Aryl boron-nitrogen-based narrow-band blue light compound and preparation method and application thereof

Abstract

The patent application discloses an aryl boron-nitrogen narrow-band blue light compound and a preparation method and application thereof. The patent application forms an organic light-emitting material with synergistic effect of short-range charge and long-range charge transfer state by introducing different electron-donating or electron-withdrawing groups into the aryl boron-nitrogen peripheral ether bond, realizes the simplification of the device structure and the improvement of the performance and the life. The patent application also discloses a preparation method and application of the material. The aryl boron-nitrogen narrow-band blue light compound can be used as a novel light-emitting molecule with high performance, high color purity and high quantum efficiency. The aryl boron-nitrogen narrow-band blue light compound has great application potential in the preparation of light-emitting materials, light-emitting devices or intelligent materials and the like, and has a significant and clear prospect in the field of display technology and solid-state lighting.

Description

Technical Field

[0001] This patent application relates to the field of organic light-emitting materials technology, and more specifically, to an aryl boron nitrogen-based narrow-band blue light compound, its preparation method, and its application. Background Technology

[0002] The use of organic light-emitting materials (OLEDs) in flat panel displays and solid-state lighting has enormous market value and application prospects, thanks to the significant advantages of OLEDs, such as thinness, low power consumption, high contrast, self-emission, flexibility, large-area and high-quality display and lighting, ultra-high resolution, and ultra-fast response speed. The vast application potential of OLEDs in flat panel displays, smartphones, and solid-state lighting has attracted widespread attention from the global academic and industrial communities.

[0003] However, in recent years, most of the research on organic light-emitting materials has focused on green and red light materials, while there has been little research on deep blue or blue light multiple resonance materials, and there are very few reports on blue light materials with high efficiency and high color purity multiple resonance.

[0004] Patent application content

[0005] To overcome one of the problems existing in the prior art, the primary objective of this patent application is to provide an arylboron-nitrogen-based narrow-band blue light-emitting compound. This arylboron-nitrogen-based narrow-band blue light-emitting compound contains an electron donor and an ether bridge. Furthermore, this arylboron-nitrogen-based narrow-band blue light-emitting compound can serve as an organic light-emitting material, and by adjusting the type and position of the electron donor, it possesses the advantages of tunable light color from deep blue to blue, high luminous efficiency, and high color purity.

[0006] Another objective of this patent application is to provide a method for preparing the above-mentioned aryl boron nitrogen-based narrow-band blue light compound.

[0007] Another objective of this patent application is to provide the application of the above-mentioned aryl boron nitrogen-based narrow-band blue light compounds.

[0008] The above-mentioned objective of this patent application is achieved through the following technical solution:

[0009] An aryl boron nitrogen-based narrow-band blue light-emitting compound, wherein the aryl boron nitrogen-based narrow-band blue light-emitting compound contains an ether bridge and can be used in organic small molecule optoelectronic functional materials, has the molecular structure shown in formula (1) below:

[0010]

[0011] Where D represents an electron-donating or electron-withdrawing group.

[0012] Preferably, in the arylborium nitrogen-based narrow-band blue light compound of this patent application, D is selected from the following...

[0013] One type of construction:

[0014]

[0015] Wherein, R is selected from H, CN, Me or t-Bu.

[0016] This patent application also provides a method for preparing the above-mentioned aryl boron nitrogen-based narrow-band blue light compound, comprising the following steps:

[0017] S1 Preparation of Intermediate 1:

[0018] 2,6-Difluoro-4-bromoiodobenzene, 3,6-di-tert-butylcarbazole and cesium carbonate were added sequentially to a reaction flask. After the nitrogen gas was replaced three times, N,N-dimethylformamide was added, and the reaction was refluxed under nitrogen. After the reaction was completed, the system was allowed to return to room temperature, and then extracted and washed with dichloromethane and saturated brine. After the organic phase was recovered and the solvent was removed, ethanol was added, heated and stirred, and filtered to obtain intermediate 1, the structure of which is shown below.

