Asymmetric thiazole cationic fluorescent material with near-infrared luminescence property, preparation method and application thereof

Abstract

This invention discloses a class of asymmetric thiazole cationic fluorescent materials with near-infrared emission properties, their preparation methods, and applications. The chemical structures of these materials are shown below. The asymmetric thiazole cationic fluorescent materials exhibiting near-infrared emission properties possess mitochondrial-specific targeting capabilities and high ROS yields. In these materials, the thiazole cationic group is the main building block. The interaction between the thiazole cationic group and hexafluorophosphate ions enhances intramolecular D-A interactions and intermolecular hydrogen bonding, effectively suppressing disordered molecular motion in the aggregated state and achieving a significant improvement in the AIE effect.

Description

Technical Field

[0001] This invention belongs to the field of near-infrared I and II zone biofluorescence imaging and diagnostic materials technology, specifically relating to a class of asymmetric thiazole cationic fluorescent materials with near-infrared luminescence properties, their preparation methods and applications. Background Technology

[0002] Near-infrared fluorescent materials have shown great application potential in biomedical imaging, diagnostic materials, and other fields. The near-infrared region possesses unique advantages in biomedical imaging due to its deeper tissue penetration, lower scattering loss, and higher signal-to-noise ratio. The DA structure is the mainstream construction strategy for organic fluorescent materials; however, symmetrical π-bridges (such as thiophene, furan, and benzene rings) are commonly used in current DA structures. The electronic structure of a symmetrical π-bridge is homogeneous, serving only as a "passive" electron channel or conjugated extension unit. Due to the symmetry of the π-bridge, the electron-pulling effect of the donor and the electron-pulling effect of the acceptor must be transmitted through identical pathways, making it difficult to independently optimize the absorption properties (mainly dominated by the D-π part) and emission properties (mainly dominated by the π-A part and the overall ICT state). This limits the ability to target the absorption and emission wavelengths. Therefore, the burden of controlling luminescence performance (especially the emission wavelength) almost entirely falls on replacing the D or A unit.

[0003] Photodynamic therapy (PDT) often faces the critical bottleneck of non-specific distribution. These substances typically lack active organelle targeting capabilities, remaining diffuse within cells. This not only leads to insufficient effective therapeutic concentrations and limited PDT efficacy, but also results in significant side effects due to the random diffusion of reactive oxygen species (ROS) in the cytoplasm, causing indiscriminate damage to normal cellular components. Mitochondria, as the cell's "energy factory" and apoptosis regulatory center, are ideal targets for achieving highly efficient and low-toxicity PDT due to their high membrane potential, abundant ROS substrates, and central role in cell death pathways.

[0004] Therefore, it is necessary to introduce asymmetric π-bridges to construct near-infrared cationic organic photosensitizers that also have mitochondrial targeting capabilities. Summary of the Invention

[0005] In order to solve the problems mentioned in the background art, the purpose of this invention is to provide a class of asymmetric thiazole cationic fluorescent materials with near-infrared luminescence properties, their preparation methods and applications.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: On one hand, the present invention provides a class of asymmetric thiazole cationic fluorescent materials with near-infrared luminescence properties, the chemical structures of which are shown below: Where D, D1, and D2 are each independent , or R1 is -OCH3, -CH3, -CN, -NO2, -F, -Cl, -Br, -I, -CF3, -C(CH3)3, -COOH or -NH2, and R2 is -OCH3, -CH3, -CN, -NO2, -F, -Cl, -Br, -I, -CF3, -C(CH3)3, -COOH or -NH2; A is , or X is -H, -NH2, -NO2, -F, -Cl, -Br, or -I.

[0007] Furthermore, the chemical structures of a class of asymmetric thiazole cationic fluorescent materials with near-infrared luminescence properties are shown below: , , , , , .

[0008] On the other hand, the present invention provides a method for preparing the above-described asymmetric thiazole cationic fluorescent material with near-infrared luminescence properties, comprising the following steps: (11) will and The reaction proceeds to obtain ; (12) The above ,and or The reaction proceeds to obtain or ; (13) The above or It reacts with iodomethane, and after the reaction is complete, the resulting product is reacted with sodium hexafluorophosphate to obtain... or ; Or (21) ,and or The reaction proceeds to obtain or ; (22) The above or It reacts with N-bromosuccinimide to give or ; (23) The above or ,and The reaction proceeds to obtain or ; (24) The above or It reacts with iodomethane, and after the reaction is complete, the resulting product is reacted with sodium hexafluorophosphate to obtain... or ; Or (31) react 4-boronate-4',4'-dimethoxytriphenylamine with 2-bromothiazole or 5-bromothiazole to obtain or ; (32) The above or It reacts with N-bromosuccinimide to give or ; (33) The above or ,and The reaction proceeds to obtain or ; (34) The above or It reacts with iodomethane, and after the reaction is complete, the resulting product is reacted with sodium hexafluorophosphate to obtain... or .

[0009] Furthermore, step (11) specifically includes the following steps: , A mixture of toluene, ethanol, and potassium carbonate solution was prepared, and the mixture was bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with water to obtain the desired product. Preferably, the , The ratio of potassium carbonate solution to tetra(triphenylphosphine)palladium is 1.2 mmol: 1 mmol: 2 mL: 0.04 mmol, and the concentration of potassium carbonate solution is 2 mol / L; preferably, the bubbling time is 5 min; preferably, the heating reaction temperature is 80°C, and the heating reaction time is 20 h. Step (21) specifically includes the following steps: or , A mixture of toluene and acetone was prepared, and the mixture was bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with a saturated potassium fluoride aqueous solution to obtain the desired product. or Preferably, the or , The ratio of tetra(triphenylphosphine)palladium is 1 mmol: 1 mmol: 0.03 mmol; preferably, the bubbling time is 10 min; preferably, the heating reaction temperature is 110°C and the heating reaction time is 24 h. Step (31) specifically includes the following steps: mixing 4-boronate-4',4'-dimethoxytriphenylamine, 2-bromothiazole or 5-bromothiazole, toluene, ethanol, and potassium carbonate solution to obtain a mixture; bubbling the mixture under a nitrogen atmosphere; adding tetra(triphenylphosphine)palladium under a nitrogen atmosphere; then heating the reaction; after the reaction is complete, cooling to room temperature; and quenching with water to obtain... or Preferably, the ratio of 4-boronate-4',4'-dimethoxytriphenylamine, 2-bromothiazole or 5-bromothiazole, potassium carbonate solution, and tetra(triphenylphosphine)palladium is 1.2 mmol: 1 mmol: 2 mL: 0.04 mmol, and the concentration of the potassium carbonate solution is 2 mol / L; preferably, the bubbling time is 5 min; preferably, the heating reaction temperature is 80°C, and the heating reaction time is 24 h.

