A phosphinoyl-modified anthracene derivative and its preparation method and application

Abstract

This application discloses a phosphino-modified anthracene derivative, its preparation method, and application. In this application, anthracene with high luminescence efficiency is used as a bridge. Triphenylphosphine oxide with a special electron-withdrawing inductive effect is introduced on one side. On the other side, phenanthroimidazole with high luminescence efficiency and bipolar transport properties or tetraphenylsilane with large steric hindrance and high thermal stability are introduced, and modified at different positions to design four phosphino-modified anthracene derivative blue light-emitting materials. These materials all have a distorted molecular conformation, which can increase the distance between the two anthracene planes between molecules and improve the luminescence efficiency. The phosphino-anthracene derivative has significant economic value in the preparation of luminescent materials, light-emitting devices, or smart materials.

Description

Technical Field

[0001] The present application relates to the technical field of organic light-emitting materials, and more specifically, to a phosphino-modified anthracene derivative and a preparation method and application thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs) have enormous potential for application in flat-panel displays, smartphones, and solid-state lighting due to their advantages, including thinness, flexibility, energy efficiency, high color contrast, wide viewing angle, and short response time. Luminescent materials are the core of OLEDs' light emission, directly influencing the efficiency and quality of their light. Therefore, properties such as the luminous efficiency, lifetime, and color of these materials all influence the performance of OLED devices.

[0003] Due to the wide band gap of blue luminescent materials, electron injection is difficult, and device efficiency and lifetime cannot meet practical application requirements. Therefore, the development of efficient and stable blue-emitting materials is urgently needed. Efficient and stable blue-emitting materials generally require high luminous efficiency, high thermal and chemical stability, appropriate energy levels, and carrier balance. Current research on blue-emitting materials has mostly focused on their emission wavelength and luminous efficiency, while often ignoring the materials' carrier injection and transport capabilities.

[0004] Therefore, there is a need for an organic electroluminescent material that has both good carrier transport capability and high luminous efficiency, which is a technical problem that needs to be solved urgently by those skilled in the art.

[0005] Patent application content

[0006] To overcome one of the problems existing in the above-mentioned prior art, the primary purpose of this application is to provide a phosphino-modified anthracene derivative. By using anthracene with high luminescence efficiency as a bridge, introducing triphenylphosphine oxide with a special electron-withdrawing inductive effect on one side, and introducing phenanthroimidazole with high luminescence efficiency and bipolar transport properties or tetraphenylsilane with high steric hindrance and high thermal stability on the other side, four phosphino-modified anthracene derivative blue light-emitting materials are designed. These materials all have a distorted molecular conformation, which can increase the distance between the two anthracene planes between molecules and improve luminescence efficiency.

[0007] Another object of the present application is to provide a preparation method of the above-mentioned phosphine-oxy-modified anthracene derivatives.

[0008] Another object of the present application is to provide the above-mentioned phosphino-modified anthracene derivatives having significant economic value in the preparation of light-emitting materials, light-emitting devices or smart materials.

[0009] The above-mentioned purpose of this application is achieved through the following technical solutions:

[0010] A phosphine-oxy modified anthracene derivative, characterized by having one of the following molecular structures:

[0011]

[0012] The present application also provides a method for preparing the above-mentioned phosphinoyl-modified anthracene derivative, comprising the following steps:

[0013] S1: (4-bromophenyl)diphenylphosphine oxide and 9-anthracene boronic acid are reacted in the presence of a catalyst of tetrakistriphenylphosphine palladium and post-treated to obtain (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide;

[0014] S2: (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide and N-bromosuccinimide are reacted in a chloroform solvent, and the reaction is followed by post-treatment to obtain (4-(10-bromoanthracen-9-yl)phenyl)diphenylphosphine oxide;

[0015] S3: 1-(4-(tert-butyl)phenyl)-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole, 1-(4-(tert-butyl)phenyl)-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole, triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole, The target products p-PIAnPO, m-PIAnPO, p-TPSAnPO and m-TPSAnPO are reacted with (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide prepared in step S2 under the action of tetrakistriphenylphosphine palladium as catalyst, respectively.

[0016] Preferably, in step S1, the molar ratio of (4-bromophenyl)diphenylphosphine oxide, 9-anthraceneboric acid and tetrakistriphenylphosphine palladium is (1.0-1.5):(1.0-2.0):(0.03-0.10), the reaction temperature is 80-100° C., and the reaction time is 12-24 h.

[0017] More preferably, in step S1, the molar ratio of (4-bromophenyl)diphenylphosphine oxide, 9-anthraceneboric acid, and tetrakistriphenylphosphine palladium is 1:1.2:0.05.

[0018] Preferably, the post-treatment in step S1 comprises cooling, extraction, rotary evaporation, and column chromatography. After the reaction is complete, the mixture is poured into water to quench the reaction, and then extracted with dichloromethane; the organic phase is collected and dried over anhydrous Na2SO4; and finally, the mixture is purified by column chromatography using a mixture of ethyl acetate and petroleum ether (1:2, v / v) as the eluent to obtain (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide.

[0019] Preferably, in step S2, the molar ratio of (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide and N-bromosuccinimide is: (1.0-2.0): (1.1-2.5), and the reaction is heated from room temperature to 60-80° C. for 3-6 h.

