A phenyl(triphenylene-2-yl)methanone derivative having room temperature phosphorescence, and a preparation method and application thereof

Abstract

This invention belongs to the technical field of pure organic small molecule room-temperature phosphorescent materials, specifically relating to a phenyl(triphenyl-2-yl) methyl ketone derivative exhibiting room-temperature phosphorescence, its preparation method, and its applications. To develop a pure organic RTP material with strong intermolecular interactions and the ability to block oxygen and water quenching, this invention designs and synthesizes a series of phenyl(triphenyl-2-yl) methyl ketone derivatives with strong intermolecular interactions. Even when crystallization is disrupted, these derivatives can maintain strong intermolecular interactions to stabilize the TT. n It also blocks the quenching of oxygen and water to a certain extent, so that it can easily emit room temperature phosphorescence regardless of whether it is in the crystalline, amorphous, nanoparticle or polymer state, which is more conducive to its production and application.

Description

Technical Field

[0001] This invention belongs to the field of pure organic small molecule room temperature phosphorescent materials technology, specifically relating to a phenyl (triphenyl-2-yl) methyl ketone derivative with room temperature phosphorescence, its preparation method and application. Background Technology

[0002] Even in the dark, "luminous pearls" emit a dazzling light, revered as rare treasures by ancient emperors, and shrouded in mystery by numerous folk tales. Essentially, "luminous pearls" are long-afterglow materials, substances that continue to glow even after the excitation source such as sunlight, ultraviolet light, or X-rays is removed. Room-temperature phosphorescent (RTP) materials are the most common, and they hold immense potential for applications in lighting, displays, sensing, anti-counterfeiting, information storage, and biology. Compared to inorganic or metallic long-afterglow materials, purely organic materials offer numerous advantages, including lower cost, lower toxicity, and better biocompatibility.

[0003] To improve the performance of purely organic RTP materials, current approaches mainly focus on two aspects: promoting the transformation from the first excited singlet state (S1) to the triplet state (T). n Intersystem crossing (ISC) of n≥1 and suppression of nonradiative transitions and quenching processes of triplet excitons are crucial. Specific measures include introducing carbonyl groups with abundant lone pair electrons and groups containing other heteroatoms (O, N, S, P), as well as heavy atom effects, crystallization, matrix rigidification, deuteration, polymerization, and crosslinking. Among these, crystallization is the simplest and most commonly used strategy for isolating oxygen quenching and promoting small molecule rigidification. However, its drawback is that when the crystallization of crystalline RTP materials is destroyed, its intermolecular interactions and ability to block oxygen and water are greatly weakened. Simultaneously, RTP emission weakens or even disappears completely, which is detrimental to its production and application. Therefore, developing a pure organic RTP material with strong intermolecular interactions and the ability to block oxygen and water quenching has significant application potential. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, the present invention provides a phenyl (triphenyl-2-yl) methyl ketone derivative, which utilizes the strong intermolecular interaction between triphenylene and the carbonyl nucleus to resist the increase in the nonradiative transition rate of triplet excitons and the decrease in oxygen barrier ability caused by crystallization. Thus, the derivative can easily emit room temperature phosphorescence regardless of whether it is crystalline, amorphous, nanoparticle or polymer-doped film.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] The first aspect of this invention provides a phenyl(triphenyl-2-yl) methyl ketone derivative exhibiting room-temperature phosphorescence, the structural formula of which is shown below:

[0007] ;

[0008] Among them, R1, R2, R3, R4, and R5 are independently selected from -H, -F, -Cl, -Br, -I, -Me, -OMe, -OEt, -CF3, -CN, -OH, -Ph, -NH2, -COOH, -COOCH3, -CHO, -COONa, and -B(OH)2. , , , , , , , , , , , , , , , .

[0009] Preferably, the phenyl(triphenyl-2-yl)methyl ketone derivative is selected from at least one of the following structural formulas:

[0010] .

[0011] The second aspect of the present invention provides a method for preparing the phenyl(triphenyl-2-yl) methyl ketone derivative with room temperature phosphorescence as described in the first aspect, specifically as follows: according to the following reaction formula, triphenylene, benzoyl chloride derivative and anhydrous ferric chloride are dissolved in an organic solvent, heated and stirred, and then dilute hydrochloric acid is added and stirred until no bubbles are generated. Then, the mixture is extracted with dilute hydrochloric acid and water in sequence, and after drying and concentration, it is purified by silica gel column chromatography to obtain the target product.

