A dihydrophenazine porous organic polymer photocatalyst and a preparation method and application thereof

Abstract

The application discloses a dihydrophenazine porous organic polymer photocatalyst and a preparation method and application thereof. The dihydrophenazine porous organic polymer photocatalyst is obtained by the following steps: subjecting a dihydrophenazine vinyl monomer and a bipyridine vinyl monomer to a free radical polymerization reaction, and then subjecting the reaction product to coordination with a nickel salt. The preparation method is simple, and the dihydrophenazine porous organic polymer photocatalyst is a high-efficiency heterogeneous catalyst. The dihydrophenazine porous organic polymer photocatalyst can be used as a photocatalyst for C-P bond coupling reaction, and can catalyze the C-P bond coupling reaction under relatively mild conditions. The reaction has the advantages of mild conditions, wide substrate application range, green sustainability and the like.

Description

Technical Field

[0001] This invention belongs to the field of organic photocatalyst technology, specifically relating to a dihydrophenazine-based porous organic polymer photocatalyst, its preparation method, and its application. Background Technology

[0002] Light energy is an inexhaustible, environmentally friendly, and sustainable resource, highly favored by chemists. Over the past decade, photo-redox catalysis has received widespread attention as a powerful synthetic strategy for achieving complex chemical transformations. However, most organic compounds cannot absorb visible light, requiring photocatalysts to act as light absorption media to realize the conversion of light energy into chemical energy.

[0003] Currently, the most commonly used photocatalysts are transition metal complexes and organic dyes. Although these catalysts have excellent catalytic activity and high conversion rates, their high price, high toxicity, unavoidable metal leaching, complicated product purification processes, poor stability, and limited reusability have hindered their practical application in large-scale organic synthesis.

[0004] In recent years, porous organic polymer (POPs) catalysts have emerged as a novel type of heterogeneous organic photocatalyst, possessing advantages such as high specific surface area, low density, good stability, and uniform pore size. Due to their recyclability and reusability, they can not only eliminate the pollution of organic products by trace amounts of homogeneous photocatalysts but also simplify processing and purification steps in large-scale reactions, demonstrating strong application prospects. However, existing porous organic polymer catalysts have complex preparation processes, demanding application conditions, and a narrow range of applicable substrates. Summary of the Invention

[0005] One of the objectives of this invention is to provide a dihydrophenazine-based porous organic polymer photocatalyst and its preparation method. The preparation method is simple, and it is a highly efficient heterogeneous catalyst that can construct CP bonds at room temperature. The reaction has the advantages of mild conditions, wide substrate applicability, and green sustainability.

[0006] The second objective of this invention is to provide an application of a dihydrophenazine-based porous organic polymer photocatalyst as a photocatalyst, which can act as a photocatalyst for CP bond coupling reactions and can catalyze CP bond coupling reactions under relatively mild conditions.

[0007] The third objective of this invention is to provide a method for CP bond coupling reaction, under nitrogen protection, to... The dihydrophenazine-based porous organic polymer photocatalyst and carbonate of this invention are added to a solvent and reacted at room temperature under blue light irradiation for 10-15 hours with stirring. After concentration and purification of the reaction solution, the product can be prepared. This method has mild reaction conditions and high yield.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A dihydrophenazine-based porous organic polymer photocatalyst is obtained by free radical polymerization of dihydrophenazine vinyl monomers and bipyridine vinyl monomers, followed by coordination with a nickel salt.

[0010] This invention also provides a method for preparing the dihydrophenazine-based porous organic polymer photocatalyst, the method comprising the following steps:

[0011] (1) Dihydrophenazine vinyl monomers, bipyridine vinyl monomers and catalysts are dissolved in a polar solvent and reacted at 70-100℃ for 6-24h in a nitrogen atmosphere. The reaction solution is centrifuged, washed and dried to prepare polymer POP2.

[0012] (2) Disperse polymer POP2 in an alcohol solvent, add an alcohol solution of nickel salt to it, stir the reaction at room temperature for 10-14 hours, pour the reaction solution into an ether solvent to precipitate the product, and then centrifuge, wash and dry to prepare dihydrophenazine porous organic polymer photocatalyst.

[0013] The structural formula of the dihydrophenazine vinyl monomer is: Wherein, R1, R2, and R3 are hydrogen, phenyl, substituted phenyl, straight-chain or branched alkyl with 6 or fewer carbons, or straight-chain or branched alkoxy with 6 or fewer carbons.

