A porous polymer based on sulfur-containing group element porphyrin, a synthesis method and red light catalytic applications thereof

Abstract

This invention discloses a porous polymer based on porphyrins containing chalcogenides, its synthesis method, and its red photocatalytic application, belonging to the field of organic photocatalytic materials. The porous polymer has one of the following structural formulas: The synthetic method uses 5,10,15,20-tetra(4-bromophenyl)porphyrin and dithienro[3,2-b:2',3'-d]thiophene or dithienro[3,2-b:2',3']thiophene-4,4-dioxide as raw materials, and synthesizes them through a direct arylation reaction. The synthesized porous polymer exhibits good photocatalytic performance and can carry out catalytic reactions under red light. It can be used as a photocatalyst for coupling reactions and C-H arylation reactions of diazonium salts. This invention provides a simple, effective, and feasible new route and approach for the design and development of red photocatalysts.

Description

A porous polymer based on porphyrins containing chalcogenides, its synthesis method and its red photocatalytic application Technical Field

[0001] This invention belongs to the field of organic photocatalytic materials, specifically relating to a porous polymer based on porphyrin containing chalcogens, its synthesis method, and its red photocatalytic application. Background Technology

[0002] Photocatalysis induced by low-energy red light has significant value in various biological and biomedical processes. Photochemical reactions using photocatalysts induced by low-energy red light can achieve organic reactions under mild conditions, suppress undesirable side reactions, and offer a wide range of substrates and good functional group tolerance. Numerous reports exist on photocatalytic organic transformation, primarily because photocatalysis is a catalytic method that uses light energy to drive chemical reactions, and its green catalytic properties make it valuable in research. However, the light sources used in photocatalysis are mainly ultraviolet and blue light, which share several major drawbacks: (i) high-energy light sources may pose health risks. For example, blue light can cause photooxidative damage to the human retina. (ii) short-wavelength photons are more easily absorbed by complex substrates or products with extended π systems, leading to more likely unintended side reactions or background reactions. (iii) short-wavelength light sources have limited penetration depth into turbid media such as reaction mixtures and tissues, restricting their application in industry and biomedicine. To overcome these limitations, researchers have turned their attention to long-wavelength red light. Red light possesses advantages such as lower energy, lower health risks, fewer side reactions, higher abundance in sunlight, and, most importantly, greater penetration depth into various media. Therefore, red light photocatalysis can serve as an alternative to ultraviolet and blue light photocatalysis, offering the advantage of being milder. Thus, the development of red light-based photocatalysts remains of great significance.

[0003] Photocatalytic heterogeneous organic conversion, as an eco-friendly and sustainable method, can effectively address persistent energy and environmental challenges. Materials based on porous organic polymers (POPs) have recently emerged as ideal photocatalysts for various organic conversions, providing a sustainable alternative to homogeneous systems relying on noble metal inorganics or organic dyes. Although there are numerous reports on the application of POPs in photocatalytic organic conversion, research reports on the application of porous organic polymers in photochemical conversion under red light, as highly promising red-light-based photocatalysts, are still lacking. Therefore, in-depth research on photocatalytic organic conversion using POPs under red light irradiation has become an urgent task.

[0004] In recent years, extensive research has been conducted on the photoresponsive behavior of polymeric organic compounds (POPs), providing valuable insights into their ability to generate charge separation under illumination. To enhance the photocatalytic activity of polymers, researchers have reported numerous effective control strategies, including adjusting the type and orientation of bonding bonds, altering the bonding positions of monomers, regulating the doping of heteroatoms such as nitrogen and oxygen, and other strategies. These efforts have demonstrated that subtle changes in polymer composition and structure play a crucial role in the photocatalytic process. However, there are few reports on bandgap engineering of POPs by adjusting the oxidation state of sulfur.