[0010] Further, step (12) specifically includes the following steps: placing the... , or A mixture of toluene and tetra(triphenylphosphine)palladium was obtained and bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was then added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with a saturated ammonium chloride solution to obtain... or Preferably, the , or The ratio of tetra(triphenylphosphine)palladium is 1 mmol: 1 mmol: 0.04 mmol; preferably, the bubbling time is 5 min; preferably, the heating reaction temperature is 110°C and the heating reaction time is 24 h; Step (22) specifically includes the following steps: under heating and light-protected conditions, the... or The reaction was carried out with N-bromosuccinimide in chloroform under stirring. After the reaction was completed, the mixture was cooled to room temperature and quenched with water to obtain the desired product. or Preferably, the or The molar ratio of N-bromosuccinimide to N-bromosuccinimide is 1:1.2; preferably, the temperature of the stirring reaction is 60°C and the stirring reaction time is 12 h. Step (32) specifically includes the following steps: under heating and light-protected conditions, the... or The reaction was carried out with N-bromosuccinimide in chloroform under stirring. After the reaction was completed, the mixture was cooled to room temperature and quenched with water to obtain the desired product. or Preferably, the or The molar ratio of N-bromosuccinimide to N-bromosuccinimide is 1:1.5; preferably, the temperature of the stirring reaction is 60°C and the stirring reaction time is 12h.

[0011] Further, step (13) specifically includes the following steps: placing the... or The product was added to N,N-dimethylformamide, followed by the dropwise addition of iodomethane and heating. After the reaction was complete, the resulting product was dissolved in acetonitrile with sodium hexafluorophosphate and the mixture was stirred under heating conditions to obtain... or ; Step (23) specifically includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] or , A mixture of toluene, ethanol, and potassium carbonate solution was prepared, and the mixture was bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with water to obtain the desired product. or ; Step (33) specifically includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] or , A mixture of toluene, ethanol, and potassium carbonate solution was prepared, and the mixture was bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with water to obtain the desired product. or .

[0012] Furthermore, the steps described in step (13) or The ratio of iodomethane and sodium hexafluorophosphate is 1 mmol: 1 mL: 2 mmol; and / or, the heating reaction temperature is 110°C and the heating reaction time is 24 h; and / or, the stirring reaction temperature is 60°C and the stirring reaction time is 24 h. The steps described in step (23) or , The ratio of potassium carbonate solution to tetra(triphenylphosphine)palladium is 1 mmol: 1.2 mmol: 2 mL: 0.04 mmol, and the concentration of potassium carbonate solution is 2 mol / L; and / or, the bubbling time is 5 min; and / or, the heating temperature is 85°C, and the heating time is 20 h. The steps described in step (33) or , The ratio of potassium carbonate solution to tetra(triphenylphosphine)palladium is 1 mmol: 1 mmol: 2 mL: 0.04 mmol, the concentration of potassium carbonate solution is 2 mol / L; and / or, the bubbling time is 5 min; and / or, the heating reaction temperature is 80 °C, and the heating reaction time is 24 h.

[0013] Furthermore, step (24) specifically includes the following steps: placing the... or The product was added to N,N-dimethylformamide, followed by the dropwise addition of iodomethane and heating. After the reaction was complete, the resulting product was dissolved in acetonitrile with sodium hexafluorophosphate and the mixture was stirred under heating conditions to obtain... or ; Step (34) specifically includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] or The product was added to N,N-dimethylformamide, followed by the dropwise addition of iodomethane and heating. After the reaction was complete, the resulting product was dissolved in acetonitrile with sodium hexafluorophosphate and the mixture was stirred under heating conditions to obtain... or .

[0014] Furthermore, the steps described in step (24) or The ratio of iodomethane and sodium hexafluorophosphate is 1 mmol: 1 mL: 2 mmol; and / or, the heating reaction temperature is 110°C and the heating reaction time is 24 h; and / or, the stirring reaction temperature is 60°C and the stirring reaction time is 24 h. The steps described in step (34) or The ratio of iodomethane and sodium hexafluorophosphate is 1 mmol: 1 mL: 2 mmol; and / or, the heating reaction temperature is 110°C and the heating reaction time is 24 h; and / or, the stirring reaction temperature is 50°C and the stirring reaction time is 24 h.

[0015] also, Belongs to D-thiazole + (PF6 - The preparation methods are similar, and the class is as follows: For example, its preparation method includes the following steps: (1) using Starting with 2-bromothiazole, the reaction was carried out in a toluene / ethanol mixed solvent (7:2, v / v) at 80 °C for 24 h under the catalysis of tetra(triphenylphosphine)palladium and potassium carbonate. The intermediate was obtained after post-treatment purification. (2) will Dissolved in N,N-dimethylformamide solvent, iodomethane was added in portions and the reaction was carried out at 110 °C for 24 h. After the reaction was completed, the obtained product was dissolved in acetonitrile with potassium hexafluorophosphate and stirred at 50 °C for 24 h to obtain... .

[0016] Belongs to DA-thiazole + (PF6 - For the preparation method of this type, please refer to [reference needed]. and Preparation of .

[0017] Belongs to D-thiazole + (PF6 - Class A, its preparation method can be found in [reference]. , Preparation of .