[0019]

[0020] S2 preparation of intermediate 2:

[0021] Intermediate 1 obtained in step S1 was dissolved in o-xylene, and n-butyllithium was slowly added under stirring. Then, boron tribromide was added under stirring, followed by N,N-diisopropylethylamine, and stirring was continued for 5 hours. After the reaction was completed, water was added to quench the reaction. The product was extracted and washed with dichloromethane and saturated brine, the organic phase was recovered and dried with anhydrous magnesium sulfate, the solvent was removed by vacuum distillation, and the crude product was then purified by column chromatography to obtain intermediate 2, the structure of which is shown below.

[0022]

[0023] S3 preparation of intermediate 3:

[0024] Intermediate 2 obtained in step S2 was dissolved in 1,4-dioxane, and pinacol diborate, 1,1-bis(diphenylphosphine)ferrocene palladium dichloride, and potassium acetate were added. After reacting under nitrogen purging for 24 hours three times, the mixture was extracted and washed with dichloromethane and saturated brine. The organic phase was recovered and dried over anhydrous magnesium sulfate. The solvent was removed by vacuum distillation, and the crude product was then purified by column chromatography to generate intermediate 3, the structure of which is shown below.

[0025]

[0026] S4 Preparation of aryl boron nitrogen-based narrow-band blue light compounds:

[0027] Intermediate 3 obtained from S3 was co-dissolved in an organic solvent with an alkaline salt, a catalyst, and a donor group. After heating and post-treatment, an aryl boron nitrogen-based narrow-band blue light compound was obtained.

[0028] Preferably, in step S1, the molar ratio of 2,6-difluoro-4-bromoiodobenzene, 3,6-di-tert-butylcarbazole and cesium carbonate is 1:(2-3):(2-3), the reaction temperature is 110-150°C, and the reaction time is 24-36 h.

[0029] Preferably, in step S2, the molar ratio of intermediate 1, n-butyllithium (2.5M) and boron tribromide is 1:(2-3):(1-2), the reaction temperature is 0 to -20°C, and the reaction time is 1 to 2 hours.

[0030] Preferably, in step S3, the molar ratio of intermediate 2 to pinacol diborate, potassium acetate, and 1,1-bis(diphenylphosphine)ferrocene palladium dichloride is 1:2:3:0.05, the reaction temperature is 100-140°C, and the reaction time is 12-24 h.

[0031] Preferably, the molar ratio of intermediate 3 to alkaline salt, catalyst and donor group in step S4 is 1:(2-8):(0.05-1):(2-2.5).

[0032] Preferably, the alkaline salt reacted in step S4 is one of sodium tert-butoxide or triethylamine, and the catalyst for the reaction is one of palladium acetate, copper acetate, or 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride.

[0033] Preferably, in step S4, the organic solvent for the reaction is one of toluene, dichloromethane, or 1,4-dioxane, the reaction temperature is 90℃~120℃, and the reaction time is 12~24h.

[0034] The application of the aryl boron nitrogen-based narrowband blue light-emitting compounds in this patent application as luminescent materials, luminescent devices, or smart materials.

[0035] Compared with the prior art, the beneficial effects of this patent application are:

[0036] The aryl boron-nitrogen narrow-band blue light-emitting compound provided in this patent application utilizes the multiple resonance properties of the aryl boron-nitrogen group. By connecting electron-donating or electron-withdrawing groups via ether bonds, it achieves effective charge transfer to regulate the excited-state properties of the molecule. The oxygen atom on the ether bond has a weak electron-donating ability, allowing the electron-withdrawing boron atoms to form a better electron cloud distribution. Furthermore, because the boron-carbazole group possesses high luminescence efficiency (91% quantum efficiency) and high color purity (23nm half-width), it can improve the external quantum efficiency of the device. The long-range charge transfer state and regulation of the excited-state properties of the molecule through ether bond connection of electron-donating or electron-withdrawing groups can effectively promote the reverse intersystem crossing process and improve the performance of thermally activated delayed fluorescence. This compound can serve as a novel luminescent molecule with good performance, low cost, and high luminescence intensity. Attached Figure Description

[0037] Figure 1 The proton NMR spectrum of compound A1 prepared in Example 1 of this patent application;