[0012] ;

[0013] The values ​​of R1, R2, R3, R4, and R5 are the same as above.

[0014] This invention designs and synthesizes a series of phenyl(triphenyl-2-yl) methyl ketone derivatives (TpPX) with strong intermolecular interactions. Since triphenylene has a near-planar rigid structure, its excited-state excitons are pure ( The configuration, the introduction of the carbonyl group, mixes ( This allows n and π groups with different excited-state configurations to achieve intermolecular electronic coupling, enabling them to leverage their respective advantages. This results in efficient intersystem crossing and a low radiative transition rate, thus emitting highly efficient RTPs. Furthermore, abundant intermolecular interactions stabilize T... n It also blocks the quenching of oxygen and water to a certain extent, thus allowing it to easily emit room-temperature phosphorescence regardless of whether it is in a crystalline, amorphous, nanoparticle, or polymer state.

[0015] Preferably, the molar ratio of triphenylene, benzoyl chloride derivative and anhydrous ferric chloride is 1:5-7:13-15.

[0016] Preferably, the heating and stirring reaction is carried out at a temperature of 55-70 °C for 12-36 h.

[0017] Preferably, the sample is extracted with dilute hydrochloric acid and water 3-5 times in sequence.

[0018] Preferably, during silica gel column chromatography purification, dichloromethane / n-hexane = 1:3 is used as the eluent.

[0019] Preferably, the applications include lighting displays, sensing, stimulus response, anti-counterfeiting, information encryption and storage, and bio-afterglow imaging.

[0020] Preferably, the organic solvent is selected from dichloromethane, but is not limited to dichloromethane.

[0021] Compared with the prior art, the beneficial effects of the present invention are:

[0022] Currently, the simplest and most common strategy to improve the performance of pure organic small molecule RTP materials is to utilize crystallization to isolate oxygen quenching and promote the rigidification of small molecules. However, a drawback is that when the crystallization of crystalline RTP materials is destroyed, their intermolecular interactions and oxygen-blocking ability are greatly weakened. Simultaneously, RTP emission weakens or even disappears completely, which is detrimental to their production and application. Therefore, this invention designs and synthesizes a series of phenyl(triphenyl-2-yl) methyl ketone derivatives (TpPX) with strong intermolecular interactions. Even when the crystallization is destroyed, these derivatives can still maintain strong intermolecular interactions to stabilize TpP. n It also blocks the quenching of oxygen and water to a certain extent, so that it can easily emit room temperature phosphorescence regardless of whether it is in the crystalline, amorphous, nanoparticle or polymer state, which is more conducive to its production and application. Attached Figure Description

[0023] Figure 1 The luminescence phenomena exhibited by the TpPX compound under 365 nm excitation and at different times after the light source was removed;

[0024] Figure 2Afterglow patterns of TpPBr compound crystals, amorphous powders, and nanoparticles were measured at room temperature with excitation light at 405 nm.

[0025] Figure 3 The afterglow pattern of a 1wt.% TpPBr@PMMA polymer-doped film was measured at room temperature with an excitation wavelength of 365 nm. Detailed Implementation

[0026] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0027] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0028] Example 1: A method for preparing a phenyl (tripylen-2-yl) methyl ketone derivative (TpPX)

[0029] Based on the following reaction formula, the preparation method of TpPX is as follows:

[0030] Triphenylene (1.00 g, 4.38 mmol), benzoyl chloride derivative (5.26 mmol), and anhydrous ferric chloride (2.13 g, 13.14 mmol) were dissolved in 40 mL of dichloromethane and stirred at 60 °C for 24 h. After the reaction was complete, the mixture was allowed to cool naturally to room temperature. Then, dilute hydrochloric acid (5%) was slowly added and stirred thoroughly until no bubbles were generated. The mixture was then extracted three times with dilute hydrochloric acid (5%) and deionized water, respectively. The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation under reduced pressure. The crude product was purified by silica gel column chromatography using dichloromethane / n-hexane (1:3) as the eluent to obtain a white product (yield 80-90%). The products included TpPF, TpPBr, TpPI, and TpPMe, with yields of 84.5%, 86.1%, 81.0%, and 88.7%, respectively.

[0031] .

[0032] The structural formulas of TpPF, TpPBr, TpPI, and TpPMe are shown below:

[0033] .

