was heated to room temperature and reacted for 2 h. The temperature was then lowered to -30 °C, and boron tribromide (1.2 equiv, 0.49 mmol, 46.50 μL) was added. The mixture was heated to room temperature and reacted for 1.5 h. The temperature was then lowered to 0 °C, and N,N-diisopropylethylamine (2.0 equiv, 0.82 mmol, 135.8 μL) was added. The mixture was heated to 150 °C and reacted for 24 h. After the reaction was complete, water was added to quench the reaction. The mixture was extracted with dichloromethane and water, and the organic phase was collected, dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (65), and the 1H NMR spectrum is shown below. Figure 2 As shown.
[0058] Example 7 The synthetic compound (81) has the following structural formula:
[0059] The synthesis principle is the same as in Example 6, except that in step 1, the 2,3-dibromofluorobenzene in Example 6 is replaced with an equal amount of formula (81)-1 to synthesize compound formula (81)-2:
[0060] Then, replace compound formula (65)-1 with compound formula (81)-2, and proceed with steps 2 and 3 to obtain compound formula (81).
[0061] Example 8 The synthetic compound (93) has the following structural formula:
[0062] The synthesis principle is the same as in Example 6, except that in step 1, the 2,3-dibromofluorobenzene in Example 6 is replaced with an equal amount of formula (93)-1 to synthesize compound formula (93)-2:
[0063] Then, replace compound formula (65)-1 with compound formula (93)-2, and proceed with steps 2 and 3 to obtain compound formula (93).
[0064] Example 9 The synthetic compound (98) has the following structural formula:
[0065] The synthesis principle is the same as in Example 6, except that in step 1, the 2,3-dibromofluorobenzene in Example 6 is replaced with an equal amount of formula (98)-1 to synthesize compound formula (98)-2:
[0066] Then, replace compound formula (65)-1 with compound formula (98)-2, and proceed with steps 2 and 3 to obtain compound formula (98).
[0067] Example 10 The synthetic compound (117) has the following structural formula:
[0068] The synthesis principle is the same as in Example 6, except that in step 1, the 2,3-dibromofluorobenzene in Example 6 is replaced with an equimolar amount of formula (117)-1 to synthesize compound formula (117)-2:
[0069] Then, replace compound formula (65)-1 with compound formula (117)-2, and proceed with steps 2 and 3 to obtain compound formula (117).
[0070] Example 11 The compound with formula (128) is synthesized, and its structural formula is as follows:
[0071] The synthesis method includes the following steps: Step 1, synthesize compound formula (128)-1:
[0072] 3,6-Di-tert-butylcarbazole (1.0 equiv, 12.00 mmol, 2.0 g), 4-fluoro-2,3-dibromotoluene (1.0 equiv, 12.00 mmol, 3.0 g), and cesium carbonate (4.0 equiv, 48.00 mmol, 15.6 g) were placed in a 100 mL round-bottom flask, purged three times, and protected with nitrogen. 24 mL of N,N-dimethylformamide solvent was added, and the mixture was stirred at 150 °C for 6 h. After the reaction was complete, water was added to quench the reaction. The mixture was extracted with dichloromethane and water, and the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (128)-1.
[0073] Step 2, synthesize compound formula (128)-3:
[0074] Formula (128)-1 (1.0 equiv, 1.13 mmol, 454.8 mg), Formula (128)-2 (1.2 equiv, 1.36 mmol, 400.00 mg), tetraphenylphosphine palladium (0.1 equiv, 0.11 mmol, 131.03 mg), and potassium carbonate (5.0 equiv, 5.67 mmol, 783.6 mg) were placed in a 50 mL Schlenk tube, purged three times, and protected with nitrogen. 10.8 mL of ethylene glycol dimethyl ether and 2.7 mL of water were added, and the mixture was stirred at 80 °C for 12 h. After the reaction was complete, the mixture was extracted with dichloromethane and water, and the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain Formula (128)-3.
