A perylene diimide-based porous organic polymer and a preparation method and photocatalytic application thereof

Abstract

The application belongs to the technical field of photocatalytic materials, and particularly relates to a porous organic polymer based on perylene diimide and a preparation method and photocatalytic application thereof. The porous organic polymer is a cross-linked polymer based on perylene diimide derivatives. The molecular structure of the perylene diimide derivatives is that the polymer is formed by the perylene diimide derivatives through a Friedel-Crafts reaction or a Suzuki coupling reaction. Under light conditions, the sulfur benzamide compound can be photocatalytically oxidized and cyclized into a 1,2,4-thiadiazole compound quickly and with high selectivity.

Description

Technical Field

[0001] This invention belongs to the field of photocatalytic materials technology, and specifically relates to a porous organic polymer based on perylene diimide, its preparation method, and its photocatalytic application. Background Technology

[0002] Over the past two decades, porous organic polymers (POPs) have experienced rapid development. To date, POPs have been classified according to their synthetic methods or typical functional groups, such as intrinsically microporous polymers (PIMs), conjugated microporous polymers (CMPs), and porous aromatic frameworks (PAFs). These porous materials often offer significant advantages in synthesis and application, particularly in integrating porosity, stable structures, and catalytically active sites into POPs, providing one of the best platforms for heterogeneous catalysts and enabling the realization of some difficult and important organic reactions in the laboratory and chemical industry.

[0003] Perylene diimide is an electron-deficient structural unit used to construct n-type organic semiconductors. Its derivatives exhibit excellent visible light harvesting ability, thermal stability, chemical stability, and chemical modification capabilities, thus finding wide application in fluorescence imaging, sensors, solar cells, electron emission, and photocatalytic materials. Currently, polymer photocatalysts developed using perylene diimide as a photosensitizing center demonstrate excellent catalytic performance in photocatalytic hydrogen and oxygen production, as well as the photodegradation of water-soluble pollutants, exhibiting excellent stability and recyclability, and showing great potential for practical applications.

[0004] Photocatalysis for the transformation of small organic molecules is an important research topic and direction in synthetic chemistry. Compounds containing 1,2,4-thiadiazole structural units have significant biological and medical value. Drugs with 1,2,4-thiadiazole as the key skeleton have shown good activity in inhibiting inflammation, central nervous system activity, and antibiotic effects, such as the most well-known commercial antibiotic cefazolin. However, most synthetic routes of 1,2,4-thiadiazole are achieved by oxidizing cyclized thiobenzamides with various oxidants (such as DDQ, iodate, and phosphovanadium molybdate), resulting in environmentally unfriendly byproducts that are detrimental to sustainable development. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a porous organic polymer based on perylene diimide: a cross-linked polymer based on perylene diimide derivatives, wherein the molecular structure of the perylene diimide derivatives is as follows:

[0006] ,

[0007] R is one of triphenylamine, carbazole, pyrrole, thiophene, benzene, quinoline, indole, phenothiazine, or tetra(2-thienyl)ethylene.

[0008] The present invention also provides a method for preparing the above-mentioned porous organic polymer based on perylene diimide, comprising the following steps:

[0009] (1) After fully dispersing the perylene diimide derivative in the solvent, add a catalyst with a molar percentage of 10% to 500% of the perylene diimide derivative and disperse it fully;

[0010] (2) Place the dispersion system obtained in step (1) in a protective atmosphere and heat it to 20-100℃ for 12-72 hours;

[0011] (3) Filter the reaction system obtained in step (2) and wash the filter cake obtained by filtration;

[0012] (4) After washing the filter cake in step (3), dry it to obtain a porous organic polymer.

[0013] Preferably, the catalyst in step (1) is one or a combination of ferric chloride, aluminum chloride, palladium dichloride, and tetra(triphenylphosphine)palladium.

[0014] Preferably, the solvent in step (1) is N , N - One or a combination of several of the following: dimethylformamide, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol.

[0015] Preferably, the protective atmosphere in step (2) is nitrogen or argon.

[0016] Preferably, in step (3), water, ether, and... N , N The filter cake is washed with one or more of the following: dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol.

[0017] As a preferred option: in step (4), the filter cake is eluted in a Soxhlet extractor by sequentially eluting it with dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol.