[0034] The 1H and 1C NMR spectra of TpPF, TpPBr, TpPI, and TpPMe are as follows:

[0035] TpPF:

[0036] 1 H NMR (400 MHz, Dichloromethane-d2) δ ppm: 9.12 (d, J = 1.7 Hz, 1H),8.82 (d, J = 8.5 Hz, 1H), 8.80 – 8.71 (m, 3H), 8.71 – 8.65 (m, 1H), 8.09 (dd,J = 8.5, 1.7 Hz, 1H), 8.06 – 7.96 (m, 2H), 7.84 – 7.68 (m, 4H), 7.35 – 7.23(m, 2H); 13 C NMR (151 MHz, Chloroform-d) δ ppm: 195.15, 166.33, 164.64,135.65, 134.12, 134.10, 132.96, 132.81, 132.75, 130.73, 130.05, 129.47,129.42, 128.95, 128.43, 127.90, 127.85, 127.63, 125.84, 124.01, 123.50,123.45, 123.43, 115.70, 115.56; HMRS (TOF MS ES+): calcd for C 25 H 16 FO,351.1180, found 351.1180。

[0037] TpPBr:

[0038] 1 H NMR (400 MHz, Chloroform-d) δ ppm: 9.09 (d, J = 1.8 Hz, 1H), 8.76(d, J = 8.6 Hz, 1H), 8.73 - 8.65 (m, 3H), 8.65 - 8.59 (m, 1H), 8.05 (dd, J =8.6, 1.8 Hz, 1H), 7.85 - 7.78 (m, 2H), 7.78 - 7.66 (m, 6H); 13C NMR (151 MHz,Chloroform-d) δ ppm: 193.53, 136.74, 134.98, 133.28, 131.93, 131.84, 130.92,130.19, 129.64, 129.53, 129.07, 128.65, 128.10, 128.00, 127.82, 127.78,127.73, 126.12, 124.20, 123.74, 123.66, 123.62, 123.59; HMRS (TOF MS ES+):calcd for C 25 H 16 BrO, 411.0379, found 411.0381。

[0039] TpPI:

[0040] 1 H NMR (400 MHz, Chloroform-d) δ ppm: 9.09 (d, J = 1.8 Hz, 1H), 8.76(d, J = 8.6 Hz, 1H), 8.73 - 8.66 (m, 3H), 8.65 - 8.59 (m, 1H), 8.05 (dd, J =8.5, 1.7 Hz, 1H), 7.96 - 7.90 (m, 2H), 7.80 - 7.68 (m, 3H), 7.66 (d, J = 1.9Hz, 2H); 13 C NMR (151 MHz, Chloroform-d) δ ppm: 196.66, 137.88, 135.77,132.93, 132.55, 130.73, 130.21, 130.03, 129.51, 129.44, 129.02, 128.46,128.39, 128.08, 127.85, 127.61, 127.55, 126.05, 124.04, 123.53, 123.50,123.44, 123.41; HMRS (TOF MS ES+): calcd for C 25 H 16 IO, 459.0240, found459.0242。

[0041] TpPMe:

[0042] 1H NMR (400 MHz, Chloroform-d) δ ppm: 9.10 (d, J = 1.7 Hz, 1H), 8.73 (d, J = 8.5 Hz, 1H), 8.71 - 8.65 (m, 3H), 8.65 - 8.60 (m, 1H), 8.07 (dd, J =8.5, 1.7 Hz, 1H), 7.85 (d, J = 8.2 Hz, 2H), 7.76 - 7.63 (m, 4H), 7.35 (d, J =7.8 Hz, 2H), 2.50 (s, 3H); 13 C NMR (151 MHz, Chloroform-d) δ ppm: 196.02,143.51, 136.28, 135.30, 132.88, 130.81, 130.58, 130.16, 129.69, 129.52,129.29, 129.21, 128.44, 128.16, 127.92, 127.71, 127.65, 126.02, 124.13,123.67, 123.61, 123.53, 123.51, 21.87; HMRS (TOF MS ES+): calcd for C 26 H 19 O [m+], 347.1430, found 347.1432.

[0043] Meanwhile, TpPX was prepared into nanoparticles: 500 μL of TpPX (10 mg / mL, DCM) was added to 5 mL of an aqueous solution containing polyoxyethylene polyoxypropylene ether (F127, 10 mg / mL). The mixture was then sonicated for 30 seconds and then stirred at high speed to evaporate and remove DCM, yielding TpPX@F127 nanoparticles.