[0005] Porphyrins are a class of natural organic dyes. Due to their strong light absorption, excellent photochemical stability, and easily modifiable structure, they have become high-performance photosensitizer molecules with wide applications in photocatalysis, photothermal therapy, and antibacterial fields. In recent years, POPs with porphyrin as their core structure have attracted widespread attention. Furthermore, theoretically, incorporating thiophene derivatives into POPs can effectively reduce the polymer's band gap, causing its absorption wavelength to redshift towards longer wavelengths. Summary of the Invention

[0006] In view of the fact that the light sources used in existing porous organic polymer photocatalysis are mainly ultraviolet and blue light, and there are few reports on photocatalytic organic conversion initiated by low-energy red light, this invention aims to provide a porous polymer based on porphyrin containing chalcogens, its synthesis method and its red photocatalytic application.

[0007] To achieve the above objectives, the present invention employs the following technical solution:

[0008] This invention provides a porous polymer based on porphyrins containing chalcogenides, the porous polymers being named Pro-DTT and Pro-DTDO, respectively, and their corresponding structural formulas are as follows:

[0009]

[0010] The Pro-DTT was synthesized by the following method: 5,10,15,20-tetrakis(4-bromophenyl)porphyrin was directly arylated with dithiopheno[3,2-b:2',3'-d]thiophene.

[0011] The Pro-DTDO was synthesized by the following method: direct arylation reaction of 5,10,15,20-tetra(4-bromophenyl)porphyrin with dithieno[3,2-b:2',3']thiophene-4,4-dioxide.

[0012] The specific synthesis process of Pro-DTT is as follows: 5,10,15,20-tetra(4-bromophenyl)porphyrin and dithiophene[3,2-b:2',3'-d]thiophene are added to a flask, along with pentanoic acid, anhydrous potassium carbonate, tris(2-methoxyphenyl)phosphine, and tris(dibenzylacetone)dipalladium(0); under nitrogen protection, anhydrous 1,2-dimethylbenzene is added to the solid mixture; after ultrasonic deoxygenation and stirring, the mixture is cooled to room temperature, precipitated, washed, filtered, and vacuum dried to obtain Pro-DTT;

[0013] The specific synthesis process of Pro-DTDO is as follows: 5,10,15,20-tetra(4-bromophenyl)porphyrin and dithiophene[3,2-b:2',3']thiophene-4,4-dioxide are added to a flask, along with pentanoic acid, anhydrous potassium carbonate, tris(2-methoxyphenyl)phosphine and tris(dibenzylideneacetone)dipalladium(0); under nitrogen protection, anhydrous 1,2-dimethylbenzene is added to the solid mixture; after ultrasonic deoxygenation and stirring, the mixture is cooled to room temperature, precipitated, washed, filtered, and vacuum dried to obtain Pro-DTDO.

[0014] The synthesis process of the dithiopheno[3,2-b:2',3']thiophene 4,4-dioxide is as follows:

[0015] Dithienro[3,2-b:2',3'-d]thiophene and anhydrous dichloromethane were added sequentially to a round-bottom flask and stirred at room temperature. 3-Chloroperoxybenzoic acid was uniformly dissolved in anhydrous dichloromethane. Then, the anhydrous dichloromethane containing dissolved 3-chloroperoxybenzoic acid was slowly added dropwise to the round-bottom flask using a syringe and stirred. The mixture was washed with potassium carbonate aqueous solution and then extracted with anhydrous dichloromethane for pretreatment. The collected organic phase was dried with anhydrous sodium sulfate and the solvent was removed by a rotary evaporator under reduced pressure. The crude product was further purified by column chromatography to obtain an orange-yellow solid, which was the target product, dithienro[3,2-b:2',3']thiophene-4,4-dioxide.

[0016] The molar ratio of dithiopheno[3,2-b:2',3'-d]thiophene to 3-chloroperoxybenzoic acid is 1:3; the stirring reaction time is 30 hours, and the reaction temperature is 25℃.

[0017] In the synthesis method of Pro-DTT, the molar ratio of 5,10,15,20-tetra(4-bromophenyl)porphyrin to dithienro[3,2-b:2',3'-d]thiophene is 1:2, and the reaction solvent is anhydrous 1,2-dimethylbenzene; in the synthesis method of Pro-DTDO, the molar ratio of 5,10,15,20-tetra(4-bromophenyl)porphyrin to dithienro[3,2-b:2',3']thiophene-4,4-dioxide is 1:2, and the reaction solvent is anhydrous 1,2-dimethylbenzene.