[0018] Preferably, the elution time is 12 to 36 hours, and the product is dried under vacuum at a temperature of 60 to 100°C for 12 to 24 hours.

[0019] The present invention also provides a photocatalytic application of the above-mentioned porous organic polymer based on perylene diimide: photocatalytic oxidative cyclization of thiobenzamide compounds into 1,2,4-thiadiazole compounds.

[0020] Preferably, the amount of porous organic polymer used for catalysis is 1% of the molar amount of the thiobenzamide compound.

[0021] The beneficial effects of this invention are as follows: Perylene diimide derivatives are prepared into porous organic polymers using Friedel-Crafts or Suzuki coupling reactions, resulting in simple synthesis and high yields. The prepared porous organic polymers exhibit excellent photocatalytic performance, rapidly and selectively oxidizing thiobenzamide compounds to 1,2,4-thiadiazole compounds under illumination. Furthermore, compared to perylene diimide derivative monomers, the polymerized photocatalyst has a wider absorption range, improving the utilization of sunlight and demonstrating potential applications in photocatalysis. In addition, the cross-linked catalyst possesses a certain porous structure, which is beneficial for increasing the specific surface area and active sites of the catalyst. Moreover, the perylene diimide porous organic polymer, as a heterogeneous photocatalyst, can be recycled and reused for photocatalytic thiobenzamide compounds, thereby achieving the goal of sustainable green chemistry. Attached Figure Description

[0022] Figure 1 Water contact angle diagram of PDI-CZ, a perylene diimide porous organic polymer prepared in Example 2;

[0023] Figure 2 Impedance diagrams of perylene diimide porous organic polymer PDI-TPA prepared in Example 1 and perylene diimide porous organic polymer PDI-CZ prepared in Example 2;

[0024] Figure 3 XRD patterns of perylene diimide porous organic polymer PDI-TPA prepared in Example 1 and perylene diimide porous organic polymer PDI-CZ prepared in Example 2;

[0025] Figure 4 TEM image of PDI-CZ, a perylene diimide porous organic polymer prepared in Example 2;

[0026] Figure 5 TGA image of PDI-CZ, a perylene diimide porous organic polymer prepared in Example 2;

[0027] Figure 6 In Application Example 1, based on the photocatalyst of this scheme, the photocatalytic oxidation of thiobenzamide into 1,2,4-thiadiazole is carried out. 1 H NMR spectrum. Detailed Implementation

[0028] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0030] A porous organic polymer based on perylene diimide is a cross-linked polymer based on perylene diimide derivatives, wherein the molecular structure of the perylene diimide derivatives is as follows:

[0031] ,

[0032] R is one of triphenylamine, carbazole, pyrrole, thiophene, benzene, quinoline, indole, phenothiazine, or tetra(2-thienyl)ethylene.

[0033] The synthesis route is as follows:

[0034] .

[0035] The synthetic preparation method includes the following steps:

[0036] (1) After fully dispersing the perylene diimide derivative in the solvent, add a catalyst at a molar percentage of 10% to 500% of the perylene diimide derivative and disperse it fully.

[0037] The catalyst is one or a combination of several of ferric chloride, aluminum chloride, palladium dichloride, and tetra(triphenylphosphine)palladium, and the solvent is... N , N - One or a combination of several of the following: dimethylformamide, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol;

[0038] (2) Place the dispersion system obtained in step (1) in a protective atmosphere and heat it to 20-100℃ for 12-72 hours.

[0039] The protective atmosphere is either nitrogen or argon.

[0040] (3) Filter the reaction system obtained in step (2) and wash the filter cake obtained by filtration;

[0041] Among them, water, ether, N ,N The filter cake is washed with one or more of the following: dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol.

[0042] (4) After washing the filter cake in step (3), dry it to obtain a porous organic polymer.

[0043] The filter cake was eluted in a Soxhlet extractor, and then eluted sequentially with dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol for 12–36 hours. After elution, the filter cake was dried under vacuum at a temperature of 60–100°C for 12–24 hours.