[0044] In addition, TpPX was prepared into a polymer-doped film: TpPX was mixed with polymethyl methacrylate (PMMA) at a certain mass percentage (wt.%), and then fully dissolved in a sample vial with tetrahydrofuran (THF) or dichloromethane (DCM). The sample vial was then placed in a water bath sonicator and sonicated for 10 min. The resulting polymer solution was then dropped onto a quartz plate of 45 mm × 12.5 mm × 1.2 mm and allowed to air dry naturally to form a film.

[0045] Example 2 Performance testing of phenyl (triphenyl-2-yl) methyl ketone derivative (TpPX)

[0046] The phosphorescence spectra of TpPX (TpPF, TpPBr, TpPI, TpPMe) were measured using an Ocean Optics spectrometer system (MayaPro2000) with 365 and 405 nm LED light sources as the excitation source.

[0047] from Figure 1-3 It can be seen that the phenyl(triphenyl-2-yl)methyl ketone derivative of this invention can produce significant afterglow in polymer, crystal, amorphous powder, and nanoparticle states, demonstrating the stability of the afterglow and its potential applications in anti-counterfeiting, information encryption, lighting, and biological afterglow imaging. Furthermore, by modifying triphenylene with different groups, its photophysical properties can be effectively controlled. Specifically, by introducing carbonyl, sulfone, and other groups onto triphenylene, its photophysical properties can be effectively modified in pure (… Based on the electronic configuration, introduce ( The electronic configuration of the phenyl (triphenyl-2-yl) methyl ketone derivatives promotes electronic coupling between molecules, thereby facilitating intersystem crossing. Simultaneously, the introduction of heteroatoms enhances van der Waals forces, suppressing nonradiative transitions of triplet excitons and ultimately regulating emission intensity and lifetime. Furthermore, the substituents have little effect on the chromophore center, thus not affecting the color of the emitted light, but they can regulate the emission intensity and lifetime. Therefore, the phenyl (triphenyl-2-yl) methyl ketone derivatives of this invention show promising applications in lighting displays, sensing, stimulus response, anti-counterfeiting, information encryption and storage, and biological afterglow imaging, with broad application prospects.

[0048] In summary, the phenyl (trimethylene-2-yl) methyl ketone (TpPX) derivatives designed and synthesized in this invention exhibit strong intermolecular interactions. Even when crystallization is disrupted, they can still maintain strong intermolecular interactions to stabilize triplet excitons and, to a certain extent, block oxygen and water quenching. This allows them to easily emit room-temperature phosphorescence regardless of whether they are in crystalline, amorphous, or nanoparticle states, making them more suitable for production and application.

[0049] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. The application of a phenyl(triphenyl-2-yl) methyl ketone derivative exhibiting room-temperature phosphorescence, characterized in that, The structural formula of the phenyl(triphenyl-2-yl) methyl ketone derivative is shown below: ； Among them, R1, R2, R4, and R5 are -H, and R3 is -F, or -Br, or -I, or -Me; The applications include lighting displays, sensing, stimulus response, anti-counterfeiting, information encryption and storage, and bio-afterglow imaging.

2. The application according to claim 1, characterized in that, The preparation method of the phenyl(triphenyl-2-yl) methyl ketone derivative is as follows: according to the following reaction formula, triphenylene, benzoyl chloride derivative and anhydrous ferric chloride are dissolved in an organic solvent, heated and stirred, and then dilute hydrochloric acid is added and stirred until no bubbles are generated. Then, it is extracted with dilute hydrochloric acid and water in sequence, and then purified by silica gel column chromatography after drying and concentration to obtain the target product. ； Among them, R1, R2, R4, and R5 are -H, and R3 is -F, -Br, -I, or -Me.

3. The application according to claim 2, characterized in that, The molar ratio of triphenylene, benzoyl chloride derivative and anhydrous ferric chloride is 1:5-7:13-15.

4. The application according to claim 2, characterized in that, The heating and stirring reaction is carried out at a temperature of 55-70 °C for a duration of 12-36 h.

5. The application according to claim 2, characterized in that, Extract with dilute hydrochloric acid and water 3-5 times in sequence.

6. The application according to claim 2, characterized in that, When purifying by silica gel column chromatography, dichloromethane / n-hexane = 1:3 is used as the eluent.

7. The application according to claim 2, characterized in that, The organic solvent is selected from dichloromethane.

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