[0014] The structural formula of the bipyridine vinyl monomer is: R4 is hydrogen, phenyl, substituted phenyl, straight-chain or branched alkyl with 6 or fewer carbons, or straight-chain or branched alkoxy with 6 or fewer carbons.

[0015] The dihydrophenazine vinyl monomer is The dipyridine vinyl monomer is

[0016] In step (1), the molar ratio of the dihydrophenazine vinyl monomer, the bipyridine vinyl monomer, and the catalyst is 1:1 to 1.2:45 to 60, preferably 1:1:50.

[0017] In step (1), the concentration of the dihydrophenazine vinyl monomer in the polar solvent is 0.01 to 0.1 M, preferably 0.05 M.

[0018] In step (1), the catalyst is azobisisobutyronitrile; the polar solvent is any one of THF, DMF, DMA, and DMSO, preferably THF.

[0019] In step (1), the washing is performed by repeatedly washing three times with ethyl acetate. In this way, the unreacted raw material monomers will dissolve in ethyl acetate and be removed, thereby obtaining high-purity polymer POP2.

[0020] In step (2), the mass ratio of polymer POP2 to nickel salt is 1:3 to 5; the nickel salt is any one of nickel chloride, nickel sulfate, and nickel bromide.

[0021] In step (2), the concentration of polymer POP2 relative to the alcohol solvent is 10-20 mg / mL.

[0022] In step (2), the concentration of the nickel salt alcohol solution is 10-20 mg / mL.

[0023] In step (2), the alcohol solvent used for the alcohol solvent and the nickel salt alcohol solution is any one of methanol, ethanol, and isopropanol, preferably methanol; the ether solvent is any one of diethyl ether, methyl ether, and petroleum ether, preferably diethyl ether.

[0024] In step (2), the washing process involves repeatedly washing three times with ether.

[0025] The present invention also provides the application of the dihydrophenazine porous organic polymer photocatalyst as a photocatalyst, which can exert a catalytic effect under blue light irradiation.

[0026] Furthermore, the present invention provides the application of the aforementioned dihydrophenazine porous organic polymer photocatalyst as a catalyst for CP bond coupling reactions.

[0027] Furthermore, the present invention provides the dihydrophenazine-based porous organic polymer photocatalyst as... and Application of catalysts for CP bond coupling reactions.

[0028] The dihydrophenazine-based porous organic polymer photocatalyst can catalyze... and The reaction was carried out to obtain the following results: Wherein, M1 and M2 are any one of aryl and alkoxy groups with 6 or fewer carbon atoms, and R is any one of hydrogen, straight-chain or branched alkoxy groups with 6 or fewer carbon atoms, straight-chain or branched alkyl groups with 6 or fewer carbon atoms, haloalkyl groups, halogroups, and phenyl groups.

[0029] Furthermore, M1 and M2 are any one of Ar and OEt, and R is any one of OMe, CH3, CF3, t-Bu, F, Cl, Br, H, and Ph.

[0030] This invention also provides a method for CP bond coupling reaction, wherein under nitrogen protection, the CP bond coupling reaction is carried out... A dihydrophenazine-based porous organic polymer photocatalyst and a carbonate are added to a solvent and reacted under blue light at room temperature with stirring for 20–24 hours. After filtration, the filtrate is extracted, concentrated, and purified to obtain the desired product.

[0031] The carbonate is any one or more of cesium carbonate, potassium carbonate, or sodium carbonate.

[0032] The ratio of dihydrophenazine porous organic polymer photocatalyst to carbonate is 0.3 mmol: 0.6 mmol: 5 mg: 0.6 mmol.

[0033] The wavelength of the blue light is 415nm.

[0034] The preparation method of the dihydrophenazine porous organic polymer photocatalyst provided by this invention is simple. The phenazine ring and the benzene ring attached to the N in the dihydrophenazine vinyl monomer are not coplanar. After polymerization, many pores are formed between multiple phenazine molecules due to the position of the benzene ring, thereby preparing a porous organic polymer. Such a structure has a large specific surface area and high catalytic efficiency.