[0038] Figure 2 The mass spectrum of compound A1 prepared in Example 1 of this patent application;

[0039] Figure 3 The proton NMR spectrum of compound A2 prepared in Example 2 of this patent application;

[0040] Figure 4 The mass spectrum of compound A2 prepared in Example 2 of this patent application;

[0041] Figure 5 Compounds A1 and A2 prepared for Examples 1 and 2 of this patent application were subjected to a temperature of 1.0 × 10⁻⁶. -5 Ultraviolet absorption spectrum of M in toluene solution;

[0042] Figure 6 Compounds A1 and A2 prepared for Examples 1 and 2 of this patent application were subjected to a temperature of 1.0 × 10⁻⁶. -5 Fluorescence emission spectrum of M in toluene solution.

[0043] Figure 7 This is a schematic diagram illustrating the principle involved in this patent application. Detailed Implementation

[0044] The embodiments of this patent application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be construed as limiting the scope of this patent application. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0045] It should be noted that:

[0046] Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0047] In this patent application, unless otherwise specified, percentage (%) or parts refer to weight percentage or parts relative to the composition.

[0048] Unless otherwise specified, the components or preferred components involved in this patent application may be combined with each other to form new technical solutions.

[0049] In this patent application, unless otherwise stated, the numerical range "a~b" represents an abbreviation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "1~5" means that all real numbers between "1~5" have been listed herein, and "1~5" is simply an abbreviation of these numerical combinations.

[0050] The “scope” disclosed in this patent application may be in the form of a lower limit and an upper limit, and may be one or more lower limits and one or more upper limits, respectively.

[0051] In this patent application, unless otherwise stated, the various reactions or operation steps may be performed sequentially or in a particular order. Preferably, the reaction methods described herein are performed sequentially.

[0052] Unless otherwise stated, the technical and scientific terms used herein have the same meanings as those familiar to a person skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be used in this patent application.

[0053] This patent application provides an aryl boron nitrogen-based narrow-band blue light compound containing an ether bridge and applicable to organic small molecule optoelectronic functional materials, having the molecular structure shown in formula (1):

[0054]

[0055] Where D represents an electron-donating or electron-withdrawing group.

[0056] The narrow-band blue light compound provided in this patent application is based on an arylboron-nitrogen system molecule containing ether bridges. The arylboron-nitrogen group serves as the core of multiple resonance luminescence. By introducing groups with different electron-donating or electron-withdrawing capabilities to its periphery, an organic light-emitting material with synergistic effects of short-range and long-range charge-transfer states is constructed. Because the arylboron-nitrogen group possesses high luminescence efficiency and high color purity, it can improve the external quantum efficiency of the device. Connecting electron-donating or electron-withdrawing groups via ether bonds enables the long-range charge-transfer state of the molecule and regulates the excited-state properties, effectively promoting the reverse intersystem crossing process and improving the performance of thermally activated delayed fluorescence, thereby reducing the severe roll-off problem of blue light devices (see...). Figure 7 This overcomes the problems of existing technologies, such as the lack of efficient, low-roll-off blue light emitting materials.

[0057] In some preferred embodiments, the arylborium nitrogen-based narrow-band blue light compound of this patent application, wherein D is selected from one of the following structural formulas:

[0058]

[0059] Wherein, R is selected from H, CN, Me or t-Bu.

[0060] Therefore, specifically, the structural formula of the above-mentioned aryl boron nitrogen-based narrow-band blue light-emitting compounds is shown in one of the following structures:

[0061]

[0062] Wherein, R is selected from H, CN, Me or t-Bu.

[0063] Therefore, this patent application is based on aryl boron nitrogen system molecules containing ether bridges, wherein the aryl boron nitrogen group is the core of multiple resonance luminescence. By introducing groups with different electron-donating or electron-withdrawing capabilities to its periphery, organic light-emitting materials with synergistic effects of short-range charge transfer state and long-range charge transfer state are formed.

[0064] In some preferred embodiments, the arylborium nitrogen-based narrow-band blue light compound of this patent application, wherein D is selected from one of the following structural formulas:

[0065]

[0066] Where R is selected from H, CN, Me or t-Bu.