[0018] Belongs to D1-thiazole + (PF6 - For the preparation method of the )-D2 type, please refer to , Preparation of .

[0019] On the other hand, the present invention provides an application of the asymmetric thiazole cationic fluorescent material with near-infrared luminescence properties described above, or the asymmetric thiazole cationic fluorescent material with near-infrared luminescence properties prepared by any of the above-described preparation methods, in the preparation of near-infrared fluorescent imaging reagents, biosensors, biofluorescent probes, tumor photothermal therapy agents, surgical guidance imaging reagents, and optoelectronic devices.

[0020] Compared with the prior art, the present invention has the following beneficial effects: (1) In the asymmetric thiazole cationic fluorescent material with near-infrared luminescence characteristics of the present invention, the thiazole cationic group is the main building unit. The intramolecular DA interaction and intermolecular hydrogen bond interaction are enhanced by the thiazole cationic group and hexafluorophosphate ion, thereby effectively suppressing the disordered movement of molecules in the aggregated state and achieving a significant improvement in the AIE (aggregation-induced emission) effect.

[0021] (2) This invention introduces thiazole cationic groups to regulate intramolecular DA interactions, and the resulting thiazole cationic isomer fluorescent materials have significant differences in absorption and emission performance, providing a strategy for efficiently constructing near-infrared fluorescent materials.

[0022] (3) The asymmetric thiazole cationic fluorescent material of the present invention has near-infrared luminescence properties covering the near-infrared I region and the near-infrared II region.

[0023] (4) The asymmetric thiazole cationic fluorescent material with near-infrared luminescence properties of the present invention has mitochondrial-specific targeting ability and high ROS yield.

[0024] (5) The preparation process of the present invention is simple, easy to purify, and has a high yield, which provides a good foundation for practical application. Attached Figure Description

[0025] Figure 1 The TB2 prepared in Example 1 of this invention 1 H NMR spectrum; Figure 2 The TB2 prepared in Example 1 of this invention 13 C NMR spectrum; Figure 3 The HR-MS spectrum of TB2 prepared in Example 1 of this invention; Figure 4 The TB5 prepared in Example 1 of this invention 1 H NMR spectrum; Figure 5 The TB5 prepared in Example 1 of this invention 13 C NMR spectrum; Figure 6 The HR-MS spectrum of TB5 prepared in Example 1 of this invention; Figure 7 The T2B prepared in Example 2 of this invention 1 H NMR spectrum; Figure 8 The T2B prepared in Example 2 of this invention 13 C NMR spectrum; Figure 9The HR-MS spectrum of T2B prepared in Example 2 of this invention; Figure 10 The T5B prepared in Example 2 of this invention 1 H NMR spectrum; Figure 11 The T5B prepared in Example 2 of this invention 13 C NMR spectrum; Figure 12 The HR-MS spectrum of T5B prepared in Example 2 of this invention; Figure 13 The left figure shows the UV-Vis absorption spectra of TB2, TB5, T2B, and T5B prepared in Example 1, respectively. Figure 13 The right figure in the figure shows the fluorescence emission spectra of TB2, TB5, T2B and T5B prepared in Example 1 of the present invention; Figure 14 The left image in the figure is a ROS generation detection image of TB2 prepared in Example 1 of the present invention. Figure 14 The right figure in the figure is a ROS generation detection diagram of TB5 prepared in Example 1 of the present invention; Figure 15 This is a mitochondrial targeting map of TB2 NCs prepared in this invention; Figure 16 It is the TPA-2TZP prepared in Example 3 of this invention. 1 H NMR spectrum; Figure 17 It is the TPA-2TZP prepared in Example 3 of this invention. 13 C NMR spectrum; Figure 18 This is the HR-MS spectrum of TPA-2TZP prepared in Example 3 of this invention; Figure 19 It is the TPA-5TZP prepared in Example 3 of this invention. 1 H NMR spectrum; Figure 20 It is the TPA-5TZP prepared in Example 3 of this invention. 13 C NMR spectrum; Figure 21 This is the HR-MS spectrum of TPA-5TZP prepared in Example 3 of this invention; Figure 22 The left figure shows the UV-Vis absorption spectra of TPA-2TZP prepared in Example 3 and TPA-5TZP prepared in Example 3 of this invention. Figure 22 The right figure in the figure shows the fluorescence emission spectra of TPA-2TZP and TPA-5TZP prepared in Example 3 of the present invention. Figure 23 The left figure in the image is a graph showing the aggregation-induced emission properties of TPA-5TZP prepared in Example 3 of the invention. Figure 23 The right figure in the figure is a test diagram of the aggregation-induced emission properties of TPA-2TZP prepared in Example 3 of the invention; Figure 24 The left figure in the figure is the optimal configuration diagram of TPA-2TZP prepared in Example 3 of the invention; Figure 24 The right figure in the figure is the optimal configuration diagram of TPA-5TZP prepared in Example 3 of the invention; Figure 25 This is a ROS generation detection image of TPA-2TZP prepared in Example 3 of the present invention; Figure 26 This is a mitochondrial targeting map of TPA-2TZP NCs prepared in Example 3 of the present invention. Detailed Implementation

[0026] To better understand the content of this invention, the following detailed description is provided in conjunction with specific implementation methods. However, the scope of protection of this invention is not limited to the following embodiments.

[0027] Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.

[0028] Example 1 Asymmetric thiazole cationic fluorescent materials with near-infrared emission properties and Preparation: (1) Add to a dry 150 mL round-bottom flask (1.2 mmol) (1 mmol), toluene (35 mL), ethanol (10 mL), and 2 mol / L potassium carbonate aqueous solution (2 mL) were bubbled under a nitrogen atmosphere for 5 min. Then, tetrakis(triphenylphosphine)palladium (0.04 mmol) catalyst was added under a nitrogen atmosphere, and the reaction was heated to 80 °C for 20 h. The reaction solution was cooled to room temperature, quenched with water (30 mL) for 30 min, and extracted three times with ethyl acetate (30 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, v / v) to obtain... .