[0035] The dihydrophenazine porous organic polymer photocatalyst provided by this invention has a significantly improved catalytic efficiency compared to traditional photocatalysts due to the confinement effect of the polymer-supported photocatalyst and metal complex. It can achieve CP bond coupling reaction under relatively mild conditions. During the CP bond coupling reaction, the phosphorus-containing substrate generates phosphorus radicals through single electron transfer, which then undergo oxidative addition with Ni in the dihydrophenazine porous organic polymer photocatalyst to generate intermediates. Finally, the target product is obtained through reductive elimination. Attached Figure Description

[0036] Figure 1 This is a schematic diagram illustrating the synthesis of dihydrophenazine-based porous organic polymer photocatalysts.

[0037] Figure 2 This is a synthetic route diagram for monomer M1;

[0038] Figure 3 The NMR spectrum of compound b is shown in the proton NMR spectrum.

[0039] Figure 4 The NMR spectrum of monomer M1 is shown below.

[0040] Figure 5 The solid-state NMR spectra of POP1 and POP2 are shown.

[0041] Figure 6 The TEM and Mapping diagram for POP1; Figure 7 XPS plot of POP2-Ni;

[0042] Figure 8 SEM image of POP2-Ni;

[0043] Figure 9 TEM image of POP2-Ni; Figure 10 Mapping diagram of POP2-Ni;

[0044] Figure 11 Tg diagrams for POP2 and POP2-Ni;

[0045] Figure 12 The solid-state UV-Vis spectra of monomers M1, POP1, POP2, and POP2-Ni are shown.

[0046] Figure 13 The fluorescence emission patterns of POP2 and POP2-Ni are shown.

[0047] Figure 14 The fluorescence lifetime diagrams are for monomers M1, POP1, POP2, and POP2-Ni.

[0048] Figure 15 The NMR spectrum of compound 1 is shown below.

[0049] Figure 16 The NMR spectrum of compound 2 is shown in the proton NMR spectrum.

[0050] Figure 17 The NMR spectrum of compound 3 is shown in the proton NMR spectrum.

[0051] Figure 18 The NMR spectrum of compound 4 is shown in the proton NMR spectrum.

[0052] Figure 19 The NMR spectrum of compound 5 is shown in the proton NMR spectrum.

[0053] Figure 20 The NMR spectrum of compound 6 is shown in the proton NMR spectrum.

[0054] Figure 21 The NMR spectrum of compound 7 is shown in the proton NMR spectrum.

[0055] Figure 22 The NMR spectrum of compound 8 is shown in the proton NMR spectrum.

[0056] Figure 23 The NMR spectrum of compound 9 is shown in the proton NMR spectrum.

[0057] Figure 24 The NMR spectrum of compound 10 is shown below.

[0058] Figure 25 This is the proton NMR spectrum of compound 11. Detailed Implementation

[0059] The present invention will now be described in detail with reference to embodiments and application examples.

[0060] The synthetic route of monomer M1 in the examples is as follows: Figure 2 As shown, its synthesis method includes the following steps:

[0061] (1) 1.82 g of compound a, 4.07 g of 4-bromobenzaldehyde, 112 mg of Pd(OAC)2, 476 mg of 2-dicyclohexylphosphine-2′,4′,6′-triisopropylbiphenyl (Xphos), and 6.63 g of Cs2CO3 were added to 150 mL of o-xylene. The mixture was degassed three times using a refrigeration pump, and then heated at 140 °C for 12 h. After the reaction was completed, the mixture was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was collected. The solvent was removed under vacuum, and the crude product was separated by silica gel column chromatography with PE:EA = 10:1 as the eluent to obtain compound b, which was a brown powder. The product was further purified by recrystallization from a mixture of CH2Cl2 and MeOH in a volume ratio of 4:1.

[0062] ¹H NMR (600 MHz, DMSO-d⁶) of compound b: δ 10.09 (s, 2H), 8.17 (d, J = 7.9 Hz, 4H), 7.64 (d, J = 7.9 Hz, 4H), 6.53–6.46 (m, 4H), 5.91–5.82 (m, 4H); Figure 3 As shown.

[0063] Compound a was prepared according to the method described in the literature Theriot, JC; Lim, CH; Yang, H.; Ryan, MD; Musgrave, CB; Miyake, GM Organocatalyzed atom transfer radical polymerization driven by visible light. Science 2016, 352, 1082-1086.