[0067] More specifically, this patent application can construct aryl boron nitrogen-based narrow-band blue light compounds as described below:

[0068]

[0069] The aryl boron nitrogen-based narrow-band blue light-emitting compound system constructed in this patent application is diverse and can achieve short-wavelength emission, such as blue light emission.

[0070] In some preferred embodiments, the D is selected from one of the following structural formulas:

[0071]

[0072] Wherein, R is selected from H, CN, Me, or t-Bu. For example, aryl boron nitrogen-based narrow-band blue light compounds can be constructed as shown below:

[0073]

[0074]

[0075] The aryl boron nitrogen-based narrow-band blue light-emitting compound systems constructed above are diverse and can achieve short-wavelength emission, such as blue light emission.

[0076] This patent application also provides a method for preparing the above-mentioned arylborium nitrogen-based narrow-band blue light compound. The method includes the following steps:

[0077] S1 Preparation of Intermediate 1:

[0078] 2,6-Difluoro-4-bromoiodobenzene, 3,6-di-tert-butylcarbazole and cesium carbonate were added sequentially to a reaction flask. After the nitrogen gas was replaced three times, N,N-dimethylformamide was added, and the reaction was refluxed under nitrogen. After the reaction was completed, the system was allowed to return to room temperature, and then extracted and washed with dichloromethane and saturated brine. After the organic phase was recovered and the solvent was removed, ethanol was added, heated and stirred, and filtered to obtain intermediate 1, the structure of which is shown below.

[0079]

[0080] S2 preparation of intermediate 2:

[0081] Intermediate 1 obtained in step S1 was dissolved in o-xylene, and n-butyllithium was slowly added under stirring. Then, boron tribromide was added under stirring, followed by N,N-diisopropylethylamine, and stirring was continued for 5 hours. After the reaction was completed, water was added to quench the reaction. The product was extracted and washed with dichloromethane and saturated brine, the organic phase was recovered and dried with anhydrous magnesium sulfate, the solvent was removed by vacuum distillation, and the crude product was then purified by column chromatography to obtain intermediate 2, the structure of which is shown below.

[0082]

[0083] S3 preparation of intermediate 3:

[0084] Intermediate 2 obtained in step S2 was dissolved in 1,4-dioxane, and pinacol diborate, 1,1-bis(diphenylphosphine)ferrocene palladium dichloride, and potassium acetate were added. After reacting under nitrogen purging for 24 hours three times, the mixture was extracted and washed with dichloromethane and saturated brine. The organic phase was recovered and dried over anhydrous magnesium sulfate. The solvent was removed by vacuum distillation, and the crude product was then purified by column chromatography to generate intermediate 3, the structure of which is shown below.

[0085]

[0086] S4 Preparation of aryl boron nitrogen-based narrow-band blue light compounds:

[0087] Intermediate 3 obtained from S3 was co-dissolved in an organic solvent with an alkaline salt, a catalyst, and a donor group. After heating and post-treatment, an aryl boron nitrogen-based narrow-band blue light compound was obtained.

[0088] In some preferred embodiments, in step S1 of the method for preparing the aryl boron nitrogen-based narrow-band blue light compound of this patent application, the molar ratio of 2,6-difluoro-4-bromoiodobenzene, 3,6-di-tert-butylcarbazole and cesium carbonate is 1:(2-3):(2-3), the reaction temperature is 110-150°C, and the reaction time is 24-36 h.

[0089] In some preferred embodiments, the molar ratio of intermediate 1, n-butyllithium (2.5M), and boron tribromide in step S2 of the preparation method of the arylborium nitrogen narrow-band blue light compound of this patent application is 1:(2-3):(1-2), the reaction temperature is 0 to -20°C, and the reaction time is 1 to 2 hours.

[0090] In some preferred embodiments, in the preparation method described in this patent application, the molar ratio of intermediate 2 to pinacol diborate, potassium acetate, and 1,1-bis(diphenylphosphine)ferrocene palladium dichloride in step S3 is 1:2:3:0.05, the reaction temperature is 100-140°C, and the reaction time is 12-24 h.