[0029] (2) Add to a dry 100 mL round-bottom flask (1 mmol) or (1 mmol) of ethyl acetate and toluene (40 mL) were bubbled under a nitrogen atmosphere for 5 min. Then, tetrakis(triphenylphosphine)palladium (0.04 mmol) catalyst was added under a nitrogen atmosphere, and the reaction was heated to 110 °C for 24 h. The reaction solution was cooled to room temperature, quenched for 30 min with saturated ammonium chloride solution (30 mL), and extracted three times with ethyl acetate (30 mL). The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (petroleum ether:ethyl acetate = 2:1, v / v) to obtain... (470.5 mg, 90% yield) or (460.2 mg, yield 88%).

[0030] (3) or 1 mmol of sodium hexafluorophosphate (NaPF6, 2 mmol) was added to N,N-dimethylformamide (DMF, 20 mL) in a 50 mL flask. Iodomethane was added dropwise in two portions, totaling 1 mL. The mixture was refluxed at 110 °C for 24 h, and then 100 mL of deionized water was added dropwise to obtain a precipitate. The precipitate was filtered and purified by column chromatography (ethyl acetate:methanol = 20:1, v / v) to obtain a dark red solid. The obtained product was dissolved in acetonitrile (50 mL) with sodium hexafluorophosphate (NaPF6, 2 mmol) and stirred at 60 °C for 24 h. After removing the solvent, the crude product was further dissolved in dichloromethane and washed three times with water to remove excess NaPF6. Finally, the precipitate was collected and dried to obtain the target product. (Referred to as TB2) (260 mg, yield 50%) 1 H NMR (400 MHz, DMSO) δ 8.64 (d, J = 3.9 Hz, 1H), 8.50 (d, J = 3.9 Hz, 1H), 8.30 (d, J = 7.6 Hz, 1H), 8.02 (d, J = 7.6 Hz, 1H), 7.96 (d, J =8.9 Hz, 2H), 7.13 (d, J = 8.9 Hz, 4H), 6.95 (d, J = 8.9 Hz, 4H), 6.85 (d, J = 8.9Hz, 2H), 4.15 (s, 3H), 3.74 (s, 6H). (e.g.) Figure 1 (as shown)13 C NMR (151 MHz, DMSO) δ 165.57, 156.99, 152.96, 152.71, 150.28, 146.10, 139.96, 139.61, 138.18, 134.53, 131.06, 128.37, 128.12, 127.29, 126.61, 126.16, 125.82, 118.04, 115.65, 115.21, 81.98, 55.80, 41.97. (e.g.) Figure 2 shown), HR-MS Calculated for [M] + C 30 H 25 N4O2S2 + : 537.1412, found: 537.1417. (e.g.) Figure 3 (as shown); or (Designated as TB5) (255 mg, yield 49%). 1 H NMR (400 MHz, DMSO) δ 10.32 (s, 1H), 9.47 (s,1H), 8.42 (d, J = 7.6 Hz, 1H), 8.00 (d, J = 7.7 Hz, 1H), 7.97 (d, J = 8.9 Hz, 2H), 7.14 (d, J = 8.9 Hz, 4H), 6.98 (d, J = 9.0 Hz, 4H), 6.89 (d, J = 8.9 Hz, 2H), 4.33 (s, 3H), 3.77 (s, 6H). (e.g.) Figure 4 (as shown) 13 C NMR (151 MHz, DMSO) δ 159.63, 156.78, 153.05, 152.06, 149.78, 139.85, 137.43, 135.82, 135.31, 130.73, 128.91, 127.84, 127.22, 126.63, 118.49, 118.25, 115.60, 55.78, 42.52. (e.g.) Figure 5 shown), HR-MS Calculated for [M] + C 30 H 25 N4O2S2 +: 537.1412, found: 537.1417. (e.g.) Figure 6 (As shown).

[0031] Example 2 Asymmetric thiazole cationic fluorescent materials with near-infrared emission properties and Preparation: (1) Add to a dry 100 mL round-bottom flask or (1 mmol) (1 mmol) and toluene (30 mL) were bubbled under a nitrogen atmosphere for 10 min. Then, under nitrogen protection, the catalyst tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 0.03 mmol) was added, and the reaction was heated to 110 °C for 24 h. The reaction solution was cooled to room temperature, and saturated potassium fluoride aqueous solution (30 mL) was added, followed by stirring and quenching for 30 min. The mixture was extracted three times with ethyl acetate (30 mL). The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (petroleum ether: dichloromethane = 1:1, v / v) to obtain... (198 mg, 90% yield) or (198 mg, yield 90%).

[0032] (2) Take or (1 mmol) was dissolved in chloroform (20 mL) in a dry 50 mL round-bottom flask. N-bromosuccinimide (NBS, 1.2 mmol) was added, and the reaction mixture was heated to 60 °C and stirred in the dark for 12 h. The reaction mixture was cooled to room temperature, quenched with water (20 mL) for 30 min, and extracted three times with dichloromethane (20 mL). The organic phases were combined and washed successively with saturated sodium thiosulfate solution and saturated brine, and dried over anhydrous sodium sulfate. After filtration, the mixture was concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether: dichloromethane = 1:1, v / v) to obtain... (250 mg, yield 83.6%) or (242.2 mg, yield 81%).

[0033] (3) Add to a dry 150 mL round-bottom flask or (1 mmol) (1.2 mmol), toluene (35 mL), ethanol (10 mL), and 2 mol / L potassium carbonate aqueous solution (2 mL). Bubbling was performed under a nitrogen atmosphere for 5 min, followed by the addition of tetrakis(triphenylphosphine)palladium catalyst (0.04 mmol) under a nitrogen atmosphere, and the reaction was heated to 85 °C for 20 h. The reaction solution was cooled to room temperature, quenched with water (30 mL) for 30 min, and extracted three times with dichloromethane (30 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane:petroleum ether = 1:2, v / v) to obtain... (444.7 mg, yield 85%) or (455.0 mg, yield 87%).