[0044] Example 1

[0045] Following the synthetic route:

[0046]

[0047] (1) 1,7-Diphenylamine[3-(dimethylamino)propyl]-perylene diimide (1.12 g, 1.07 mmol) and 100 mL of chloroform were added to a 250 mL Shlenk flask. After stirring and mixing for 30 minutes under a nitrogen atmosphere, ferric chloride (0.69 g, 4.28 mmol) was added to the Shlenk flask in three equal batches while keeping the mixture stirred. After each batch of ferric chloride was added, it was stirred and dispersed in the Shlenk flask before adding the next batch.

[0048] (2) After all the ferric chloride in step (1) has been added, the resulting dispersion system is kept under a nitrogen atmosphere and stirred at room temperature (25°C, the same below) for 72 hours.

[0049] (3) Filter the reaction system obtained in step (2), and then sequentially rinse the filter cake with water, N , N Washing with dimethylformamide, dichloromethane, and methanol;

[0050] (4) Place the filter cake washed in step (3) into a Soxhlet extractor and elute it with dichloromethane, acetone, tetrahydrofuran, acetonitrile and methanol for a total of 36 hours (the elution time of each eluent is similar, the same below). Transfer the eluted filter cake to a vacuum drying oven and dry it at 60°C for 24 hours to obtain perylene diimide porous organic polymer PDI-TPA with a yield of 93% (yield = weight of perylene diimide porous organic polymer obtained after drying ÷ mass of perylene diimide derivative raw material in step (1) × 100%, the same below).

[0051] Example 2

[0052] Following the synthetic route:

[0053]

[0054] (1) 1,7-bis(9H-carbazole-9-yl)phenyl[3-(dimethylamino)propyl]-perylene diimide (1.12 g, 1.07 mmol) and 100 mL of chloroform were added to a 250 mL Shlenk flask. After stirring and mixing for 30 minutes under a nitrogen atmosphere, ferric chloride (0.69 g, 4.28 mmol) was added to the Shlenk flask in three equal batches while keeping the mixture stirred. After each batch of ferric chloride was added, it was stirred and dispersed in the Shlenk flask before adding the next batch.

[0055] (2) After all the ferric chloride in step (1) has been added, the resulting dispersion system is kept under a nitrogen atmosphere and stirred at room temperature for 72 hours.

[0056] (3) Filter the reaction system obtained in step (2), and then sequentially rinse the filter cake with water, N , N Washing with dimethylformamide, dichloromethane, and methanol;

[0057] (4) The filter cake washed in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, acetone, tetrahydrofuran, acetonitrile and methanol for a total of 12 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried at 100°C for 12 hours to obtain perylene diimide porous organic polymer PDI-CZ with a yield of 95%.

[0058] The water contact angle diagram of the porous organic polymer PDI-CZ prepared in Example 2 is attached. Figure 1 As shown, the porous organic polymer PDI-CZ exhibits good hydrophilicity, and therefore can also be well dispersed in water, which is beneficial to the mass transfer effect and thus to the photocatalytic performance.

[0059] The impedance diagrams of the porous organic polymer PDI-TPA prepared in Example 1 and the porous organic polymer PDI-CZ prepared in Example 2 are attached. Figure 2 As shown, in comparison, the impedance curve curvature diameter of PDI-CZ prepared in Example 2 is significantly smaller, indicating that PDI-CZ has less resistance to electron migration, that is, stronger carrier separation and migration efficiency, and better photocatalytic performance.

[0060] Example 3

[0061] Following the synthetic route:

[0062]

[0063] (1) 1,7-Dipyrrole[3-(dimethylamino)propyl]-perylene diimide (0.74 g, 1.07 mmol) and 100 mL of chloroform were added to a 250 mL Shlenk flask. After stirring and mixing for 30 minutes under a nitrogen atmosphere, ferric chloride (0.86 g, 5.35 mmol) was added to the Shlenk flask in four equal batches while keeping the mixture stirred. After each batch of ferric chloride was added, it was stirred and dispersed in the Shlenk flask before adding the next batch.

[0064] (2) After all the ferric chloride in step (1) has been added, the resulting dispersion system is kept under a nitrogen atmosphere and stirred at room temperature for 72 hours.

[0065] (3) Filter the reaction system obtained in step (2), and then sequentially rinse the filter cake with water, N , N Washing with dimethylformamide, dichloromethane, and methanol;

[0066] (4) The filter cake washed in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, acetone, tetrahydrofuran, acetonitrile and methanol for a total of 20 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried at 70°C for 18 hours to obtain perylene diimide porous organic polymer PDI-Py with a yield of 92%.