[0091] In some preferred embodiments, in the preparation method described in this patent application, the molar ratio of intermediate 3 to alkaline salt, catalyst and donor group in step S4 is 1:(2-8):(0.05-1):(2-2.5).

[0092] In some preferred embodiments, the alkaline salt reacted in step S4 of this patent application is one of sodium tert-butoxide or triethylamine, and the catalyst for the reaction is one of palladium acetate, copper acetate, or 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride.

[0093] In some preferred embodiments, the organic solvent for step S4 of this patent application is one of toluene, dichloromethane, or 1,4-dioxane, the reaction temperature is 90°C to 120°C, and the reaction time is 12 to 24 hours.

[0094] This patent application also provides the application of aryl boron nitrogen-based narrowband blue light compounds as luminescent materials, luminescent devices, or smart materials.

[0095] The preparation method of the aryl boron nitrogen-based narrow-band blue light compound of formula (I) will be described in detail below.

[0096] Example 1

[0097] This embodiment provides an aryl boron nitrogen-based narrow-band blue light compound, with the structural formula shown in A1:

[0098]

[0099] The preparation method of this compound is as follows:

[0100] S1. Preparation of Intermediate 1:

[0101] 2,6-Difluoro-4-bromoiodobenzene (20 mmol, 6.38 g), 3,6-di-tert-butylcarbazole (25 mmol, 13.97 g), and cesium carbonate (30 mmol, 19.55 g) were sequentially added to a 250 mL two-necked flask. After purging with nitrogen three times, 80 mL of N,N-dimethylformamide was added via syringe. The reaction was carried out at 150 °C for 24 hours under nitrogen atmosphere. After the reaction was completed, the system was allowed to return to room temperature, and then extracted and washed with dichloromethane and saturated brine. The organic phase was recovered, the solvent was removed, and ethanol was added. The mixture was heated and stirred, and then filtered to obtain intermediate 1 with a yield of 75%. The structural formula of intermediate 1 is shown below:

[0102]

[0103] The reaction equations in the above preparation method are as follows:

[0104]

[0105] S2. Preparation of intermediate 2;

[0106] At a low temperature of -10°C, intermediate 1 (1 mmol, 837.7 mg) was dissolved in 20 mL of o-xylene. 2.1 mL of n-butyllithium (2.5 M) (1.8 mmol, 0.4 mL) was slowly added with stirring. After stirring for 1 hour, boron tribromide (1.5 mmol, 375 mg) was added with stirring. After two hours, N,N-diisopropylethylamine (2.0 mmol, 258.48 mg) was added, and the mixture was heated to 120°C and reacted for 12 hours. After the reaction was complete, water was added to quench the reaction. The mixture was then extracted and washed with dichloromethane and saturated brine. The organic phase was recovered and dried over anhydrous magnesium sulfate. The solvent was removed by vacuum distillation, and the crude product was purified by column chromatography to obtain intermediate 2 in 30% yield. The structural formula of intermediate 2 is shown below:

[0107]

[0108] The reaction equation in the above preparation method is as follows:

[0109]

[0110] S3. Preparation of intermediate 3;

[0111] Intermediate 2 (1 mmol, 719.6 mg) was dissolved in 1,4-dioxane, and pinacol diboronate (2 mmol, 507.88 mg), 1,1-bis(diphenylphosphine)ferrocene palladium dichloride (0.05 mmol, 36.59 mg), and potassium acetate (3 mmol, 294.42 mg) were added. The mixture was purged with nitrogen three times and reacted at 110 °C for 24 hours. The mixture was then extracted and washed with dichloromethane and saturated brine. The organic phase was recovered and dried over anhydrous magnesium sulfate. The solvent was removed by vacuum distillation, and the crude product was purified by column chromatography to yield intermediate 3 in 60% yield. The structural formula of intermediate 3 is shown below.