[0034] (4) or 1 mmol of methyl iodide was added to N,N-dimethylformamide (DMF, 20 mL) in a 50 mL flask. Iodomethane was added dropwise in two portions, totaling 1 mL. The mixture was refluxed at 110 °C for 24 h, followed by the addition of 100 mL of deionized water to obtain a precipitate. The precipitate was filtered and purified by column chromatography (ethyl acetate:methanol = 20:1, v / v) to obtain a deep red solid. The product was dissolved in acetonitrile (50 mL) with sodium hexafluorophosphate (NaPF6, 2 mmol) and stirred at 60 °C for 24 h to remove the solvent. The crude product was further dissolved in dichloromethane and washed three times with water to remove excess NaPF6. Finally, the precipitate was collected and dried to obtain the target product. (Designated as T2B) (265 mg, yield 51%) 1 H NMR (400 MHz, DMSO) δ 9.30 (s, 1H), 8.30 (d, J = 7.1 Hz, 1H), 8.25 (d, J = 8.8 Hz, 1H), 7.91 (dd, J = 8.8, 7.2 Hz, 1H), 7.75 – 7.72 (m,2H), 7.26 – 7.23 (m, 4H), 7.02 – 6.99 (m, 4H), 6.79 – 6.76 (m, 2H), 4.17 (s,3H), 3.75 (s, 6H).(such as Figure 7 (as shown) 13C NMR (151 MHz, DMSO) δ 169.81, 158.01, 154.87, 153.31, 151.12, 138.09, 137.75, 132.06, 132.00, 130.61, 129.05, 127.77, 123.64, 120.81, 116.11, 115.93, 114.02, 55.88. (e.g.) Figure 8 shown), HR-MSCalculated for [M] + C 30 H 25 N4O2S2 + : 537.1412, found: 537.1417. (e.g.) Figure 9 (as shown); or (Designated as T5B) (262 mg, yield 50%) 1 H NMR (400 MHz, DMSO) δ 8.96(s, 1H), 8.48 (d, J = 8.8 Hz, 1H), 8.32 (d, J = 7.1 Hz, 1H), 8.03 – 7.97 (m,1H), 7.61 (d, J = 8.7 Hz, 2H), 7.13 (d, J = 8.8 Hz, 4H), 6.96 (d, J = 8.9 Hz, 4H), 6.77 (d, J = 8.7 Hz, 2H), 4.14 (s, 3H), 3.74 (s, 6H). (e.g.) Figure 10 (as shown) 13 C NMR (151 MHz, DMSO) δ 160.83, 157.32, 154.73, 151.66, 151.31, 142.20, 139.08, 134.26, 133.83, 130.08, 128.44, 128.23, 126.84, 118.01, 117.83, 117.48, 115.75, 55.81, 42.42. (e.g.) Figure 11 shown), HR-MS Calculated for [M] + C 30 H 25 N4O2S2 + :537.1412, found: 537.1417. (e.g.) Figure 12 (As shown).

[0035] Add 2.5 mL of dimethyl sulfoxide solution (DMSO) of TB2, TB5, T2B, and T5B respectively to a quartz cuvette. -4 (mol / L), its UV-Vis absorption spectrum and fluorescence emission spectrum were measured, and the results are as follows: Figure 13 As shown. From Figure 13 As can be seen, the fluorescent materials exhibit the following characteristics in dimethyl sulfoxide solvent: the main absorption peaks of TB2 and TB5 are located around 500 nm, the main emission peak of TB2 is located at 820 nm, and the main emission peak of TB5 is located at 720 nm. Overall, the emission spectra basically cover 600-1100 nm. The main absorption peaks of T2B and T5B are located around 450 nm, the main emission peak of T2B is located at 710 nm, and the main emission peak of T5B is located at 680 nm. Overall, the emission spectra basically cover 600-1100 nm.

[0036] 50 μL of a solution with a concentration of 2.5 × 10⁻⁶ -4 Add mol / L DCFH-DA aqueous solution to 4 mL, resulting in a concentration of 1×10⁻⁶. - 4 The TB2 emission spectrum was measured after thorough mixing in a mol / L tetrahydrofuran solution, with records taken every 30 s to evaluate the ability of TB2 to induce reactive oxygen species generation. The results are as follows: Figure 14 As shown in the left figure. From Figure 14 The left figure shows that the fluorescence intensity of the solution continuously increases with increasing illumination time. 50 μL of a solution with a concentration of 2.5 × 10⁻⁶ was used. -4 Add mol / L DCFH-DA aqueous solution to 4 mL, resulting in a concentration of 1×10⁻⁶. -4 The TB5 emission spectrum was measured after thorough mixing in a mol / L tetrahydrofuran solution, with records taken every 30 s to evaluate the ability of TB5 to induce reactive oxygen species (ROS) generation. The results are as follows: Figure 14 As shown in the right figure. From Figure 14 As shown in the right figure, the fluorescence intensity of the solution continuously increases with increasing illumination time. This indicates that TB2 and TB5 are highly efficient photosensitizers for generating ROS (reactive oxygen species).

[0037] TB2 (0.5 mg) and DSPE-PEG2000 (1 mg) were mixed at a mass ratio of 1:2 and dissolved in 0.5 mL of tetrahydrofuran (THF). Then, 100 μL of the solution was added to 5 mL of ultrapure water and stirred for 2 h to prepare TB2 NCs. Mitochondrial targeting imaging was performed on the TB2 NCs, and the results are shown below. Figure 15 As shown. From Figure 15As can be seen, compared with the commercial mitochondrial dye MTG, the red fluorescence of TB2 NCs and the green fluorescence of MTG highly overlap, indicating that TB2 NCs have good mitochondrial targeting.