[0067] Example 4

[0068] Following the synthetic route:

[0069]

[0070] (1) 1,7-Dithiophene[3-(dimethylamino)propyl]-perylene diimide (0.78 g, 1.07 mmol) and 100 mL of chloroform were added to a 250 mL Shlenk flask. After stirring and mixing for 30 minutes under a nitrogen atmosphere, ferric chloride (0.52 g, 3.21 mmol) was added to the Shlenk flask in two equal batches while keeping the mixture stirred. After each batch of ferric chloride was added, it was stirred and dispersed in the Shlenk flask before adding the next batch.

[0071] (2) After all the ferric chloride in step (1) has been added, the resulting dispersion system is kept under a nitrogen atmosphere and stirred at room temperature for 72 hours.

[0072] (3) Filter the reaction system obtained in step (2), and then sequentially rinse the filter cake with water, N ,N Washing with dimethylformamide, dichloromethane, and methanol;

[0073] (4) The filter cake washed in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, acetone, tetrahydrofuran, acetonitrile and methanol for a total of 15 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried at 80°C for 15 hours to obtain perylene diimide porous organic polymer PDI-TP with a yield of 93%.

[0074] Example 5

[0075] Following the synthetic route:

[0076]

[0077] (1) 1,7-Diphenyl[3-(dimethylamino)propyl]-perylene diimide (0.76 g, 1.07 mmol) and 100 mL of chloroform were added to a 250 mL Shlenk flask. After stirring and mixing for 30 minutes under a nitrogen atmosphere, ferric chloride (0.034 g, 0.21 mmol) was added to the Shlenk flask while stirring and stirred until fully dispersed.

[0078] (2) The dispersion system obtained in step (1) was kept under a nitrogen atmosphere and stirred at room temperature for 72 hours;

[0079] (3) Filter the reaction system obtained in step (2), and then sequentially rinse the filter cake with water, N , N Washing with dimethylformamide, dichloromethane, and methanol;

[0080] (4) The filter cake washed in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, acetone, tetrahydrofuran, acetonitrile and methanol for a total of 20 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried at 80°C for 12 hours to obtain perylene diimide porous organic polymer PDI-Ph with a yield of 96%.

[0081] Example 6

[0082] Following the synthetic route:

[0083]

[0084] (1) 1,7-Diquinoline[3-(dimethylamino)propyl]-perylene diimide (0.88 g, 1.07 mmol) and 100 mL of chloroform were added to a 250 mL Shlenk flask. After stirring and mixing for 30 minutes under a nitrogen atmosphere, ferric chloride (0.86 g, 5.35 mmol) was added to the Shlenk flask in four equal batches while keeping the mixture stirred. After each batch of ferric chloride was added, it was stirred and dispersed in the Shlenk flask before adding the next batch.

[0085] (2) After all the ferric chloride in step (1) has been added, the resulting dispersion system is kept under a nitrogen atmosphere and stirred at room temperature for 72 hours.

[0086] (3) Filter the reaction system obtained in step (2), and then sequentially rinse the filter cake with water, N , N Washing with dimethylformamide, dichloromethane, and methanol;

[0087] (4) The filter cake washed in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, acetone, tetrahydrofuran, acetonitrile and methanol for a total of 14 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried at 75°C for 16 hours to obtain perylene diimide porous organic polymer PDI-QL with a yield of 95%.

[0088] Example 7

[0089] Following the synthetic route:

[0090]

[0091] (1) 1,7-Diindole[3-(dimethylamino)propyl]-perylene diimide (0.845 g, 1.07 mmol) and 100 mL of chloroform were added to a 250 mL Shlenk flask. After stirring and mixing for 30 minutes under a nitrogen atmosphere, ferric chloride (0.52 g, 3.21 mmol) was added to the Shlenk flask in two equal batches while keeping the mixture stirred. After each batch of ferric chloride was added, it was stirred and dispersed in the Shlenk flask before adding the next batch.

[0092] (2) After all the ferric chloride in step (1) has been added, the resulting dispersion system is kept under a nitrogen atmosphere and stirred at room temperature for 48 hours.