[0112]

[0113] The reaction equations involved in the above preparation steps are as follows:

[0114]

[0115] Preparation of S4.A1:

[0116] Intermediate 3 (1 mmol, 766.48 mg), phenol (2.5 mmol, 417.5 mg), copper acetate (0.1 mmol, 29.1 mg), and triethylamine (0.1 mmol, 91.5 mg) were sequentially added to a 100 mL two-necked flask. 40 mL of toluene was added via syringe. The mixture was refluxed at 110 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature and extracted three times with ethyl acetate and saturated brine. The organic phase was collected and evaporated under reduced pressure to obtain the crude product. The crude product was then purified by silica gel column chromatography using dichloromethane / petroleum ether as the eluent, with a yield of 65%. The structural formula of the final compound A1 is shown below:

[0117]

[0118] The reaction equation in the above preparation method is as follows:

[0119]

[0120] Example 2

[0121] This embodiment provides another aryl boron nitrogen-based narrow-band blue light compound, the preparation method of which is basically the same as that in Example 1. The difference is that, unlike in Example 1, the group of R is... The aryl boron nitrogen-based narrow-band blue light compound A2 was obtained. The structural formula of A2 is shown below:

[0122]

[0123] Performance testing

[0124] The aryl boron nitrogen narrow-band blue light compounds A1 and A2 prepared in Examples 1 and 2 were characterized and their performance was tested.

[0125] The testing method is as follows:

[0126] Compound structure determination: Bruker 400MHz superconducting nuclear magnetic resonance spectrometer, deuterated chloroform or deuterated dimethyl sulfoxide as solvent;

[0127] Mass spectrometry detection: A1 and A2 obtained in Examples 1 and 2 were dissolved in dichloromethane to prepare a solution with a concentration of 1 mg / mL, and mass spectrometry was performed using a liquid chromatography-mass spectrometry (LCMS-2020) instrument.

[0128] Ultraviolet absorption spectroscopy detection: Shimadzu UV-2700 UV-Vis spectrophotometer was used, with a scanning range of 200–450 nm;

[0129] Emission spectroscopy detection: A steady-state / transient fluorescence spectrometer (FLS980) was used with an excitation wavelength of 310 nm and a test temperature of 300 K under nitrogen protection.

[0130] The test results are as follows:

[0131] The 1H NMR spectrum of the arylborium nitrogen-based narrow-band blue light compound A1 prepared in Example 1 is as follows: Figure 1 As shown. From Figure 1 It can be seen that: 1 ¹H NMR (400MHz, Chloroform-d) δ 9.11 (d, J = 1.9Hz, 2H), 8.43 (d, J = 1.8Hz, 2H), 8.24 (d, J = 2.1Hz, 2H), 8.06 (d, J = 8.8Hz, 2H), 7.91 (s, 2H), 7.63-7.44 (m, 4H), 7.36 (dd, J = 7.9, 3.3Hz, 3H), 1.67 (s, 18H), 1.51 (s, 18H). The ¹H NMR peak energies of this molecular spectrum correspond one-to-one with the target product, and the number is reasonable. The mass spectrum of compound A1 prepared in Example 1 of this patent application is as follows: Figure 2 As shown. From Figure 2 As can be seen in the figure, the relative molecular mass is 732.82, which is consistent with the relative molecular mass of the synthesized A1. Combining the results of the above proton NMR spectrum and mass spectrum, it can be concluded that the product obtained in Example 1 is A1.

[0132] The 1H NMR spectrum of the arylborium nitrogen-based narrow-band blue light compound A2 prepared in Example 2 is as follows: Figure 3 As shown. From Figure 3 It can be seen that: 1 ¹H NMR (400MHz, Chloroform-d) δ 9.06(s, 2H), 8.44(s, 2H), 8.24(s, 2H), 8.09(d, J = 8.8Hz, 2H), 7.93(s, 2H), 7.82(d, J = 9.4Hz, 1H), 7.57(d, J = 8.9Hz, 3H), 7.28(d, J = 7.6Hz, 1H), 7.17(d, J = 8.5Hz, 1H), 1.66(s, 18H), 1.51(s, 18H). The ¹H NMR molecular peak energies correspond one-to-one with the target product, and the number is reasonable. The mass spectrum of compound A2 prepared in Example 2 of this patent application is as follows: Figure 4 As shown. From Figure 4 As can be seen in the figure, the relative molecular mass is 757.83, which is consistent with the relative molecular mass of the synthesized A2. Combining the above NMR and mass spectrometry results, it can be concluded that the product obtained in Example 2 is A2.