[0038] Example 3 Asymmetric thiazole cationic fluorescent materials with near-infrared emission properties and Preparation: (1) In a dry 150 mL round-bottom flask, add 1.2 mmol of 4-boronate-4',4'-dimethoxytriphenylamine, 1 mmol of 2-bromothiazole or 5-bromothiazole, 35 mL of toluene, 10 mL of ethanol, and 2 mL of 2 mol / L potassium carbonate solution. Bubbling is carried out for 5 min under a nitrogen atmosphere. Then, 0.04 mmol of tetra(triphenylphosphine)palladium catalyst is added under a nitrogen atmosphere, and the temperature is raised to 80 °C for 24 h. The reaction solution is cooled to room temperature, quenched with 30 mL of water for 30 min, and extracted three times with 30 mL of dichloromethane. The organic phases are combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by silica gel column chromatography (dichloromethane: petroleum ether = 1:3, v / v) to obtain (Referred to as Compound 1) (349.6 mg, yield 89%) or (Referred to as compound 4) (349.6 mg, yield 89%).

[0039] (2) Compound 1 or compound 4 (1 mmol) was added to a dry 150 mL round-bottom flask, dissolved in 30 mL of chloroform, and N-bromosuccinimide (1.5 mmol) was added. The mixture was stirred at 60 °C in the dark for 12 h. The reaction solution was cooled to room temperature, quenched with water (20 mL) for 30 min, and extracted three times with dichloromethane (20 mL). The organic phases were combined and washed successively with saturated sodium thiosulfate solution and saturated brine, and dried over anhydrous sodium sulfate. After filtration, the mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (petroleum ether: dichloromethane = 1:1, v / v) to obtain... (Referred to as compound 2) (397.2 mg, yield 85%) or (Referred to as compound 5) (397.2 mg, yield 85%).

[0040] (3) Add compound 2 or compound 5 (1 mmol) to a dry 150 mL round-bottom flask. (1 mmol), toluene (35 mL), ethanol (10 mL), and 2 mol / L potassium carbonate solution (2 mL) were bubbled under a nitrogen atmosphere for 5 min. Then, tetrakis(triphenylphosphine)palladium (0.04 mmol) catalyst was added under a nitrogen atmosphere, and the reaction was heated to 80 °C for 24 h. The reaction solution was cooled to room temperature, quenched with water (30 mL) for 30 min, and extracted three times with dichloromethane (30 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane: petroleum ether = 1:3, v / v) to obtain... (Designated as compound 3) (460.1 mg, yield 81%) or (Referred to as compound 6) (460.1 mg, yield 81%).

[0041] (4) Compound 3 or 6 (1 mol) was added to N,N-dimethylformamide (DMF, 20 mL) in a 50 mL flask. Iodomethane was added dropwise in two portions, totaling 1 mL. The mixture was refluxed at 110 °C for 24 h, and then deionized water (100 mL) was added dropwise to obtain a precipitate. The precipitate was filtered and purified by column chromatography (ethyl acetate:methanol = 20:1, v / v) to obtain a dark red solid. The obtained product was dissolved in acetonitrile (50 mL) with sodium hexafluorophosphate (NaPF6, 2.00 mmol) and stirred at 50 °C for 24 h to remove the solvent. The crude product was further dissolved in dichloromethane and washed three times with water to remove excess NaPF6. Finally, the precipitate was collected and dried to obtain the target product. (Designated as TPA-2TZP) (260 mg, yield 50%) 1 H NMR (400 MHz, DMSO-) d 6) δ 8.65 (s, 1H), 7.66 (d, J = 9.0 Hz, 2H), 7.57 (d, J = 8.9Hz, 2H), 7.25 (d, J = 8.9 Hz, 4H), 7.03 (d, J = 8.9 Hz, 4H), 6.83 (d, J = 9.0Hz, 2H), 6.78 (d, J = 9.0 Hz, 2H), 4.07 (s, 3H), 3.78 (s, 6H), 3.00 (s, 6H) (e.g.) Figure 16 (as shown) 13 C NMR (151 MHz, DMSO- d 6) δ 168.56, 157.91, 152.92, 151.94, 138.88, 138.20, 132.28, 131.67, 128.97, 127.69, 116.15, 115.90, 114.61, 114.35, 112.73, 55.85 (e.g.) Figure 17 shown), HR-MS Calculated for [M] + C 32 H 32 N3O2S: 522.2232, found: 522.2223 (e.g.) Figure 18 (as shown); or (Designated as TPA-5TZP) (260 mg, yield 50%) 1 HNMR (400 MHz) δ 10.09 (s, 1H), 7.21 (d, J = 8.9 Hz, 2H), 7.05 (d, J = 8.9 Hz, 6H), 6.90 (d, J = 9.0 Hz, 4H), 6.78 (d, J = 8.9 Hz, 2H), 6.52 (d, J = 8.9 Hz, 2H), 3.79 (s, 3H), 3.70 (s, 6H), 2.94 (s, 6H). (e.g.) Figure 19 (as shown) 13 C NMR (101 MHz, DMSO- d 6) δ 157.21, 150.28, 143.17, 139.05, 138.29, 131.89, 129.74, 128.46, 118.58, 117.09, 115.67, 115.48, 113.10, 112.55, 55.77. (e.g.) Figure 20 shown), HR-MSCalculated for [M] + C 32 H 32 N3O2S: 522.2232, found: 522.2252 (e.g.) Figure 21 (As shown).

[0042] Add 2.5 mL of dimethyl sulfoxide solution (DMSO) of TPA-2TZP and TPA-5TZP to quartz cuvettes, respectively. -4 (mol / L), its UV-Vis absorption spectrum and fluorescence emission spectrum were measured, and the results are as follows: Figure 22 As shown. From Figure 22 It can be seen that the fluorescent material TPA-2TZP exhibits the following characteristics in dimethyl sulfoxide solvent: the UV-Vis absorption spectrum at 280 nm can be attributed to π-π absorption, and the maximum absorption peak at 440 nm can be attributed to n-π absorption, with a molar extinction coefficient of 2.6 × 10⁻⁶. 3 M -1 ·cm -1 The fluorescence emission spectrum covers the near-infrared I (NIR-I) region of 500-850 nm. The fluorescent material TPA-5TZP exhibits the following characteristics in dimethyl sulfoxide solvent: the UV-Vis absorption spectrum shows absorption at 280 nm at an attributed to π-π absorption, and a maximum absorption peak at 380 nm at an attributed to n-π absorption; the fluorescence emission spectrum covers 450-850 nm.