[0064] (2) 390 mg of compound b, 786 mg of PPh3CH3Br and 216 mg of sodium hydride were added to 50 mL of THF and stirred under nitrogen for 12 hours. After the reaction was completed, 50 mL of distilled water was slowly added to remove excess sodium hydride. After extraction with dichloromethane and water, the organic phase was collected and the solvent was removed under vacuum. The crude product was separated by silica gel column chromatography with PE:EA = 20:1 as the eluent to obtain 193 mg of monomer M1, which was a pale yellow powder.

[0065] Monomer M1 1 H NMR (600MHz, CD6): δ7.21(d,J=8.0Hz,4H), 7.11(d,J=8.0Hz,4H), 6.52(dd,J=17.6,10.9Hz, 2H), 6.35–6.31 (m, 4H), 5.89–5.85 (m, 4H), 5.57 (d, J = 17.6Hz, 2H), 5.11 (d, J = 10.9Hz, 2H). Such as Figure 4 As shown.

[0066] Monomer M2 was prepared according to the method described in the literature Hai-Jing Nie, Jiannian Yao, Yu-Wu Zhong, Synthesis of Vinyl-Substituted Polypyridyl Ligands through Suzuki-Miyaura Cross-Coupling of Potassium Vinyltrifluoroborate with Bromopolypyridines, J.Org.Chem. 2011, 76, 4771–4775.

[0067] Example 1

[0068] A method for preparing a dihydrophenazine-based porous organic polymer photocatalyst includes the following steps:

[0069] (1) Synthesis of POP2: Monomer M1 (36.8 mg, 0.1 mmol), monomer M2 (25.8 mg, 0.1 mmol) and AIBN (0.4 mg, 0.002 mmol) were added to a 10 mL Schlenk tube containing 2 mL THF. The Schlenk tube was cooled in liquid nitrogen to solidify the THF to prevent it from being removed during subsequent vacuuming. The tube was purged with dry nitrogen three times and stirred at 75 °C for 24 h. After the reaction was completed, a yellow precipitate was formed. The precipitate was centrifuged and washed three times with ethyl acetate. Finally, it was dried under vacuum to obtain a yellow gel-like polymer POP2. The product was then ground into powder using a mortar and pestle for later use.

[0070] (2) Synthesis of POP2-Ni: 62.6 mg of polymer POP2 was ultrasonically dispersed in 5 mL of MeOH, and then NiCl2 dissolved in 10 mL of methanol was added. . The dihydrophenazine porous organic polymer photocatalyst POP2-Ni was prepared by stirring a 6H2O (230 mg, 1.0 mmol) solution at room temperature for 12 hours, then centrifuging to collect the precipitate, washing it three times with methanol, and finally drying it under vacuum. The target polymer was a light green solid.

[0071] In this embodiment, the structural formula of monomer M1 is as follows:

[0072]

[0073] The structural formula of monomer M2 is as follows:

[0074]

[0075] The solid-state NMR of the polymer POP2 prepared in this embodiment is as follows: Figure 5 As shown in the figure, the signals at δ100-170 ppm represent the C signals on the aromatic ring, and the signals at δ40-50 ppm represent the methylene signals. This demonstrates that the polymer POP2 was successfully synthesized in this embodiment. Its relationship with... Figure 5 Compared to the solid-state NMR of the homopolymer POP1 of monomer M1, POP2 exhibits more and more complex peaks in the aromatic region, and is a yellow gel-like polymer. This indicates that POP2 is a cross-linked polymer formed by the polymerization of monomers M1 and M2. The preparation method of the homopolymer POP1 of monomer M1 is as follows: Monomer M1 (36.8 mg, 0.1 mmol) and AIBN (0.4 mg, 0.002 mmol) are added to a 10 mL Schlenk tube containing 1 mL of THF. The Schlenk tube is cooled in liquid nitrogen to solidify the THF to prevent it from being removed during subsequent vacuuming. The tube is purged three times with dry nitrogen and stirred at 75°C for 24 h. After the reaction is complete, a yellow precipitate forms. The precipitate is centrifuged, washed three times with ethyl acetate, and finally dried under vacuum to obtain the yellow gel-like polymer POP1. The TEM image and mapping image of POP1 are shown below. Figure 6 As shown.