[0020] More preferably, the molar ratio of (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide to N-bromosuccinimide in step S2 is 1:1.2.

[0021] Preferably, in step S3, (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide, 1-(4-(tert-butyl)phenyl)-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthrene[9,10-d]imidazole or 1-(4-(tert-butyl)phenyl)-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthrene[9,1 The molar ratio of tetrakis(triphenylphosphine)palladium is: (1.0-1.5): (1.2-2.0): (0.03-0.10), the reaction temperature is 80-100°C, and the reaction time is 12-24h.

[0022] More preferably, the (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide, 1-(4-(tert-butyl)phenyl)-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole or 1-(4-(tert-butyl)phenyl)-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole described in step S3 The molar ratio of triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole or triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane or triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and tetrakistriphenylphosphine palladium is: 1:1.2:0.05.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] The phosphino-modified anthracene derivatives in this application use anthracene with high luminescence efficiency as a bridge, introducing triphenylphosphine oxide with a special electron-withdrawing inductive effect on one side, and modifying the other side at different positions by introducing phenanthroimidazole with high luminescence efficiency and bipolar transport properties or tetraphenylsilane with large steric hindrance and high thermal stability. Four phosphino-modified anthracene derivative blue light-emitting materials are designed. These materials all have a distorted molecular conformation, which can increase the distance between the two anthracene planes between molecules and improve the luminescence efficiency. The phosphino-anthracene derivatives have significant economic value in the preparation of luminescent materials, light-emitting devices, or smart materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The compound p-PIAnPO prepared in Example 1 1 HMNR diagram.

[0026] Figure 2 The compound m-PIAnPO prepared in Example 2 1 HMNR diagram.

[0027] Figure 3 The compound p-TPSAnPO prepared in Example 3 1 HMNR diagram.

[0028] Figure 4 The compound m-TPSAnPO prepared in Example 4 1 HMNR diagram.

[0029] Figure 5 This is the mass spectrum of the compound p-PIAnPO prepared in Example 1.

[0030] Figure 6 This is the mass spectrum of the compound m-PIAnPO prepared in Example 2.

[0031] Figure 7 This is the mass spectrum of the compound p-TPSAnPO prepared in Example 3.

[0032] Figure 8 This is the mass spectrum of the compound m-TPSAnPO prepared in Example 4.

[0033] Figure 9 These are the UV-visible absorption spectra and fluorescence emission spectra of the compounds prepared in Examples 1 and 2 in toluene solution.

[0034] Figure 10 These are the UV-visible absorption spectra and fluorescence emission spectra of the compounds prepared in Examples 3 and 4 in toluene solution.

[0035] Figure 11 This is a graph of the absolute fluorescence quantum yield of Example 1 in toluene solution.

[0036] Figure 12 This is a graph of the absolute fluorescence quantum yield of Example 2 in toluene solution.

[0037] Figure 13 This is a graph of the absolute fluorescence quantum yield of Example 3 in toluene solution.

[0038] Figure 14 This is a graph of the absolute fluorescence quantum yield of Example 4 in toluene solution.

[0039] Figure 15 Thermogravimetric analysis and differential scanning calorimetry analysis of the compounds prepared in Examples 1 and 2.

[0040] Figure 16 Thermogravimetric analysis and differential scanning calorimetry of the compounds prepared in Examples 3 and 4

[0041] Figure 17 Electroluminescence spectra of molecules p-PIAnPO and m-PIAnPO in the device.

[0042] Figure 18 This is a graph showing the relationship between the external quantum efficiency and brightness of the molecules p-PIAnPO and m-PIAnPO in the device.

[0043] Figure 19 Electroluminescence spectra of molecules p-TPSAnPO and m-TPSAnPO in the device.

[0044] Figure 20 This is a diagram showing the relationship between the external quantum efficiency and brightness of the molecules p-TPSAnPO and m-TPSAnPO in the device. DETAILED DESCRIPTION

[0045] The embodiments of the present application will be described in detail below with reference to the examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, the conditions are carried out according to conventional conditions or manufacturer recommendations. The reagents or instruments used are not specified by the manufacturer and are conventional products that can be purchased commercially.

[0046] It should be noted that:

[0047] In this application, unless otherwise specified, all the embodiments and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.

[0048] In this application, unless otherwise specified, percentages (%) or parts refer to percentages or parts by weight relative to the composition.

[0049] In this application, unless otherwise specified, the components involved or their preferred components can be combined with each other to form a new technical solution.

[0050] In this application, unless otherwise specified, the numerical range "a-b" is an abbreviation for any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "1-5" indicates that all real numbers between "1-5" are listed herein, and "1-5" is merely an abbreviation for these numerical combinations.

[0051] The "ranges" disclosed in this application are in the form of lower limits and upper limits, which can be one or more lower limits, and one or more upper limits, respectively.

[0052] In this application, unless otherwise stated, each reaction or operation step can be carried out sequentially or in a sequential manner. Preferably, the reaction method herein is carried out sequentially.

[0053] Unless otherwise indicated, the professional and scientific terms used herein are the same as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the described content may also be applied to this application.