[0043] The aggregation-induced emission properties of TPA-5TZP were tested, and the results are as follows: Figure 23 The left figure shows the aggregation-induced emission properties of TPA-2TZP. The results are as follows: Figure 23 As shown in the right figure. From Figure 23 As can be seen from this, the AIE index of TPA-2TZP and TPA-5TZP ( α AIE The values ​​reached 1.52 and 0.37 respectively, indicating that the fluorescent material TPA-2TZP can effectively overcome the fluorescence quenching effect caused by the expansion of the π-conjugated system and exhibit high brightness fluorescence emission performance in the aggregated state.

[0044] The optimal configuration of TPA-2TZP is as follows: Figure 24 The left figure shows the optimal configuration of TPA-5TZP. Figure 24 As shown in the right figure. From Figure 24 As can be seen, both TPA-2TZP and TPA-5TZP have unique electron-donating and electron-withdrawing twisted structures, namely unique D-π-A type electronic structure systems, and the TPA-2TZP molecule has a more twisted configuration.

[0045] 50 μL of a solution with a concentration of 2.5 × 10⁻⁶ -4 Add mol / L DCFH-DA aqueous solution to 4 mL, resulting in a concentration of 1×10⁻⁶. - 4 The TPA-2TZP was mixed thoroughly in a mol / L TB2 tetrahydrofuran solution, and its emission spectrum was measured. Recordings were taken every 30 seconds to evaluate the ability of TPA-2TZP to induce reactive oxygen species generation. The results are as follows: Figure 25 As shown. From Figure 25As can be seen, the fluorescence intensity of the solution continues to increase with the increase of illumination time, indicating that TPA-2TZP is a highly efficient photosensitizer for generating ROS.

[0046] TPA-2TZP (0.5 mg) and DSPE-PEG2000 (1 mg) were mixed at a mass ratio of 1:2 and dissolved in 0.5 mL of THF. Then, 100 μL of the solution was added to 5 mL of ultrapure water and stirred for 2 h to prepare TPA-2TZP NCs. Mitochondrial targeting imaging was performed on the TPA-2TZP NCs, and the results are as follows... Figure 26 As shown. From Figure 26 As can be seen, compared with the commercial mitochondrial dye MTG, the red fluorescence of TPA-2TZPNCs almost completely overlaps with the green fluorescence of MTG, indicating that TPA-2TZPNCs have excellent mitochondrial targeting.

[0047] The above description is only a specific embodiment of the present invention and not all embodiments. Any equivalent modifications made by those skilled in the art to the technical solutions of the present invention by reading the present invention specification shall be covered by the claims of the present invention.

Claims

1. A class of asymmetric thiazole cationic fluorescent materials with near-infrared luminescence properties, the chemical structures of which are shown below: in, D is , or R1 is -OCH3, -CH3, -CN, -NO2, -F, -Cl, -Br, -I, -CF3, -C(CH3)3, -COOH or -NH2, and R2 is -OCH3, -CH3, -CN, -NO2, -F, -Cl, -Br, -I, -CF3, -C(CH3)3, -COOH or -NH2; A is , or X is -H, -NH2, -NO2, -F, -Cl, -Br, or -I; D1 is , or R1 is -OCH3, -CH3, -CN, -NO2, -F, -Cl, -Br, -I, -CF3, -C(CH3)3, -COOH, or -NH2; R2 is -OCH3, -CH3, -CN, -NO2, -F, -Cl, -Br, -I, -CF3, -C(CH3)3, -COOH, or -NH2; D2 is... , or R1 is -OCH3, -CH3, -CN, -NO2, -F, -Cl, -Br, -I, -CF3, -C(CH3)3, -COOH or -NH2, and R2 is -OCH3, -CH3, -CN, -NO2, -F, -Cl, -Br, -I, -CF3, -C(CH3)3, -COOH or -NH2.

2. The asymmetric thiazole cationic fluorescent material with near-infrared luminescence properties according to claim 1, characterized in that, Their chemical structures are shown below: 、 、 、 、 、 。 3. The method for preparing the asymmetric thiazole cationic fluorescent material with near-infrared luminescence properties according to claim 2, characterized in that, Includes the following steps: (11) will and The reaction proceeds to obtain ; (12) The above ,and or The reaction proceeds to obtain or ; (13) The above or It reacts with iodomethane, and after the reaction is complete, the resulting product is reacted with sodium hexafluorophosphate to obtain... or ; Or (21) ,and or The reaction proceeds to obtain or ; (22) The above or It reacts with N-bromosuccinimide to give or ; (23) The above or ,and The reaction proceeds to obtain or ; (24) The above or It reacts with iodomethane, and after the reaction is complete, the resulting product is reacted with sodium hexafluorophosphate to obtain... or ; Or (31) react 4-boronate-4',4'-dimethoxytriphenylamine with 2-bromothiazole or 5-bromothiazole to obtain or ; (32) The above or It reacts with N-bromosuccinimide to give or ; (33) The above or ,and The reaction proceeds to obtain or ; (34) The above or It reacts with iodomethane, and after the reaction is complete, the resulting product is reacted with sodium hexafluorophosphate to obtain... or .