[0075] Step 3, synthesize compound formula (128):
[0076] Formula (128)-3 (1.0 equiv, 0.41 mmol, 200.00 mg) was placed in a 20 mL Schlenk tube, purged three times, and protected with nitrogen. 3.2 mL of tert-butylbenzene solvent was added, followed by n-butyllithium (2.0 equiv, 0.82 mmol, 0.51 mL) at -30 °C. The mixture was heated to room temperature and reacted for 2 h. The temperature was then lowered to -30 °C, and boron tribromide (1.2 equiv, 0.49 mmol, 46.50 μL) was added. The mixture was heated to room temperature and reacted for 1.5 h. The temperature was then lowered to 0 °C, and N,N-diisopropylethylamine (2.0 equiv, 0.82 mmol, 135.8 μL) was added. The mixture was heated to 150 °C and reacted for 24 h. After the reaction was complete, the mixture was quenched with water, extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (128), and the 1H NMR spectrum is shown below. Figure 3 As shown.
[0077] Example 12 The synthetic compound (138) has the following structural formula:
[0078] The synthesis principle is the same as in Example 11, except that in step 1, 4-fluoro-2,3-dibromotoluene in Example 11 is replaced with an equal amount of formula (138)-1 to synthesize compound formula (138)-2:
[0079] Then, replace compound formula (128)-1 with compound formula (138)-2, and proceed with steps 2 and 3 to obtain compound formula (138).
[0080] Example 13 The synthetic compound (150) has the following structural formula:
[0081] The synthesis principle is the same as in Example 11, except that in step 1, 4-fluoro-2,3-dibromotoluene in Example 11 is replaced with an equal amount of formula (150)-1 to synthesize compound formula (150)-2:
[0082] Then, replace compound formula (128)-1 with compound formula (150)-2, and proceed with steps 2 and 3 to obtain compound formula (150).
[0083] Example 13 The synthetic compound (161) has the following structural formula:
[0084] The synthesis principle is the same as in Example 11, except that in step 1, 4-fluoro-2,3-dibromotoluene in Example 11 is replaced with an equal amount of formula (161)-1 to synthesize compound formula (161)-2:
[0085] Then, replace compound formula (128)-1 with compound formula (161)-2, and proceed with steps 2 and 3 to obtain compound formula (161).
[0086] Example 14 The synthetic compound (173) has the following structural formula:
[0087] The synthesis principle is the same as in Example 11, except that in step 1, 4-fluoro-2,3-dibromotoluene in Example 11 is replaced with an equal amount of formula (173)-1 to synthesize compound formula (173)-2:
[0088] Then, replace compound formula (128)-1 with compound formula (173)-2, and proceed with steps 2 and 3 to obtain compound formula (173).
[0089] Example 15 The compound with formula (192) is synthesized, and its structural formula is as follows:
[0090] The synthesis method includes the following steps: Step 1, synthesize compound formula (192)-1:
[0091] 3,6-Di-tert-butylcarbazole (1.0 equiv, 12.00 mmol, 2.0 g), 4-fluoro-2,3-dibromotoluene (1.0 equiv, 12.00 mmol, 3.0 g), and cesium carbonate (4.0 equiv, 48.00 mmol, 15.6 g) were placed in a 100 mL round-bottom flask, purged three times, and protected with nitrogen. 24 mL of N,N-dimethylformamide solvent was added, and the mixture was stirred at 150 °C for 6 h. After the reaction was complete, water was added to quench the reaction. The mixture was extracted with dichloromethane and water, and the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (192)-1.
[0092] Step 2, synthesize compound formula (192)-3:
[0093] Formula (192)-1 (1.0 equiv, 1.13 mmol, 454.8 mg), Formula (192)-2 (1.2 equiv, 1.36 mmol, 400.00 mg), tetraphenylphosphine palladium (0.1 equiv, 0.11 mmol, 131.03 mg), and potassium carbonate (5.0 equiv, 5.67 mmol, 783.6 mg) were placed in a 50 mL Schlenk tube, purged three times, and protected with nitrogen. 10.8 mL of ethylene glycol dimethyl ether and 2.7 mL of water were added, and the mixture was stirred at 80 °C for 12 h. After the reaction was complete, the mixture was extracted with dichloromethane and water, and the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain Formula (192)-3.