[0133] Using a Shimadzu UV-2700 UV-Vis spectrophotometer, A1 and A2 obtained in the example were dissolved in dichloromethane solution to prepare a 1×10⁻⁶ solution. -3The stock solution was prepared at mol / L and then diluted to 1×10⁻⁶. -5 The test was conducted using a mol / L toluene solution.

[0134] Figure 5 The A1 and A2 prepared in Examples 1 and 2 are in a 1×10⁻⁶ range. -5 The UV-Vis absorption spectrum of toluene in mol / L. Figure 5 It can be seen that the main absorption peaks of A1 and A2 are both located at 453 nm.

[0135] Fluorescence emission spectroscopy was used: an FLS980 fluorescence spectrometer was used to prepare a solution of 1×10⁻⁶ A1 and A2 obtained in the example by dissolving them in dichloromethane. -3 The stock solution, initially at mol / L, was diluted to 1×10⁻⁶ for testing. -5 A solution of mol / L.

[0136] Figure 6 The A1 and A2 prepared in Examples 1 and 2 are in a 1×10⁻⁶ range. -5 Fluorescence emission spectrum of a mol / L toluene solution. From Figure 6 It is known that the main emission peaks of A1 and A2 are located at 469 nm and 466 nm, respectively, both of which emit blue light. Furthermore, the half-width of A1 and A2 is 21 nm, which means that short-wavelength emission is achieved. Therefore, the aryl boron nitrogen-based narrow-band blue light compound system provided in this patent application is diverse and can achieve short-wavelength emission, such as blue light emission.

[0137] In summary, the arylboron-nitrogen-based narrow-band blue light-emitting compound provided in this patent application exhibits short-wavelength blue light emission and can serve as a novel luminescent molecule with high performance, high color purity, and high quantum efficiency. This arylboron-nitrogen-based narrow-band blue light-emitting compound has enormous application potential in the preparation of luminescent materials, luminescent devices, or smart materials, and shows great promise in the fields of full-color displays and solid-state lighting.

[0138] Meanwhile, this patent application enables the controllable preparation of aryl boron nitrogen-based narrow-band blue light compounds; the preparation cost is low, the raw material sources are wide-ranging, and large-scale production can be achieved, thus having broad commercial prospects.

[0139] This patent application is based on arylboron-nitrogen (ANB) molecule systems containing ether bridges, where the ANB serves as the multiple resonance luminescence core. By introducing groups with different electron-donating or electron-withdrawing capabilities to its periphery, organic light-emitting materials with synergistic effects of short-range and long-range charge transfer states are constructed. Because the ANB group possesses high luminescence efficiency and high color purity, it can improve the external quantum efficiency of the device. Connecting electron-donating or electron-withdrawing groups via ether bonds enables the long-range charge transfer state of the molecule and regulates the excited-state properties, effectively promoting the reverse intersystem crossing process, improving the performance of thermally activated delayed fluorescence, and thus reducing the severe roll-off problem in blue light devices. Figure 7 As shown, this overcomes the problems of existing technologies, such as the lack of efficient, high-color-purity, and low-roll-off blue light emitting materials.

[0140] Therefore, the aryl boron nitrogen-based narrow-band blue light compound provided in this patent application can be used as a luminescent material or smart material, and has good application prospects in the fields of full-color display and solid-state lighting.

[0141] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with an embodiment or example is included in at least one embodiment or example of this patent application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0142] Although several embodiments of this patent application have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of this patent application, the scope of which is defined by the claims and their equivalents.