4. The preparation method according to claim 3, characterized in that, Step (11) specifically includes the following steps: , A mixture of toluene, ethanol, and potassium carbonate solution was prepared, and the mixture was bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with water to obtain the desired product. Preferably, the , The ratio of potassium carbonate solution to tetra(triphenylphosphine)palladium is 1.2 mmol: 1 mmol: 2 mL: 0.04 mmol, and the concentration of potassium carbonate solution is 2 mol / L; preferably, the bubbling time is 5 min; preferably, the heating reaction temperature is 80°C, and the heating reaction time is 20 h. Step (21) specifically includes the following steps: or , A mixture of toluene and acetone was prepared, and the mixture was bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with a saturated potassium fluoride aqueous solution to obtain the desired product. or Preferably, the or , The ratio of tetra(triphenylphosphine)palladium is 1 mmol: 1 mmol: 0.03 mmol; preferably, the bubbling time is 10 min; preferably, the heating reaction temperature is 110°C and the heating reaction time is 24 h; Step (31) specifically includes the following steps: mixing 4-boronate-4',4'-dimethoxytriphenylamine, 2-bromothiazole or 5-bromothiazole, toluene, ethanol, and potassium carbonate solution to obtain a mixture; bubbling the mixture under a nitrogen atmosphere; adding tetra(triphenylphosphine)palladium under a nitrogen atmosphere; then heating the reaction; after the reaction is complete, cooling to room temperature; and quenching with water to obtain... or Preferably, the ratio of 4-boronate-4',4'-dimethoxytriphenylamine, 2-bromothiazole or 5-bromothiazole, potassium carbonate solution, and tetra(triphenylphosphine)palladium is 1.2 mmol: 1 mmol: 2 mL: 0.04 mmol, and the concentration of the potassium carbonate solution is 2 mol / L; preferably, the bubbling time is 5 min; preferably, the heating reaction temperature is 80°C, and the heating reaction time is 24 h.

5. The preparation method according to claim 3, characterized in that, Step (12) specifically includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] , or A mixture of toluene and tetra(triphenylphosphine)palladium was obtained and bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was then added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with a saturated ammonium chloride solution to obtain... or Preferably, the , or The ratio of tetra(triphenylphosphine)palladium is 1 mmol: 1 mmol: 0.04 mmol; preferably, the bubbling time is 5 min; preferably, the heating reaction temperature is 110°C and the heating reaction time is 24 h; Step (22) specifically includes the following steps: under heating and light-protected conditions, the... or The reaction was carried out with N-bromosuccinimide in chloroform under stirring. After the reaction was completed, the mixture was cooled to room temperature and quenched with water to obtain the desired product. or Preferably, the or The molar ratio of N-bromosuccinimide to N-bromosuccinimide is 1:1.2; preferably, the temperature of the stirring reaction is 60°C and the stirring reaction time is 12 h. Step (32) specifically includes the following steps: under heating and light-protected conditions, the... or The reaction was carried out with N-bromosuccinimide in chloroform under stirring. After the reaction was completed, the mixture was cooled to room temperature and quenched with water to obtain the desired product. or Preferably, the or The molar ratio of N-bromosuccinimide to N-bromosuccinimide is 1:1.5; preferably, the temperature of the stirring reaction is 60°C and the stirring reaction time is 12h.

6. The preparation method according to claim 3, characterized in that, Step (13) specifically includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] or The product was added to N,N-dimethylformamide, followed by the dropwise addition of iodomethane and heating. After the reaction was complete, the resulting product was dissolved in acetonitrile with sodium hexafluorophosphate and the mixture was stirred under heating conditions to obtain... or ; Step (23) specifically includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] or , A mixture of toluene, ethanol, and potassium carbonate solution was prepared, and the mixture was bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with water to obtain the desired product. or ; Step (33) specifically includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] or , A mixture of toluene, ethanol, and potassium carbonate solution was prepared, and the mixture was bubbled under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium was added under a nitrogen atmosphere, followed by heating. After the reaction was complete, the mixture was cooled to room temperature and quenched with water to obtain the desired product. or .

7. The preparation method according to claim 6, characterized in that, The steps described in step (13) or The ratio of iodomethane and sodium hexafluorophosphate is 1 mmol: 1 mL: 2 mmol; and / or, the heating reaction temperature is 110°C and the heating reaction time is 24 h; and / or, the stirring reaction temperature is 60°C and the stirring reaction time is 24 h. The steps described in step (23) or , The ratio of potassium carbonate solution to tetra(triphenylphosphine)palladium is 1 mmol: 1.2 mmol: 2 mL: 0.04 mmol, and the concentration of potassium carbonate solution is 2 mol / L; and / or, the bubbling time is 5 min; and / or, the heating temperature is 85°C, and the heating time is 20 h. The steps described in step (33) or , The ratio of potassium carbonate solution to tetra(triphenylphosphine)palladium is 1 mmol: 1 mmol: 2 mL: 0.04 mmol, the concentration of potassium carbonate solution is 2 mol / L; and / or, the bubbling time is 5 min; and / or, the heating reaction temperature is 80 °C, and the heating reaction time is 24 h.

8. The preparation method according to claim 3, characterized in that, Step (24) specifically includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] or The product was added to N,N-dimethylformamide, followed by the dropwise addition of iodomethane and heating. After the reaction was complete, the resulting product was dissolved in acetonitrile with sodium hexafluorophosphate and the mixture was stirred under heating conditions to obtain... or ; Step (34) specifically includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] or The product was added to N,N-dimethylformamide, followed by the dropwise addition of iodomethane and heating. After the reaction was complete, the resulting product was dissolved in acetonitrile with sodium hexafluorophosphate and the mixture was stirred under heating conditions to obtain... or .

9. The preparation method according to claim 8, characterized in that, The steps described in step (24) or The ratio of iodomethane and sodium hexafluorophosphate is 1 mmol: 1 mL: 2 mmol; and / or, the heating reaction temperature is 110°C and the heating reaction time is 24 h; and / or, the stirring reaction temperature is 60°C and the stirring reaction time is 24 h. The steps described in step (34) or The ratio of iodomethane and sodium hexafluorophosphate is 1 mmol: 1 mL: 2 mmol; and / or, the heating reaction temperature is 110°C and the heating reaction time is 24 h; and / or, the stirring reaction temperature is 50°C and the stirring reaction time is 24 h.

10. The application of the asymmetric thiazole cationic fluorescent material with near-infrared luminescence properties as described in any one of claims 1-2 or the asymmetric thiazole cationic fluorescent material with near-infrared luminescence properties prepared by the preparation method described in any one of claims 3-9 in the preparation of near-infrared fluorescent imaging reagents, biosensors, biofluorescent probes, tumor photothermal therapy agents, surgical guidance imaging reagents, and optoelectronic devices.

Images