[0094] Step 3, synthesize compound formula (192):
[0095] Formula (192)-3 (1.0 equiv, 0.41 mmol, 200.00 mg) was placed in a 20 mL Schlenk tube, purged three times, and protected with nitrogen. 3.2 mL of tert-butylbenzene solvent was added, followed by n-butyllithium (2.0 equiv, 0.82 mmol, 0.51 mL) at -30 °C. The mixture was heated to room temperature and reacted for 2 h. The temperature was then lowered to -30 °C, and boron tribromide (1.2 equiv, 0.49 mmol, 46.50 μL) was added. The mixture was heated to room temperature and reacted for 1.5 h. The temperature was then lowered to 0 °C, and N,N-diisopropylethylamine (2.0 equiv, 0.82 mmol, 135.8 μL) was added. The mixture was heated to 150 °C and reacted for 24 h. After the reaction was complete, the mixture was quenched with water, extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (192), and the 1H NMR spectrum is shown below. Figure 4 As shown.
[0096] Example 16 The synthetic compound formula (197) has the following structural formula:
[0097] The synthesis principle is the same as in Example 15, except that in step 1, 4-fluoro-2,3-dibromotoluene in Example 15 is replaced with an equal amount of formula (197)-1 to synthesize compound formula (197)-2:
[0098] Then, replace compound formula (192)-1 with compound formula (197)-2, and proceed with steps 2 and 3 to obtain compound formula (192).
[0099] Example 17 The synthetic compound (214) has the following structural formula:
[0100] The synthesis principle is the same as in Example 15, except that in step 1, 4-fluoro-2,3-dibromotoluene in Example 15 is replaced with an equimolar amount of formula (214)-1, resulting in compound formula (214)-2:
[0101] Then, replace compound formula (192)-1 with compound formula (214)-2, and proceed with steps 2 and 3 to obtain compound formula (214).
[0102] Example 18 The synthetic compound (228) has the following structural formula:
[0103] The synthesis principle is the same as in Example 15, except that in step 1, 4-fluoro-2,3-dibromotoluene in Example 15 is replaced with an equal amount of formula (228)-1 to synthesize compound formula (228)-2:
[0104] Then, replace compound formula (192)-1 with compound formula (228)-2, and proceed with steps 2 and 3 to obtain compound formula (228).
[0105] Example 19 The synthetic compound (234) has the following structural formula:
[0106] The synthesis principle is the same as in Example 15, except that in step 1, 4-fluoro-2,3-dibromotoluene in Example 15 is replaced with an equimolar amount of formula (234)-1 to synthesize compound formula (234)-2: Then, replace compound formula (192)-1 with compound formula (234)-2, and proceed with steps 2 and 3 to obtain compound formula (234).
[0107] Test case The fluorescence emission properties of compounds of formula (1), (65), (128), and (192) were tested, and the results are as follows: Figures 5-8 As shown.
[0108] The emission wavelength of compound (1) is 423 nm and the half-width at half-maximum (WHM) is 16 nm; the emission wavelength of compound (65) is 446 nm and the WHM is 21 nm; the emission wavelength of compound (128) is 435 nm and the WHM is 20 nm; the emission wavelength of compound (192) is 454 nm and the WHM is 22 nm.
[0109] The compounds of this invention expand the narrowband emitting molecular framework system by introducing BN polar covalent bonds into the B, N molecular framework exhibiting multiple resonance (MR) effects, while retaining the MR effect when B and N are in the para position. By using BN covalent bonds to dope the MR resonance framework to construct novel organic narrow-spectrum luminescent materials, the insertion of BN bonds maintains the planar structure of the MR framework and simultaneously acquires unique photophysical properties, such as bipolar carrier transport capability and intermolecular dipole... Dipole interactions, etc. By optimizing the material structure through the parent core, peripheral substituents, and fused ring parallel arrangements, the fluorescence spectra of the compounds in this invention exhibit a full width at half maximum (FWHM) of only 16-30 nm, demonstrating high brightness and greatly enriching the multiple resonance spectrum. The material system with thermally activated delayed fluorescence has promising application prospects.