[0093] (3) Filter the reaction system obtained in step (2), and then sequentially rinse the filter cake with water, N , NWashing with dimethylformamide, dichloromethane, and methanol;

[0094] (4) The filter cake washed in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, acetone, tetrahydrofuran, acetonitrile and methanol for a total of 32 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried at 65°C for 22 hours to obtain perylene diimide porous organic polymer PDI-ID with a yield of 95%.

[0095] Example 8

[0096] Following the synthetic route:

[0097]

[0098] (1) 1,7-Dithiophenazine[3-(dimethylamino)propyl]-perylene diimide (0.99 g, 1.07 mmol) and 100 mL of chloroform were added to a 250 mL Shlenk flask. After stirring and mixing for 30 minutes under a nitrogen atmosphere, ferric chloride (0.52 g, 3.21 mmol) was added to the Shlenk flask in two equal batches while keeping the mixture stirred. After each batch of ferric chloride was added, it was stirred and dispersed in the Shlenk flask before adding the next batch.

[0099] (2) After all the ferric chloride in step (1) has been added, the resulting dispersion system is kept under a nitrogen atmosphere and stirred at room temperature for 72 hours.

[0100] (3) Filter the reaction system obtained in step (2), and then sequentially rinse the filter cake with water, N , N Washing with dimethylformamide, dichloromethane, and methanol;

[0101] (4) The filter cake washed in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, acetone, tetrahydrofuran, acetonitrile and methanol for a total of 24 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried at 70°C for 18 hours to obtain perylene diimide porous organic polymer PDI-PTZ with a yield of 98%.

[0102] Example 9

[0103] Following the synthetic route:

[0104]

[0105] (1) 1,7-Dibromo[3-(dimethylamino)propyl]-perylene diimide (1.15 g, 2.1 mmol), tetra(4-boronylthiophene)ethylene (3.3 g, 6.27 mmol) and 100 mL of tetrahydrofuran were added to a 250 mL Shlenk flask. After stirring and mixing for 30 minutes under a nitrogen atmosphere, potassium carbonate (1.66 g, 12 mmol) was dissolved in 6 mL of water. The potassium carbonate aqueous solution was added dropwise to the Shlenk flask while stirring. Then tetra(triphenylphosphine)palladium (0.24 g, 0.21 mmol) was added to the Shlenk flask and stirred to disperse it thoroughly.

[0106] (2) Keep the dispersion system obtained in step (1) under a nitrogen atmosphere, heat it to 70°C and stir for 72 hours;

[0107] (3) Filter the reaction system obtained in step (2), and then sequentially rinse the filter cake with water, N , N Washing with dimethylformamide, dichloromethane, and methanol;

[0108] (4) The filter cake washed in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, acetone, tetrahydrofuran, acetonitrile and methanol for a total of 30 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried at 85°C for 16 hours to obtain perylene diimide porous organic polymer PDI-FTV with a yield of 94%.

[0109] Application Example 1

[0110] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0111]

[0112] 10.4 mg of each of the perylene diimide porous organic polymers prepared in Examples 1 to 9 were weighed as photocatalysts and added to reaction flasks along with thiobenzamide (68.6 mg, 0.5 mmol) and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flasks were placed in a constant-temperature reactor and maintained at 25°C with continuous stirring. A 30 W white LED lamp was used as the photocatalytic reaction source to irradiate the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of irradiation, the photocatalyst and reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds. 1 H NMR image attached Figure 6As shown in Table 1, the yields of 1,2,4-thiadiazole compounds were calculated (yield of 1,2,4-thiadiazole compounds = moles of dried 1,2,4-thiadiazole compounds × 2 ÷ moles of reactant thiobenzamide × 100%).

[0113] Table 1

[0114]

[0115] Application Example 2

[0116] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0117]

[0118] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with 75.6 mg (0.5 mmol) of 4-methylthiobenzamide and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant-temperature reactor and kept at 25°C with continuous stirring. A 30 W white LED lamp was used as the photocatalytic reaction source to irradiate the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of irradiation, the photocatalyst and reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds with a yield of 83%.

[0119] Application Example 3

[0120] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0121]

[0122] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with 83.6 mg (0.5 mmol) of 4-methoxythiobenzamide and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant-temperature reactor and kept at 25°C with continuous stirring. A 30 W white LED lamp was used as the photocatalytic reaction source to irradiate the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of irradiation, the photocatalyst and reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds with a yield of 82%.