[0054] The present application provides a phosphinothracene derivative having one of the following molecular structures:

[0055]

[0056] In this application, anthracene with high luminescence efficiency is used as a bridge, triphenylphosphine oxide with a special electron-withdrawing inductive effect is introduced on one side, and four phosphino-modified anthracene derivative blue light materials are designed by introducing phenanthracene imidazole with high luminescence efficiency and bipolar transmission characteristics or tetraphenylsilane with large steric hindrance and high thermal stability through modification at different positions on the other side. These materials all have a distorted molecular conformation, which can increase the distance between the two anthracene planes between molecules and improve the luminescence efficiency (the fluorescence quantum efficiencies of p-PIAnPO, m-PIAnPO, p-TMSAnPO and m-TMSAnPO were measured to be 78%, 75%, 83% and 91% respectively). The phosphino-anthracene derivative has significant economic value in the preparation of luminescent materials, light-emitting devices or smart materials.

[0057] The present application also includes a method for preparing the phosphinoyl-modified anthracene derivative, comprising the following steps:

[0058] S1. (4-bromophenyl)diphenylphosphine oxide and 9-anthraceneboric acid are reacted with tetrakistriphenylphosphine palladium as a catalyst to obtain (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide (ie, compound 1) by Suzuki reaction;

[0059]

[0060] S2. (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide and N-bromosuccinimide were subjected to an electrophilic substitution reaction in chloroform solvent to obtain (4-(10-bromoanthracen-9-yl)phenyl)diphenylphosphine oxide (i.e., compound 2);

[0061]

[0062] S3. (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide, 1-(4-(tert-butyl)phenyl)-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthrene[9,10-d]imidazole or 1-(4-(tert-butyl)phenyl)-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthrene[9,10-d]imidazole -d]imidazole or triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane or triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane is reacted with tetrakistriphenylphosphine palladium as a catalyst to prepare the target products p-PIAnPO, m-PIAnPO, p-TPSAnPO and m-TPSAnPO through Suzuki reaction.

[0063]

[0064]

[0065] In some preferred embodiments, the molar ratio of (4-bromophenyl)diphenylphosphine oxide, 9-anthraceneboric acid and tetrakistriphenylphosphine palladium in step S1 is (1.0-1.5):(1.0-2.0):(0.03-0.10), the reaction temperature is 80-100° C., and the reaction time is 12-24 h.

[0066] In some more preferred embodiments, the molar ratio of (4-bromophenyl)diphenylphosphine oxide, 9-anthraceneboric acid, and tetrakistriphenylphosphine palladium in step S1 is 1:1.2:0.05.

[0067] In some preferred embodiments, the solvent for the Suzuki reaction in step S1 is anhydrous toluene.

[0068] In some preferred embodiments, the Suzuki reaction in step S1 is catalyzed by an inorganic base; the inorganic base is potassium carbonate or sodium carbonate.

[0069] In some preferred embodiments, the Suzuki reaction in step S1 is carried out under reflux under an inert gas atmosphere. In some preferred embodiments, the inert gas in step S1 is nitrogen, argon, or helium. In some more preferred embodiments, the inert gas in step S1 is nitrogen. In some preferred embodiments, the reaction temperature is 80-100°C and the reaction time is 12-24 hours. In some more preferred embodiments, the reaction temperature is 90°C and the reaction time is 24 hours.

[0070] In some preferred embodiments, the post-treatment described in step S1 is cooling, extraction, rotary evaporation, and column chromatography. After the reaction is completed, the mixture is poured into water to quench the reaction and then extracted with dichloromethane. The organic phase is collected and dried over anhydrous Na2SO4. Finally, it is purified by column chromatography using a mixed system of ethyl acetate and petroleum ether (1:2, v / v) as the eluent to obtain (4-(anthracene-9-yl)phenyl)diphenylphosphine oxide.

[0071] In some preferred embodiments, the preferred step S2 is that the molar ratio of (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide and N-bromosuccinimide in step S2 is: (1.0-2.0): (1.1-2.5), and the reaction is heated from room temperature to 60-80°C, and the reaction time is 3-6h.

[0072] More preferably, the molar ratio of (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide to N-bromosuccinimide in step S2 is 1:1.2.

[0073] In some preferred embodiments, the solvent for the electrophilic substitution reaction in step S2 is anhydrous chloroform.

[0074] In some preferred embodiments, the electrophilic substitution reaction in step S2 is carried out under reflux under an inert gas atmosphere. In some preferred embodiments, the inert gas in step S2 is nitrogen, argon, or helium. In some more preferred embodiments, the inert gas in step S2 is nitrogen. In some preferred embodiments, the reaction temperature is 60-80°C and the reaction time is 3-6 hours. In some more preferred embodiments, the reaction temperature is 70°C and the reaction time is 4 hours.

[0075] In some preferred embodiments, the aftertreatment described in step S2 is cooling, extraction, rotary evaporation, rinse, and oven dry. After the reaction is complete, the mixture is poured into an aqueous solution of saturated sodium thiosulfate to remove residual N-bromosuccinimide, and then extracted with dichloromethane. The organic phase is collected, dried over anhydrous Na2SO4, rinsed with ethanol, and finally dried in a vacuum drying oven to obtain (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide.