[0018] The stirring reaction conditions in the synthesis method of Pro-DTT are: 100℃, 72 hours; the stirring reaction conditions in the synthesis method of Pro-DTDO are: 100℃, 72 hours.

[0019] In the method for synthesizing the porous polymer, the solvent used for washing is any one of methanol, water, or dichloromethane.

[0020] Application of the porous polymer in red photocatalytic coupling reaction.

[0021] Application of the porous polymer in the red photocatalytic arylation reaction of furan with diazonium salt.

[0022] Application of the porous polymer in the red photocatalytic arylation reaction of coumarin with diazonium salt.

[0023] Application of the porous polymer in the red photocatalytic arylation reaction of thiophenols and diazonium salts.

[0024] Application of the porous polymer in the red photocatalytic arylation reaction of diselenide and diazonium salt.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The porous polymers Pro-DTT and Pro-DTDO, based on porphyrins containing chalcogenides, disclosed in this invention, exhibit red photocatalytic effects. Pro-DTDO enhances the dipole moment of the polymer by regulating the oxidation state of sulfur in the monomer, thereby enhancing the separation and transport of photogenerated charge carriers in the polymer. This facilitates the accumulation of more energy and charge during the photocatalytic process, thereby improving the reaction rate and yield, making it a promising candidate for a wide range of applications in the field of photocatalysis. It also shows excellent performance in red photocatalytic coupling reactions and the arylation reactions of furan, coumarin, thiophenol, and diselenide with diazonium salts. Attached Figure Description

[0027] Figure 1 is a flowchart of the synthesis process of the porous polymer of the present invention;

[0028] Figure 2 is the Fourier transform infrared spectrum of the porous polymer described in this invention;

[0029] Figure 3 is a thermogravimetric analysis curve of the porous polymer described in this invention;

[0030] Figure 4 is a scanning electron microscope image of the porous polymer synthesized in Example 1 of the present invention;

[0031] Figure 5 is an X-ray powder diffraction pattern of the porous polymer described in this invention;

[0032] Figure 6 is an electrochemical impedance spectroscopy diagram of the porous polymer described in this invention;

[0033] Figure 7 is a photocurrent diagram of the porous polymer described in this invention;

[0034] Figure 8 is a mechanism diagram of the photocatalytic cross-dehydrogenation coupling reaction of the porous polymer Pro-DTT described in this invention.

[0035] Figure 9 is a mechanism diagram of the photocatalytic cross-dehydrogenation coupling reaction of the porous polymer Pro-DTDO described in this invention. Detailed Implementation

[0036] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0037] Example 1

[0038] This embodiment is an example of the synthesis method of the porous polymer described in this invention.

[0039] The synthetic process of the porous polymers described in this invention is shown in Figure 1. This invention relates to two compounds, one named Pro-DTT and the other named Pro-DTDO. The synthetic processes of these two porous polymers are described in detail below.

[0040] 1. Synthesis of Pro-DTT

[0041] 5,10,15,20-tetra(4-bromophenyl)porphyrin (Pro) (233.0 mg, 0.25 mmol) was added to a flask along with dithieno[3,2-b:2',3'-d]thiophene (DTT) (98.0 mg, 0.5 mmol), terpentine (30.6 mg, 0.3 mmol), anhydrous potassium carbonate (207.3 mg, 1.5 mmol), tris(2-methoxyphenyl)phosphine (10.6 mg, 0.03 mmol), and tris(dibenzylideneacetone)dipalladium(O) (13.7 mg, 0.015 mmol). Under nitrogen protection, anhydrous 1,2-dimethylbenzene (5 mL) was added to the solid mixture. The mixture was then subjected to repeated sonication to remove oxygen. The reaction was stirred at 100℃ for 72 hours. After the reaction, the mixture was cooled to room temperature, and the precipitate was collected, washed, filtered, and vacuum dried to obtain a porous polymer based on porphyrins containing chalcogenides. This porous polymer was named Pro-DTT, and the product was a purplish-brown powder. The synthesis process is shown in the upper part of Figure 1.