[0123] Application Example 4

[0124] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0125]

[0126] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with 76.6 mg (0.5 mmol) of 4-hydroxythiobenzamide and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant-temperature reactor and kept at 25°C with continuous stirring. A 30 W white LED lamp was used as the photocatalytic reaction source to irradiate the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of irradiation, the photocatalyst and reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds, with a yield of 39%.

[0127] Application Example 5

[0128] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0129]

[0130] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with 102.6 mg (0.5 mmol) of 4-trifluoromethylthiobenzamide and 5 mL of chloroform. The mixture was ultrasonically dispersed (240 W) for 10 minutes and then placed in a constant-temperature reactor. The reactor was maintained at 25°C with continuous stirring, and a 30 W white LED lamp was used as the photocatalytic reaction source to irradiate the dispersion. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of irradiation, the photocatalyst and reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds, with a yield of 60%.

[0131] Application Example 6

[0132] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0133]

[0134] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with 71.6 mg (0.5 mmol) of thiophene 2-thioformamide and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant-temperature reactor and kept at 25°C with continuous stirring. A 30 W white LED lamp was used as the photocatalytic reaction source to irradiate the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of irradiation, the photocatalyst and reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds with a yield of 91%.

[0135] Application Example 7

[0136] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0137]

[0138] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with 77.6 mg (0.5 mmol) of 4-fluorothiobenzamide and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant-temperature reactor and kept at 25°C with continuous stirring. A 30 W white LED lamp was used as the photocatalytic reaction source to irradiate the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of irradiation, the photocatalyst and reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds, with a yield of 59%.

[0139] Application Example 8

[0140] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0141]

[0142] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with 85.8 mg (0.5 mmol) of 4-chlorothiobenzamide and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant-temperature reactor and kept at 25°C with continuous stirring. A 30 W white LED lamp was used as the photocatalytic reaction source to irradiate the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of irradiation, the photocatalyst and reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds, with a yield of 50%.

[0143] Application Example 9

[0144] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0145]

[0146] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with 108 mg (0.5 mmol) of 4-bromothiobenzamide and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant-temperature reactor and kept at 25°C with continuous stirring. A 30 W white LED lamp was used as the photocatalytic reaction source to irradiate the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of irradiation, the photocatalyst and reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds, with a yield of 43%.

[0147] Application Example 10

[0148] The perylene diimide porous organic polymer prepared in Example 2 above was used as a photocatalyst, and the white light was replaced with blue light. All other operations were the same as in Application Example 1.

[0149] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0150]

[0151] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with thiobenzamide (68.6 mg, 0.5 mmol) and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant temperature reactor and kept at 25 °C with continuous stirring. A 30 W blue LED lamp was used as the photocatalytic reaction light source to catalyze the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of illumination, the photocatalyst and the reaction solution were separated by centrifugation. The reaction solution was separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds with a yield of 29%.

[0152] Application Example 11

[0153] The perylene diimide porous organic polymer prepared in Example 2 above was used as a photocatalyst, and the white light was replaced with red light. All other operations were the same as in Application Example 1.

[0154] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0155]

[0156] 10.4 mg of the perylene diimide porous organic polymer prepared in Example 2 was weighed as a photocatalyst and added to a reaction flask along with thiobenzamide (68.6 mg, 0.5 mmol) and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant temperature reactor and kept at 25°C with continuous stirring. A 30 W red LED lamp was used as the photocatalytic reaction light source to catalyze the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of illumination, the photocatalyst and the reaction solution were separated by centrifugation. The reaction solution was separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compound with a yield of 18%.

[0157] Compare with application example 1

[0158] The monomer 1,7-bis(9H-carbazole-9-yl)phenyl[3-(dimethylamino)propyl]-perylenediimide, which was used before crosslinking polymerization in Example 2 above, was used as a photocatalyst, and the white light was replaced with blue light. All other operations were the same as in Application Example 1.