[0076] In some preferred embodiments, the (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide, 1-(4-(tert-butyl)phenyl)-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthrene[9,10-d]imidazole or 1-(4-(tert-butyl)phenyl)-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthrene in step S3 is preferably selected from the group consisting of: The molar ratio of [9,10-d]imidazole or triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane or triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and tetrakistriphenylphosphine palladium is: (1.0-1.5):(1.2-2.0):(0.03-0.10), the reaction temperature is 80-100°C, and the reaction time is 12-24h.

[0077] In some preferred embodiments, the (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide, 1-(4-(tert-butyl)phenyl)-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole or 1-(4-(tert-butyl)phenyl)-2-(3-(4,4,5,5-tetramethyl- The molar ratio of triphenyl(1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole or triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane or triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and tetrakistriphenylphosphine palladium is 1:1.2:0.05.

[0078] In some preferred embodiments, the Suzuki reaction conditions and post-treatment in step S3 are the same as those in step S1. Finally, the target products p-PIAnPO, m-PIAnPO, p-TPSAnPO, and m-TPSAnPO are obtained by column chromatography using a mixture of ethyl acetate and petroleum ether (1:2, v / v) as the eluent.

[0079] The present application also provides the use of the above-mentioned phosphino-modified anthracene derivatives in the preparation of blue light-emitting materials, light-emitting devices or smart materials.

[0080] At the same time, the preparation process of the phosphinoyl-modified anthracene derivatives in the present application is simple, convenient, and can be prepared in large quantities, which is conducive to factory-based production and promotion of its application.

[0081] The following is a further description of the preparation method of the phosphino-modified anthracene derivatives in the present application in conjunction with specific embodiments, but the examples do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the examples of the present invention are conventionally purchased raw materials and reagents.

[0082] Example 1 Preparation of phosphinoyl-modified anthracene derivative p-PIAnPO, also known as (4-(10-(4-(1-(4-(tert-butyl)phenyl)-1H-phenanthracene[9,10-d]imidazol-2-yl)phenyl)anthracen-9-yl)phenyl

[0083] S1. Preparation of (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide (i.e., compound 1):

[0084] (4-Bromophenyl)diphenylphosphine oxide (10.0 g, 28.0 mmol), 9-anthraceneboronic acid (7.5 g, 33.6 mmol), K2CO3 (10.2 g, 80 mmol), and tetrakistriphenylphosphine palladium (1.62 mg, 1.4 mmol) were placed in a 500 ml two-necked flask. Then, 40 ml of distilled water, 100 ml of toluene, and 40 ml of ethanol were added. The two-necked flask was evacuated using a vacuum pump and replaced with nitrogen three times. The mixture was reacted at 90°C for 24 h. After the reaction was complete, the mixture was poured into water to quench the reaction, and then extracted with dichloromethane. The organic phase was collected and dried over anhydrous Na2SO4. Finally, it was purified by column chromatography using a mixture of ethyl acetate and petroleum ether (1:2, v / v) as the eluent to obtain a yellow solid (9.80 g, yield: 77%).

[0085] The reaction equation is as follows:

[0086]

[0087] S2. Preparation of (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide (i.e., compound 2):

[0088] Compound 1 (9.8 g, 21.6 mmol), N-bromosuccinimide (4.6 g, 26 mmol) and 100 ml of chloroform were placed in a 250 ml two-necked flask. The two-necked flask was evacuated with a vacuum pump and replaced with nitrogen three times, and the mixture was reacted at 70° C. for 4 h. The post-treatment described in step S2 was cooling, extraction, rotary evaporation, rinsing, and drying. After the reaction was completed, the mixture was poured into a saturated aqueous solution of sodium thiosulfate to remove residual N-bromosuccinimide, and then extracted with dichloromethane. The organic phase was collected, dried over anhydrous Na2SO4, rinsed with ethanol, and finally dried in a vacuum drying oven to obtain a yellow solid (9.53 g, yield: 83%).

[0089] The reaction equation is as follows:

[0090]

[0091] S3. Preparation of (4-(10-(4-(1-(4-(tert-butyl)phenyl)-1H-phenanthren[9,10-d]imidazol-2-yl)phenyl)anthracen-9-yl)phenyl (i.e., target product p-PIAnPO)

[0092] Compound 2 (2.1 g, 4 mmol), 1-(4-(tert-butyl)phenyl)-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole (2.65 g, 4.8 mmol), K2CO3 (2.56 g, 20 mmol), and tetrakistriphenylphosphine palladium (0.23 g, 0.2 mmol) were placed in a 100 ml two-necked flask. Then, 10 ml of distilled water, 30 ml of toluene, and 10 ml of ethanol were added. The two-necked flask was evacuated with a vacuum pump and replaced with nitrogen three times, and the mixture was reacted at 90°C for 24 h. After the reaction was completed, the mixture was poured into water to quench the reaction, and then extracted with dichloromethane. The organic phase was collected and dried over anhydrous Na2SO4. Finally, the product was purified by column chromatography using a mixture of ethyl acetate and petroleum ether (1:2, v / v) as the eluent to obtain a yellow solid (2.3 g, yield: 66%).