[0042] The reaction equation is as follows:

[0043]

[0044] 2. Synthesis of Pro-DTDO

[0045] (1) Preparation of dithiopheno[3,2-b:2',3']thiophene-4,4-dioxide (DTDO):

[0046] Please refer to Figure 1 (lower left) for the structural formula of DTDO. The preparation method is as follows: Dithienro[3,2-b:2',3'-d]thiophene (DTT) (588.9 mg, 3.0 mmol) and anhydrous dichloromethane (3 mL) are added sequentially to a round-bottom flask and stirred at 25°C.

[0047] 3-Chloroperoxybenzoic acid was uniformly dissolved in anhydrous dichloromethane. Then, a solution of 18 mL of anhydrous dichloromethane containing 1554.0 mg (9.0 mmol) of 3-chloroperoxybenzoic acid was slowly added dropwise to the round-bottom flask using a syringe, and the mixture was stirred at 25°C for 30 hours. The mixture was then pretreated by washing with potassium carbonate aqueous solution and extracting with anhydrous dichloromethane. The collected organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure. The crude product was further purified by column chromatography to obtain a yellow solid, DTDO. The reaction process is as follows:

[0048]

[0049] (2) Synthesis of Pro-DTDO

[0050] 5,10,15,20-tetra(4-bromophenyl)porphyrin (Pro) (233.0 mg, 0.25 mmol) was added to a flask along with dithieno[3,2-b:2',3']thiophene-4,4-dioxide (DTDO) (114.2 mg, 0.5 mmol), pentyl acid (30.6 mg, 0.3 mmol), anhydrous potassium carbonate (207.3 mg, 1.5 mmol), tris(2-methoxyphenyl)phosphine (10.6 mg, 0.03 mmol), and tris(dibenzylideneacetone)dipalladium(O) (13.7 mg, 0.015 mmol). Under nitrogen protection, anhydrous 1,2-dimethylbenzene (5 mL) was added to the solid mixture. The mixture was then subjected to repeated sonication to remove oxygen. The reaction was stirred at 100℃ for 72 hours. After the reaction, the mixture was cooled to room temperature, and a precipitate was formed. The precipitate was collected, washed, filtered, and vacuum dried to obtain Pro-DTDO, a porous polymer based on porphyrins containing chalcogenides. The product was a dark brown powder. The synthesis process is shown in the lower half of Figure 1.

[0051] The reaction equation is as follows:

[0052]

[0053] Figure 2 shows the Fourier transform infrared spectra of Pro-DTT and Pro-DTDO of the present invention. Both polymers contain the NH stretching vibration (3315 cm⁻¹) of the pyrrole ring of porphyrin. -1 ) and in-plane rocking vibration of NH (960 cm) -1 This indicates that both contain porphyrin structures; furthermore, Pro-DTT exhibits CS tensile vibration (1310 cm⁻¹). -1 Pro-DTDO contains sulfone stretching vibrations (1310 cm⁻¹). -1 1135cm -1 The presence of dithiophene[3,2-b:2',3'-d]thiophene and dithiophene[3,2-b:2',3']thiophene-4,4-dioxide indicates that they contain dithiophene[3,2-b:2',3']thiophene-4,4-dioxide, respectively.

[0054] Figure 3 shows the thermogravimetric curves of the sulfur-containing porphyrin porous polymers Pro-DTT and Pro-DTDO of this invention. The thermogravimetric curves describe the change in sample mass as the temperature increases. As can be seen from Figure 3, as the temperature gradually increases, Pro-DTT and Pro-DTDO show significant weight loss at 400℃. The sample mass gradually decreases with increasing temperature, indicating that Pro-DTT and Pro-DTDO have good thermal stability.

[0055] Figure 4 shows the scanning electron microscope test results of Pro-DTT and Pro-DTDO synthesized using the method of Example 1. It can be seen from the figure that both exhibit irregular granular structures with uneven size.

[0056] Figure 5 shows the X-ray powder diffraction patterns of the porous polymers Pro-DTT and Pro-DTDO described in this invention. As can be seen from the figure, there are no obvious diffraction peaks, indicating that both Pro-DTT and Pro-DTDO are amorphous structures.