[0110] The above description is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. An arylboron nitrogen compound, characterized in that, The general structural formula is as follows: Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 The halogen atom X is substituted or unsubstituted aryl or heteroaryl, alkyl, alkenyl, alkynyl, hydrogen, or a single substituted halogen atom; X1, X2, X3, X4, X5, X6, X7, and X8 are each independently represented as B, N, or C.
2. The arylboron nitrogen compound according to claim 1, characterized in that, Its structural formula is shown in equations (1) to (252):
3. The method for preparing the arylborium nitrogen compound according to claim 1, characterized in that, Prepared by the following steps: Step 1: Add raw material I and raw material II to a solvent with a base to carry out a nucleophilic substitution reaction, and separate and purify to obtain intermediate I; Step 2: Intermediate I, raw material III, and Suzuki reagent are added to a solvent for coupling reaction, and intermediate II is obtained by separation and purification. Step 3: Add intermediate II and n-butyllithium to the solvent to perform halolithium exchange, then add boron tribromide to react and generate a boron-containing intermediate, and finally add N,N-diisopropylethylamine to heat and react to obtain the aryl boron nitrogen compound, i.e., product I. The synthesis route is shown below:
4. The preparation method according to claim 3, characterized in that, In step 1, the alkali is cesium carbonate. 1.0 equivalent of raw material I, 1.0~1.5 equivalents of raw material II, and 4.0~6.0 equivalents of cesium carbonate are mixed in a solvent and reacted at 150~160℃ for 7~12 hours. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, and the organic layer is collected, dried, and purified to obtain intermediate I. The solvent is preferably DMF, and the solvent is preferably dichloromethane.
5. The preparation method according to claim 3, characterized in that, In step 2, under the protection of a protective gas, 1.0 equivalent of intermediate I, 1.0~1.5 equivalent of raw material III, 0.1~0.5 equivalent of tetra-triphenylphosphine palladium, and 5.0~10.0 equivalent of potassium carbonate are added to a solvent and mixed. The mixture is reacted at 80~90℃ for 8~14h. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, the organic layer is collected, dried, and purified to obtain intermediate II. The solvent is preferably ethylene glycol dimethyl ether and water, with ethylene glycol dimethyl ether:water = 2:1~6:1, and the solvent is preferably dichloromethane.
6. The preparation method according to claim 3, characterized in that, In step 3, under the protection of a protective gas, 1.0 equivalent of intermediate II is added to a solvent, and 3.0 to 5.0 equivalents of n-butyllithium are added at -30℃ to 40℃. The mixture is then reacted at room temperature for 2 to 4 hours. Then, 3.0 to 5.0 equivalents of boron tribromide are added at -30℃ to 40℃, and the mixture is reacted at room temperature for 1 to 2 hours. Finally, 5.0 to 10.0 equivalents of N,N-diisopropylethylamine are added at 0℃ to 10℃, and the mixture is heated to 150℃ to 160℃ and reacted for 24 to 48 hours. After the reaction is complete, the reaction mixture is dissolved in a solvent, washed, and the organic layer is collected, dried, and purified to obtain product I. The solvent is preferably tert-butylbenzene, and the solvent is preferably dichloromethane.
7. The application of the aryl boron nitrogen compounds as described in claim 1 in organic light-emitting materials.
8. The application as described in claim 7, characterized in that, The application of the aryl boron nitrogen compounds as light-emitting layer materials in organic electroluminescent devices.
9. An organic electroluminescent device, characterized in that, It includes a first electrode, a second electrode, and one or more organic layers inserted between the first electrode and the second electrode, wherein the organic layer includes at least one arylboron nitrogen compound as described in claim 1.
10. An electronic product, characterized in that, Including the organic electroluminescent device as described in claim 9, preferably, the electronic product is a lighting fixture, a mobile phone, or a computer.