[0093] The reaction equation is as follows:

[0094]

[0095] The NMR spectrum of compound p-PIAnPO is as follows Figure 1 As shown. Figure 1 It can be seen that its characteristic wave number (ppm) is 1H NMR (400 MHz, CDCl3) δ 8.97 (s, 1H), 8.81 (d, J = 8.4 Hz, 1H), 8.75 (d, J = 8.4 Hz, 1H), 7.94-7.75 (m, 9H), 7.73-7.51 (m, 18H), 7.44-7.28 (m, 8H), 1.45 (s, 9H). The peaks corresponded one-to-one with the hydrogen atoms on the phenanthroimidazole, triphenylphosphine oxide, and anthracene ring, and the number of peaks was reasonable, indicating that the compound p-PIAnPO has a simple structure and high purity.

[0096] Example 2 Preparation of phosphinoyl modified anthracene derivative m-PIAnPO, also known as (4-(10-(3-(1-(4-(tert-butyl)phenyl)-1H-phenanthracene[9,10-d]imidazol-2-yl)phenyl)anthracene-9-yl)phenyl

[0097] Compound 2 prepared in step S2 of Example 1 can also be used to prepare m-PIAnPO.

[0098] S3. Preparation of (4-(10-(3-(1-(4-(tert-butyl)phenyl)-1H-phenanthren[9,10-d]imidazol-2-yl)phenyl)anthracen-9-yl)phenyl (i.e., target product m-PIAnPO)

[0099] Compound 2 (2.1 g, 4 mmol), 1-(4-(tert-butyl)phenyl)-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole (2.65 g, 4.8 mmol), K2CO3 (2.56 g, 20 mmol), and tetrakistriphenylphosphine palladium (0.23 g, 0.2 mmol) were placed in a 100 ml two-necked flask. Then, 10 ml of distilled water, 30 ml of toluene, and 10 ml of ethanol were added. The two-necked flask was evacuated with a vacuum pump and replaced with nitrogen three times, and the mixture was reacted at 90°C for 24 h. After the reaction was completed, the mixture was poured into water to quench the reaction, and then extracted with dichloromethane. The organic phase was collected and dried over anhydrous Na2SO4. Finally, the product was purified by column chromatography using a mixture of ethyl acetate and petroleum ether (1:2, v / v) as the eluent to obtain a yellow solid (2.1 g, yield: 60%).

[0100] The reaction equation is as follows:

[0101]

[0102] The NMR spectrum of compound m-PIAnPO is as follows Figure 2 As shown. Figure 2 It can be seen that its characteristic wave number (ppm) is 1H NMR (400 MHz, CDCl3) δ 8.92 (s, 1H), 8.76 (d, J = 8.4 Hz, 1H), 8.71 (d, J = 8.3 Hz, 1H), 8.15 (d, J = 7.6 Hz, 1H), 7.95-7.82 (m, 6H), 7.78-7.72 (m, 1H), 7.69-7.47 (m, 15H), 7.40 (s, 5H), 7.37-7.28 (m, 5H), 7.25-7.18 (m, 2H), 1.09 (s, 9H). The peaks corresponded one-to-one with the hydrogen atoms on the phenanthroimidazole, triphenylphosphine oxide, and anthracene ring, and the number of peaks was reasonable. This indicates that the compound m-PIAnPO has a simple structure and high purity.

[0103] Example 3 Preparation of a Phosphinyloxy-Modified Anthracene Derivative p-TPSAnPO, Also Known as Diphenyl(4-(10-(4-(Triphenylsilyl)phenyl)anthracen-9-yl)phenyl)phosphine Oxide

[0104] Compound 2 prepared in step S2 of Example 1 can also be used to prepare p-TPSAnPO.

[0105] S3. Preparation of (4-(10-(4-(triphenylsilyl)phenyl)anthracene-9-yl)phenyl)phosphine oxide (i.e., target product p-TPSAnPO)

[0106] Compound 2 (2.1 g, 4 mmol), triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (2.22 g, 4.8 mmol), K2CO3 (2.56 g, 20 mmol), and tetrakistriphenylphosphine palladium (0.23 g, 0.2 mmol) were placed in a 100 ml two-necked flask. Then, 10 ml of distilled water, 30 ml of toluene, and 10 ml of ethanol were added. The two-necked flask was evacuated using a vacuum pump and replaced with nitrogen three times. The mixture was reacted at 90°C for 24 h. After the reaction was completed, the mixture was poured into water to quench the reaction, and then extracted with dichloromethane. The organic phase was collected and dried over anhydrous Na2SO4. Finally, it was purified by column chromatography using a mixture of ethyl acetate and petroleum ether (1:2, v / v) as the eluent to obtain a yellow solid (2.1 g, yield: 68%).

[0107] The reaction equation is as follows:

[0108]

[0109] The NMR spectrum of compound p-TPSAnPO is as follows Figure 3 As shown. Figure 3 It can be seen that its characteristic wave number (ppm) is 1H NMR (400 MHz, CDCl3) δ 7.94-7.80 (m, 8H), 7.77-7.69 (m, 8H), 7.66-7.54 (m, 10H), 7.47 (qdd, J = 8.5, 4.5, 2.0 Hz, 11H), 7.40-7.34 (m, 4H). The peaks corresponded one-to-one with the hydrogen atoms on tetraphenylsilane, triphenylphosphine oxide, and the anthracene ring, and the number of peaks was reasonable, indicating that the p-TPSAnPO compound had a simple structure and high purity.