Claims

1. An aryl boron nitrogen-based narrow-band blue light compound, characterized in that, The aryl boron nitrogen-based narrow-band blue light compound contains an ether bridge and can be used in organic small molecule optoelectronic functional materials. It has one of the following molecular structures: 、 。 2. The method for preparing arylborium nitrogen-based narrow-band blue light compounds according to claim 1, characterized in that, Includes the following steps: S1. Preparation of intermediate 1: 2,6-Difluoro-4-bromoiodobenzene, 3,6-di-tert-butylcarbazole and cesium carbonate were added sequentially to a reaction flask. After the nitrogen gas was replaced three times, N,N-dimethylformamide was added, and the reaction was refluxed under nitrogen. After the reaction was completed, the system was allowed to return to room temperature, and then extracted and washed with dichloromethane and saturated brine. After the organic phase was recovered and the solvent was removed, ethanol was added, heated and stirred, and filtered to obtain intermediate 1, the structure of which is shown below. ； S2. Preparation of intermediate 2: Intermediate 1 obtained in step S1 was dissolved in o-xylene, and n-butyllithium was slowly added under stirring. Then, boron tribromide was added under stirring, followed by N,N-diisopropylethylamine, and stirring was continued for 5 hours. After the reaction was completed, water was added to quench the reaction. The product was extracted and washed with dichloromethane and saturated brine, the organic phase was recovered and dried with anhydrous magnesium sulfate, the solvent was removed by vacuum distillation, and the crude product was then purified by column chromatography to obtain intermediate 2, the structure of which is shown below. ； S3. Preparation of intermediate 3: Intermediate 2 obtained in step S2 was dissolved in 1,4-dioxane, and pinacol diboronate, 1,1-bis(diphenylphosphine)ferrocene palladium dichloride, and potassium acetate were added. After reacting for 24 hours with nitrogen purging three times, the mixture was extracted and washed with dichloromethane and saturated brine. The organic phase was recovered and dried over anhydrous magnesium sulfate. The solvent was removed by vacuum distillation, and the crude product was then purified by column chromatography to generate intermediate 3, the structure of which is shown below. ； S4. Preparation of aryl boron nitrogen-based narrow-band blue light compounds: Intermediate 3 obtained from S3 was co-dissolved in an organic solvent with triethylamine, a catalyst, and a donor group compound. After heating and reaction and post-treatment, the aryl boron nitrogen-based narrow-band blue light compound was obtained.

3. The method for preparing the arylborium nitrogen-based narrow-band blue light compound according to claim 2, characterized in that, In step S1, the molar ratio of 2,6-difluoro-4-bromoiodobenzene, 3,6-di-tert-butylcarbazole and cesium carbonate is 1:(2~3):(2~3), the reaction temperature is 110~150℃, and the reaction time is 24~36 h.

4. The method for preparing the aryl boron nitrogen-based narrow-band blue light compound according to claim 2, characterized in that, In step S2, the molar ratio of intermediate 1, n-butyllithium, and boron tribromide is 1:(2~3):(1~2), the reaction temperature is -20~0℃, and the reaction time is 1~2 h.

5. The method for preparing the arylborium nitrogen-based narrow-band blue light compound according to claim 2, characterized in that, In step S3, the molar ratio of intermediate 2 to pinacol diborate, potassium acetate, and 1,1-bis(diphenylphosphine)ferrocene palladium dichloride is 1:2:3:0.05, the reaction temperature is 100~140 ℃, and the reaction time is 12~24 h.

6. The method for preparing the arylborium nitrogen-based narrow-band blue light compound according to claim 2, characterized in that, The molar ratio of intermediate 3 to triethylamine, catalyst and donor group compound in step S4 is 1:(2~8):(0.05~1):(2~2.5).

7. The method for preparing the arylborium nitrogen-based narrow-band blue light compound according to claim 6, characterized in that, In step S4, the catalyst is one of palladium acetate, copper acetate, or 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride.

8. The method for preparing the arylborium nitrogen-based narrow-band blue light compound according to claim 7, characterized in that, The organic solvent used in step S4 is one of toluene, dichloromethane, or 1,4-dioxane. The reaction temperature is 90℃~120℃, and the reaction time is 12~24h.

9. The application of the aryl boron nitrogen-based narrow-band blue light-emitting compound of claim 1 as a luminescent material or smart material.

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