[0159] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0160]

[0161] 10.4 mg of 1,7-bis(9H-carbazole-9-yl)phenyl[3-(dimethylamino)propyl]-perylenediimide was weighed as a photocatalyst and added to a reaction flask along with thiobenzamide (68.6 mg, 0.5 mmol) and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant-temperature reactor and kept at 25 °C with continuous stirring. A 30 W blue LED lamp was used as the photocatalytic reaction light source to catalyze the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of illumination, the photocatalyst and the reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds with a yield of 25%.

[0162] Compare with application example 2

[0163] The monomer 1,7-bis(9H-carbazole-9-yl)phenyl[3-(dimethylamino)propyl]-perylenediimide, which was used before crosslinking polymerization in Example 2 above, was used as a photocatalyst, and the rest of the operation was the same as in Application Example 1 (also irradiated with white light).

[0164] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0165]

[0166] 10.4 mg of 1,7-bis(9H-carbazole-9-yl)phenyl[3-(dimethylamino)propyl]-perylenediimide was weighed as a photocatalyst and added to a reaction flask along with thiobenzamide (68.6 mg, 0.5 mmol) and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant temperature reactor and kept at 25 °C with continuous stirring. A 30 W white LED lamp was used as the photocatalytic reaction light source to catalyze the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of illumination, the photocatalyst and the reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds with a yield of 34%.

[0167] Compare with application example 3

[0168] The monomer 1,7-bis(9H-carbazole-9-yl)phenyl[3-(dimethylamino)propyl]-perylenediimide, which was used before crosslinking polymerization in Example 2 above, was used as a photocatalyst, and the white light was replaced with red light. All other operations were the same as in Application Example 1.

[0169] The photocatalytic synthesis of 1,2,4-thiadiazole compounds follows the following synthetic route:

[0170]

[0171] 10.4 mg of 1,7-bis(9H-carbazole-9-yl)phenyl[3-(dimethylamino)propyl]-perylenediimide was weighed as a photocatalyst and added to a reaction flask along with thiobenzamide (68.6 mg, 0.5 mmol) and 5 mL of chloroform. After ultrasonic dispersion for 10 minutes at 240 W, the flask was placed in a constant temperature reactor and kept at 25 °C with continuous stirring. A 30 W red LED lamp was used as the photocatalytic reaction light source to catalyze the dispersion system in the reactor. Thin-layer chromatography (TLC) was used to monitor the reaction. After 8 hours of illumination, the photocatalyst and the reaction solution were separated by centrifugation. The reaction solution was then separated by silica gel column chromatography to obtain the product 1,2,4-thiadiazole compounds with a yield of 4%.

[0172] The above application examples 1 (the photocatalyst prepared in Example 2), 10, 11, control application example 1, control application example 2, and control application example 3 are summarized in Table 2:

[0173] Table 2

[0174]

[0175] As shown in the table above, when used for photocatalysis before monomer polymerization, the photocatalytic yield reaches 34% under mixed light (white light) irradiation, while the photocatalytic yield reaches 25% when irradiated with blue light alone, accounting for most of the effectiveness of mixed light and white light. Therefore, the light absorption range of this monomer before polymerization is mainly in the blue light band.

[0176] After self-crosslinking polymerization, the photocatalytic yield under blue light irradiation was 29%, a relatively limited improvement compared to photocatalysis in its monomeric state. However, the photocatalytic yield under white light irradiation increased significantly to 93%. Further testing revealed that the photocatalytic yield of this polymer under red light alone reached 18%. Therefore, it is believed that the self-crosslinking polymerization of these monomers resulted in a significant red shift, effectively increasing the absorption range of light wavelengths for the catalyst and improving light utilization.

Claims

1. A photocatalytic application of a porous organic polymer, characterized in that: The porous organic polymer is a cross-linked polymer based on perylene diimide derivatives, wherein the molecular structure of the perylene diimide derivatives is as follows: ， R is one of triphenylamine, carbazole, pyrrole, thiophene, benzene, quinoline, indole, phenothiazine, and tetra(2-thienyl)ethylene. The porous organic polymer is used as a photocatalyst to photocatalytically oxidize and cyclize thiobenzamide compounds into 1,2,4-thiadiazole compounds.

2. The photocatalytic application of the porous organic polymer as described in claim 1, characterized in that: The amount of the porous organic polymer used for catalysis is 1% of the molar number of the thiobenzamide compound.

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