[0110] Example 4 Preparation of a Phosphinyloxy-Modified Anthracene Derivative m-TPSAnPO, Also Known as Diphenyl (4-(10-(3-(Triphenylsilyl)phenyl)anthracen-9-yl)phenyl)phosphine Oxide

[0111] Compound 2 prepared in step S2 of Example 1 can also be used to prepare m-TPSAnPO.

[0112] S3. Preparation of (4-(10-(3-(triphenylsilyl)phenyl)anthracene-9-yl)phenyl)phosphine oxide (i.e., target product m-TPSAnPO)

[0113] Compound 2 (2.1 g, 4 mmol), triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (2.22 g, 4.8 mmol), K2CO3 (2.56 g, 20 mmol), and tetrakistriphenylphosphine palladium (0.23 g, 0.2 mmol) were placed in a 100 ml two-necked flask. Then, 10 ml of distilled water, 30 ml of toluene, and 10 ml of ethanol were added. The two-necked flask was evacuated using a vacuum pump and replaced with nitrogen three times. The mixture was reacted at 90°C for 24 h. After the reaction was completed, the mixture was poured into water to quench the reaction, and then extracted with dichloromethane. The organic phase was collected and dried over anhydrous Na2SO4. Finally, it was purified by column chromatography using a mixture of ethyl acetate and petroleum ether (1:2, v / v) as the eluent to obtain a yellow solid (2.1 g, yield: 65%).

[0114] The reaction equation is as follows:

[0115]

[0116] The NMR spectrum of compound m-TPSAnPO is as follows Figure 4 As shown. Figure 4 It can be seen that its characteristic wave number (ppm) is 1H NMR (400 MHz, Chloroform-d) δ 7.95-7.80 (m, 6H), 7.80-7.70 (m, 4H), 7.68-7.51 (m, 18H), 7.45-7.31 (m, 13H). The peaks corresponded to tetraphenylsilane, triphenylphosphine oxide, and hydrogen atoms on the anthracene ring, with reasonable quantities. This indicates that the m-TPSAnPO compound has a simple structure and high purity.

[0117] Figures 1 to 4 The H NMR spectra of compounds p-PIAnPO, m-PIAnPO, p-TPSAnPO and m-TPSAnPO were measured using a Bruker 400 MHz superconducting NMR spectrometer, and the solvent was deuterated chloroform. Figures 5 to 8 High-resolution mass spectra of the molecules p-PIAnPO, m-PIAnPO, p-TPSAnPO, and m-TPSAnPO were measured using a Thermo Fisher ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometer* / TSQ Endura.

[0118] Figure 5 This is the HRMS diagram (i.e., mass spectrum) of the phosphine oxide modified anthracene derivative molecule p-PIAnPO prepared in Example 1. After calculation, the theoretical value of the phosphine oxide modified anthracene derivative molecule p-PIAnPO is C 63 H 48 N2OP[(M+H) + The actual m / z value determined by mass spectrometry is 879.3494, which is consistent with the relative molecular mass of the synthesized anthracene-phosphine-oxygen-modified anthracene derivative molecule p-PIAnPO.

[0119] Figure 6 This is the HRMS diagram (i.e., mass spectrum) of the phosphine oxide modified anthracene derivative molecule m-PIAnPO prepared in Example 2. After calculation, the theoretical value of the phosphine oxide modified anthracene derivative molecule m-PIAnPO is C 63 H 48 N2OP[(M+H) + The actual m / z value determined by mass spectrometry is 879.3492, which is consistent with the relative molecular mass of the synthesized anthracene-phosphine-oxygen-modified anthracene derivative molecule m-PIAnPO.

[0120] Figure 7 This is the HRMS diagram (i.e., mass spectrum) of the phosphine oxide modified anthracene derivative molecule p-TPSAnPO prepared in Example 3. After calculation, the theoretical value of the phosphine oxide modified anthracene derivative molecule p-TPSAnPO is C 56 H 42 OPSi[(M+H) +]:789.2664, and the actual m / z value tested by mass spectrometry was: 789.2736, which is consistent with the relative molecular mass of the synthesized anthracene-phosphine-oxygen-modified anthracene derivative molecule p-TPSAnPO.

[0121] Figure 8 This is the HRMS diagram (i.e., mass spectrum) of the phosphine oxide modified anthracene derivative molecule m-TPSAnPO prepared in Example 4. After calculation, the theoretical value of the phosphine oxide modified anthracene derivative molecule m-TPSAnPO is C 56 H 42 OPSi[(M+H) + ]:789.2664, and the actual m / z value tested by mass spectrometry was: 789.2728, which is consistent with the relative molecular mass of the synthesized anthracene-phosphine-oxygen-modified anthracene derivative molecule m-TPSAnPO.

[0122] Characterization and performance testing

[0123] The compounds p-PIAnPO, m-PIAnPO, p-TPSAnPO and m-TPSAnPO prepared in Examples 1 to 4 were used as test objects to test their photophysical properties. The test results are as follows: Figures 9 to 20 shown.