[0057] Figure 6 shows the electrochemical impedance spectroscopy of the sulfur-containing porphyrin porous polymers Pro-DTT and Pro-DTDO of the present invention. As can be seen from Figure 6, Pro-DTDO has a smaller Nyquist plot radius, indicating that it has a smaller impedance and is more conducive to charge separation.

[0058] Figure 7 shows the photocurrent of the sulfur-containing porphyrin porous polymers Pro-DTT and Pro-DTDO of the present invention. It can be seen from the figure that Pro-DTDO has a stronger photocurrent than Pro-DTT, indicating that Pro-DTDO can generate more photoinduced carriers.

[0059] Example 2

[0060] The specific process of the photocatalytic coupling reaction based on the synthesized Pro-DTT and Pro-DTDO is as follows:

[0061] 1. Photocatalytic coupling reaction of Pro-DTT

[0062] The photocatalytic coupling reaction was carried out using Pro-DTT prepared in Example 1: 41.8 mg (0.2 mmol) of N-phenyl-tetrahydroisoquinoline, ethyl diazonate (0.6 mmol, 3.0 eq) and Pro-DTT (5.0 mg) were mixed in 1 mL of dichloromethane and stirred under a red LED lamp at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as the eluent to obtain the target product.

[0063] The reaction equation is as follows:

[0064]

[0065] 2. Photocatalytic coupling reaction of Pro-DTDO

[0066] The photocatalytic coupling reaction was carried out using Pro-DTDO prepared in Example 1: 41.8 mg (0.2 mmol) of N-phenyl-tetrahydroisoquinoline, ethyl diazonate (0.6 mmol, 3.0 eq) and Pro-DTDO (5.0 mg) were mixed in 1 mL of dichloromethane and stirred under a red LED lamp at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as the eluent to obtain the target product.

[0067] The reaction equation is as follows:

[0068]

[0069] Example 3

[0070] This example demonstrates the photocatalytic arylation reaction of furan with diazonium salts based on synthesized Pro-DTT and Pro-DTDO.

[0071] 1. Photocatalytic arylation reaction of furan with diazonium salt by Pro-DTT

[0072] The photocatalytic arylation reaction of furan and diazonium salt was carried out using Pro-DTT prepared in Example 1: 45.2 mg (0.2 mmol) of diazonium salt, furan (0.4 mmol, 2.0 eq) and Pro-DTT (5.0 mg) were mixed in 1 mL of dimethyl sulfoxide and stirred under a red LED lamp at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as the eluent to obtain the target product.

[0073] The reaction equation is as follows:

[0074]

[0075] 2. Photocatalytic arylation reaction of pro-DTDO with furan and diazonium salt

[0076] The photocatalytic arylation reaction of furan and diazonium salt was carried out using Pro-DTDO prepared in Example 1: 45.2 mg (0.2 mmol) of diazonium salt, furan (0.4 mmol, 2.0 eq) and Pro-DTDO (5.0 mg) were mixed in 1 mL of dimethyl sulfoxide and stirred under red LEDs at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as eluent to obtain the target product.

[0077] The reaction equation is as follows:

[0078]

[0079] Example 4

[0080] This example is based on the photocatalytic arylation reaction of synthesized Pro-DTT and Pro-DTDO coumarin with diazonium salts.

[0081] 1. Photocatalytic arylation reaction of coumarin with diazonium salt using Pro-DTT

[0082] The photocatalytic arylation reaction of coumarin with diazonium salt was carried out using Pro-DTT prepared in Example 1: 45.2 mg (0.2 mmol) of diazonium salt, coumarin (0.4 mmol, 2.0 eq) and Pro-DTT (5.0 mg) were mixed in 1 mL of dimethyl sulfoxide and stirred under a red LED lamp at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as eluent to obtain the target product.

[0083] The reaction equation is as follows:

[0084]

[0085] 2. Photocatalytic arylation reaction of pro-DTDO with coumarin and diazonium salt

[0086] The photocatalytic arylation reaction of coumarin with diazonium salt was carried out using Pro-DTDO prepared in Example 1: 45.2 mg (0.2 mmol) of diazonium salt, coumarin (0.4 mmol, 2.0 eq) and Pro-DTDO (5.0 mg) were mixed in 1 mL of dimethyl sulfoxide and stirred under a red LED lamp at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as the eluent to obtain the target product.