[0124] Figure 9 Normalized UV-visible absorption and fluorescence emission spectra of p-PIAnPO and m-PIAnPO in toluene solution, measured using a Shimadzu UV-2700 UV-visible spectrophotometer and an Edinburgh FLS 980 transient and steady-state fluorescence spectrometer. p-PIAnPO and m-PIAnPO exhibit deep blue emission in toluene, with peaks at 440 nm and 434 nm, respectively. Figure 11 , 12 are diagrams of the absolute fluorescence quantum yields of the molecules p-PIAnPO and m-PIAnPO in toluene solution measured by Edinburgh FLS 980 transient steady-state fluorescence phosphorescence spectrometer. It can be concluded from the above schematic diagram that the absolute fluorescence quantum yields of the molecules p-PIAnPO and m-PIAnPO in toluene solution are 78% and 75%, respectively.

[0125] Figure 10 Normalized UV-visible absorption and fluorescence emission spectra of p-TPSAnPO and m-TPSAnPO in toluene solution, measured using a Shimadzu UV-2700 UV-visible spectrophotometer and an Edinburgh FLS 980 transient and steady-state fluorescence spectrometer. p-TPSAnPO and m-TPSAnPO exhibit a deep blue emission with a fine structure in toluene solution, with peaks at 426 nm and 435 nm, and 424 nm and 434 nm, respectively. Figure 13, 14 are diagrams of the absolute fluorescence quantum yields of the molecules p-TPSAnPO and m-TPSAnPO in toluene solution measured by Edinburgh FLS 980 transient steady-state fluorescence phosphorescence spectrometer. It can be concluded from the above schematic diagram that the absolute fluorescence quantum yields of the molecules p-TPSAnPO and m-TPSAnPO in toluene solution are 83% and 91%, respectively.

[0126] Figure 15 The left figure shows the relationship between the sample mass and temperature of the molecules p-PIAnPO and m-PIAnPO in a nitrogen atmosphere, measured by a Perkin Elmer thermogravimetric analyzer in the United States. The right figure shows the relationship between the heat flow and temperature of the molecules p-PIAnPO and m-PIAnPO in a nitrogen atmosphere, measured by a Perkin Elmer differential scanning calorimeter in the United States. The decomposition temperature (T d , corresponding to 5% mass loss) were as high as 506℃ and 501℃, respectively, and the glass transition temperature (T g ) are 189°C and 182°C, respectively. This means that the two compounds have excellent thermal stability in high temperature environments, indicating that the two compounds can be used to prepare devices by vacuum deposition.

[0127] Figure 16 The left figure shows the relationship between the sample mass and temperature of the molecules p-TPSAnPO and m-TPSAnPO in a nitrogen atmosphere, as measured by a Perkin Elmer thermogravimetric analyzer. The right figure shows the relationship between the heat flow and temperature of the molecules p-TPSAnPO and m-TPSAnPO in a nitrogen atmosphere, as measured by a Perkin Elmer differential scanning calorimeter. The decomposition temperature (T d , corresponding to 5% mass loss) were as high as 482℃ and 465℃, respectively, and the glass transition temperature (T g ) are 153°C and 133°C, respectively. The excellent thermal stability indicates that these two compounds can be used to prepare devices via vacuum deposition.

[0128] Non-doped devices were prepared using compounds p-PIAnPO and m-PIAnPO as light-emitting layers. The structures were ITO / HATCN (10nm) / TAPC (40nm) / mCP (10nm) / p-PIAnPO or m-PIAnPO (20nm) / TPBi (40nm) / LiF (1nm) / Al (150nm), where HATCN and LiF were hole and electron injection layers, respectively; TAPC and TPBi were hole and electron transport layers, respectively; mCP was used as an electron blocking layer, and ITO and Al were used as anode and cathode, respectively. The electroluminescent properties were tested, and the test results are shown in Figure 2. Figures 17 and 18 shown.

[0129] Figure 17 The electroluminescence spectra of the p-PIAnPO and m-PIAnPO molecules in the device are shown in Figure 2. The emission wavelengths of the p-PIAnPO and m-PIAnPO molecules are 448 nm and 466 nm, respectively, indicating deep blue and pure blue emission.

[0130] Figure 18 The figure shows the relationship between the external quantum efficiency and brightness of the molecules p-PIAnPO and m-PIAnPO in the device. The maximum external quantum efficiency of p-PIAnPO and m-PIAnPO molecules are 4.2% and 6.0%, respectively. The OLED device based on p-PIAnPO shows only 1.7% efficiency roll-off at 1000 nits brightness, even at 10000 cd m -2 At a brightness of 100 nm, its EQE can still be maintained at 5.3%, with an efficiency roll-off of only 12%. Such a high maximum external quantum efficiency and slight efficiency roll-off are attributed to its high luminous efficiency and excellent transmission characteristics.

[0131] A doped device was prepared with compounds p-TPSAnPO and m-TPSAnPO as the light-emitting layer and CBP as the main material. Its structure is ITO / HATCN (6nm) / TAPC (25nm) / TCTA (15nm) / CBP: (15wt%) emitters (20nm) / TmPyPB (40nm) / LiF (1nm) / Al (150nm). Among them, HATCN and LiF are hole and electron injection layers, respectively; TAPC and TmPyPB are hole and electron transport layers, respectively; TCTA is an electron blocking layer, and ITO and Al are used as anode and cathode, respectively. Its electroluminescent properties were tested, and the test results are as follows: Figures 19 to 20 shown

[0132] Figure 19 The electroluminescence spectra of the p-TPSAnPO and m-TPSAnPO molecules in the device are shown. Both p-TPSAnPO and m-TPSAnPO molecules emit at 448 nm, exhibiting deep blue light, meeting the deep blue material standards specified in BT.2020 (0.131, 0.046).