[0087] The reaction equation is as follows:

[0088]

[0089] Example 5

[0090] This example is based on the photocatalytic arylation reaction of thiophenols and diazonium salts using synthesized Pro-DTT and Pro-DTDO.

[0091] 1. Photocatalytic arylation reaction of thiophenols and diazonium salts using Pro-DTT

[0092] The photocatalytic arylation reaction of thiophenols with diazonium salts was carried out using Pro-DTT prepared in Example 1:

[0093] 45.2 mg (0.2 mmol) of diazonium salt, thiophenol (0.4 mmol, 2.0 eq), and Pro-DTT (5.0 mg) were mixed in 1 mL of dimethyl sulfoxide and stirred under red LEDs at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as the eluent to obtain the target product.

[0094] The reaction equation is as follows:

[0095]

[0096] 2. Photocatalytic arylation reaction of thiophenols and diazonium salts using Pro-DTDO

[0097] The Pro-DTDO prepared in Example 1 was used for the photocatalytic arylation reaction of thiophenols with diazonium salts:

[0098] 45.2 mg (0.2 mmol) of diazonium salt, thiophenol (0.4 mmol, 2.0 eq), and Pro-DTDO (5.0 mg) were mixed in 1 mL of dimethyl sulfoxide and stirred under red LEDs at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as the eluent to obtain the target product.

[0099] The reaction equation is as follows:

[0100]

[0101] Example 6

[0102] This example is based on the arylation reaction of the synthesized photocatalytic diselenide compounds Pro-DTT and Pro-DTDO with diazonium salts.

[0103] 1. Photocatalytic arylation reaction of diselenide compounds with diazonium salts by Pro-DTT:

[0104] The photocatalytic arylation reaction of diselenide compound with diazonium salt was carried out using Pro-DTT prepared in Example 1: 45.2 mg (0.2 mmol) of diazonium salt, diselenide (0.4 mmol, 2.0 eq) and Pro-DTT (5.0 mg) were mixed in 1 mL of dimethyl sulfoxide and stirred under a red LED lamp at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as eluent to obtain the target product.

[0105] The reaction equation is as follows:

[0106]

[0107] 2. The Pro-DTDO prepared in Example 1 was used for the photocatalytic arylation reaction of diselenide compounds with diazonium salts:

[0108] 45.2 mg (0.2 mmol) of diazonium salt, diselenide (0.4 mmol, 2.0 eq), and Pro-DTDO (5.0 mg) were mixed in 1 mL of dimethyl sulfoxide and stirred under red LEDs at 640-660 nm for 24 hours. The solvent was removed by rotary evaporation, and the product was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (50 / 1) as the eluent to obtain the target product.

[0109] The reaction equation is as follows:

[0110]

[0111] Figure 8 illustrates the photocatalytic mechanism of the porous polymer Pro-DTT described in this invention:

[0112] Photoexcitation process: When the porous polymer Pro-DTT described in this invention is irradiated with red light, the energy of these photons is absorbed by the polymer, causing its electrons to transition from the ground state to the excited state. This is the initial step of the photocatalytic reaction, which enables the polymer to have the energy and activity required for subsequent chemical reactions.

[0113] Free radical generation: When a polymer is excited to an excited state, the electron distribution inside it changes, forming free radicals;

[0114] Electron transfer process: The generated free radicals then transfer electrons to the catalytic substrate, which is the core step in the photocatalytic reaction and determines the reaction rate and the type of product. In the system of sulfur-containing porphyrin porous polymers, electrons are rapidly transferred to the catalytic substrate through polymer chains or pore structures.

[0115] The completion of the catalytic process: During the transfer and conversion of electrons, the catalytic substrate undergoes a redox reaction to generate the desired product, thus completing the entire catalytic process.

[0116] Figure 9 illustrates the photocatalytic mechanism of the porous polymer Pro-DTDO described in this invention:

[0117] Photoexcitation process: When the porous polymer Pro-DTDO described in this invention is irradiated with red light, the energy of these photons is absorbed by the polymer, causing its electrons to transition from the ground state to the excited state. This is the initial step of the photocatalytic reaction, which enables the polymer to have the energy and activity required for subsequent chemical reactions.