[0133] Figure 20 The relationship between the external quantum efficiency (EQE) and brightness of the p-TPSAnPO and m-TPSAnPO molecules in the device is shown in Figure 2. The maximum EQEs of the p-TPSAnPO and m-TPSAnPO molecules are 10.0% and 10.8%, respectively. These high EQEs indicate that the fluorescence quantum efficiencies of the two molecules in their solid-state thin film aggregates are very high.

[0134] This application discloses a phosphino-modified anthracene derivative, its preparation method, and application. This application uses anthracene with high luminescence efficiency as a bridge, introduces triphenylphosphine oxide with a special electron-withdrawing inductive effect, and designs four phosphino-modified anthracene derivative blue light-emitting materials by introducing phenanthroimidazole with high luminescence efficiency and bipolar transport properties or tetraphenylsilane with large steric hindrance and high thermal stability through modification at different positions. These materials all have a distorted molecular conformation, which can increase the distance between the two anthracene planes between molecules and improve luminescence efficiency. The phosphino-anthracene derivative has significant economic value in the preparation of luminescent materials, light-emitting devices, or smart materials.

[0135] In summary, the anthracene-based deep blue light-emitting material provided in the present application has significant economic value in the application of preparing luminescent materials, light-emitting devices or smart materials.

[0136] At the same time, the present application realizes a simple and convenient preparation process of an anthracene-based deep blue light material compound, which can be prepared in batches on a large scale, is conducive to factory-based production and preparation, and is conducive to the promotion of its application.

[0137] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that a specific feature, structure, material, or characteristic described in conjunction with an embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations 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 any one or more embodiments or examples.

[0138] Although several embodiments of the present application have been shown and described, those skilled in the art will appreciate that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and purpose of the present application, and that the scope of the present application is defined by the claims and their equivalents.

Claims

1. A phosphino-modified anthracene derivative, characterized in that: Has one of the following molecular structures: 、 。 2. The method for preparing the phosphinoyl-modified anthracene derivative according to claim 1, characterized in that: The following steps are involved: S1, reacting (4-bromophenyl)diphenylphosphine oxide and 9-anthracene boronic acid in the presence of a catalyst of tetrakistriphenylphosphine palladium and post-treating to obtain (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide; S2, reacting (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide and N-bromosuccinimide in a chloroform solvent, and post-treating to obtain (4-(10-bromoanthracen-9-yl)phenyl)diphenylphosphine oxide; S3, respectively reacting triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane or triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane with (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide obtained in step S2 under the action of tetrakistriphenylphosphine palladium catalyst to obtain target products p-TPSAnPO and m-TPSAnPO.

3. The method for preparing the phosphinoyl-modified anthracene derivative according to claim 2, characterized in that: In step S1, the molar ratio of (4-bromophenyl)diphenylphosphine oxide, 9-anthraceneboric acid, and tetrakistriphenylphosphine palladium is (1.0-1.5): (1.0-2.0): (0.03-0.10), the reaction temperature is 80-100° C., and the reaction time is 12-24 h.

4. The method for preparing a phosphinoyl-modified anthracene derivative according to claim 3, wherein: In step S1, the molar ratio of (4-bromophenyl)diphenylphosphine oxide, 9-anthraceneboric acid and tetrakistriphenylphosphine palladium is 1:1.2:0.

05.

5. The method for preparing the phosphinoyl-modified anthracene derivative according to claim 3, characterized in that: The post-treatment in step S1 is cooling, extraction, rotary evaporation, and column chromatography: after the reaction is completed, the mixture is poured into water to quench the reaction, and then extracted with dichloromethane; the organic phase is collected and dried over anhydrous Na2SO4; and finally, it is purified by column chromatography with an eluent of a mixed system of ethyl acetate and petroleum ether to obtain (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide.

6. The method for preparing the phosphinoyl-modified anthracene derivative according to claim 2, characterized in that: The molar ratio of (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide to N-bromosuccinimide in step S2 is (1.0-2.0): (1.1-2.5), and the reaction is heated from room temperature to 60-80°C for 3-6 hours.

7. The method for preparing a phosphinoyl-modified anthracene derivative according to claim 6, characterized in that: In step S2, the molar ratio of (4-(anthracen-9-yl)phenyl)diphenylphosphine oxide and N-bromosuccinimide in step S2 is 1:1.

2.

8. The method for preparing the phosphinoyl-modified anthracene derivative according to claim 2, characterized in that: In step S3, the molar ratio of (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide, triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane or triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and tetrakistriphenylphosphine palladium is: (1.0-1.5): (1.2-2.0): (0.03-0.10), the reaction temperature is 80-100 °C, and the reaction time is 12-24 h.

9. The method for preparing a phosphinoyl-modified anthracene derivative according to claim 8, characterized in that: The molar ratio of (4-(10-bromoanthracene-9-yl)phenyl)diphenylphosphine oxide, triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane or triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and tetrakistriphenylphosphine palladium in step S3 is 1:1.2:0.

05.

10. Use of the phosphinoyl-modified anthracene derivative according to claim 1 in the preparation of blue light-emitting materials, light-emitting devices or smart materials.

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