[0118] Free radical generation: When a polymer is excited to an excited state, the electron distribution inside it changes, forming free radicals;

[0119] Electron transfer process: The generated free radicals then transfer electrons to the catalytic substrate, which is the core step in the photocatalytic reaction and determines the reaction rate and the type of product. In the system of sulfur-containing porphyrin porous polymers, electrons are rapidly transferred to the catalytic substrate through polymer chains or pore structures.

[0120] The completion of the catalytic process: During the transfer and conversion of electrons, the catalytic substrate undergoes a redox reaction to generate the desired product, thus completing the entire catalytic process.

[0121] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A porous polymer based on porphyrins containing chalcogenides, characterized in that, The porous polymers are named Pro-DTT and Pro-DTDO, and their corresponding structural formulas are as follows: 。 2. The porous polymer according to claim 1, characterized in that, The Pro-DTT was synthesized by the following method: 5,10,15,20-tetra(4-bromophenyl)porphyrin was directly arylated with dithieno[3,2-b:2',3'-d]thiophene; the Pro-DTDO was synthesized by the following method: 5,10,15,20-tetra(4-bromophenyl)porphyrin was directly arylated with dithieno[3,2-b:2',3']thiophene-4,4-dioxide.

3. The method for synthesizing the porous polymer according to claim 1, characterized in that, The specific synthesis process is as follows: The synthesis process of Pro-DTT is as follows: 5,10,15,20-tetra(4-bromophenyl)porphyrin and dithiophene[3,2-b:2',3'-d]thiophene are added to a flask, along with pentanoic acid, anhydrous potassium carbonate, tris(2-methoxyphenyl)phosphine, and tris(dibenzylacetone)dipalladium(O); under nitrogen protection, anhydrous 1,2-dimethylbenzene is added to the solid mixture; after ultrasonic deoxygenation and stirring, the mixture is cooled to room temperature, precipitated, washed, filtered, and vacuum dried to obtain Pro-DTT; The synthesis process of Pro-DTDO is as follows: 5,10,15,20-tetra(4-bromophenyl)porphyrin and dithiophene[3,2-b:2',3']thiophene-4,4-dioxide are added to a flask, along with pentanoic acid, anhydrous potassium carbonate, tris(2-methoxyphenyl)phosphine and tris(dibenzylideneacetone)dipalladium(0); under nitrogen protection, anhydrous 1,2-dimethylbenzene is added to the solid mixture; after ultrasonic deoxygenation and stirring, the mixture is cooled to room temperature, precipitated, washed, filtered, and vacuum dried to obtain Pro-DTDO.

4. The method for synthesizing the porous polymer according to claim 3, characterized in that, In the synthesis of Pro-DTT, the molar ratio of 5,10,15,20-tetra(4-bromophenyl)porphyrin to dithienro[3,2-b:2',3'-d]thiophene is 1:2, and the reaction solvent is anhydrous 1,2-dimethylbenzene; in the synthesis of Pro-DTDO, the molar ratio of 5,10,15,20-tetra(4-bromophenyl)porphyrin to dithienro[3,2-b:2',3']thiophene-4,4-dioxide is 1:2, and the reaction solvent is anhydrous 1,2-dimethylbenzene.

5. The method for synthesizing the porous polymer according to claim 3, characterized in that, The stirring reaction conditions during the synthesis of Pro-DTT were: 100℃ for 72 hours; the stirring reaction conditions during the synthesis of Pro-DTDO were: 100℃ for 72 hours.

6. The application of the porous polymer according to claim 1 in red photocatalytic coupling reaction.

7. The application of the porous polymer according to claim 1 in the red photocatalytic arylation reaction of furan with diazonium salt.

8. The application of the porous polymer according to claim 1 in the red photocatalytic arylation reaction of coumarin with diazonium salt.

9. The application of the porous polymer according to claim 1 in the red light-catalyzed arylation reaction of thiophenol with diazonium salt or the arylation reaction of diselenide with diazonium salt.

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