[0076] The XPS pattern of the POP2-Ni prepared in this embodiment is as follows: Figure 7 As shown in the figure, the signals of Ni and Cl can be seen, indicating that POP2 and NiCl2 successfully coordinated to form POP2-Ni. The SEM image of POP2-Ni is shown below. Figure 8 As shown in the figure, it has a porous structure with a large specific surface area; the TEM image of POP2-Ni is shown below. Figure 9 As shown, the mapping graph is as follows: Figure 10 As shown in the figure, the presence of Ni element indicates the successful synthesis of POP2-Ni.

[0077] The TG curves of POP2 and POP2-Ni are as follows: Figure 11 As shown in the figure, at 800℃, POP2-Ni loses less weight than POP2 because the Ni in POP2-Ni is not thermally decomposed, which also indicates the successful coordination of Ni.

[0078] The solid-state UV-Vis spectra of monomers M1, POP1, POP2, and POP2-Ni are as follows: Figure 12 As shown in the figure, POP1 exhibits a redshift in absorption relative to monomer M1, with a broad new absorption peak in the 500-800 nm range. This is due to the increased conjugation after polymerization, resulting in a redshift in the absorption wavelength. POP2 shows less significant absorption relative to POP1 in the 500-800 nm range. This is because the copolymerization of monomer M2 results in a relatively higher absorption intensity of M2 relative to M1, suppressing the redshift of POP1. This indicates that POP2 is a cross-linked polymer formed by the polymerization of monomers M1 and M2. POP2-Ni shows a significant redshift in absorption relative to POP2, exhibiting strong absorption in the 600-800 nm range, and the MLCT peak of Ni metal was observed, confirming successful coordination of Ni.

[0079] The fluorescence emission spectra of POP2 and POP2-Ni are as follows: Figure 13 As shown in the figure, due to the successful coordination of Ni, the fluorescence of POP2-Ni relative to POP2 was quenched in the 460-560nm range, which indirectly proves the successful coordination of Ni and demonstrates the fluorescence quenching effect of metallic Ni.

[0080] The transient fluorescence lifetimes of monomers M1, POP1, POP2, and POP2-Ni are as follows: Figure 14 As shown in the figure, the fluorescence lifetime of POP1, POP2, and POP2-Ni is several times higher than that of the small molecule photocatalyst M1. This is an important reason why porous organic polymers can effectively improve catalytic performance. Due to the metal coordination, POP2-Ni undergoes energy transfer relative to POP2, resulting in a decrease in fluorescence lifetime. This also proves that Ni metal has been successfully coordinated onto POP2.

[0081] Application Example 1

[0082] Preparation of compound 1: The steps are as follows:

[0083] Under a nitrogen atmosphere, 0.3 mmol of 4-iodoanisole, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, and 3 mL of anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the mixture was stirred and reacted for 24 hours at room temperature under 3W, 415 nm blue LED illumination. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 1, which was a white solid with a yield of 95%.

[0084] Compound 1 1 H NMR (400MHz, CDCl3) δ (ppm) 7.73–7.63 (m, 4H), 7.59 (dd, J = 11.4, 8.7Hz, 2H), 7 .55–7.48(m,2H),7.46–7.42(m,4H),6.96(dd,J=8.7,2.1Hz,2H),3.82(s,3H); 1 H NMR such as Figure 15 As shown.

[0085] Application Example 2

[0086] Preparation of compound 2: The steps are as follows:

[0087] Under a nitrogen atmosphere, 0.3 mmol of 4-iodotoluene, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, and 3 mL of anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the reaction was stirred for 24 hours at room temperature under 3 W, 415 nm blue LED irradiation. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 2, which was a white solid with a yield of 94%.

[0088] 1 H NMR (400MHz, CDCl3) δ (ppm) 7.60–7.55 (m, 4H), 7.50–7.31 (m, 8H), 7.17 (d, J = 7.1Hz, 2H), 2.30 (s, 3H); 1 H NMR such as Figure 16 As shown.

[0089] Application Example 3

[0090] Preparation of compound 3: The steps are as follows:

[0091] Under a nitrogen atmosphere, 0.3 mmol of 4-tert-butyliodobenzene, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, and 3 mL of anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the reaction was stirred for 24 hours at room temperature under 3W, 415 nm blue LED irradiation. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 3, which was a white solid with a yield of 94%.

[0092] 1 H NMR (400MHz, CDCl3) δ (ppm) 7.78–7.65 (m, 6H), 7.54–7.40 (m, 8H), 1.33 (s, 9H); 1 H NMR such as Figure 17 As shown.

[0093] Application Example 4

[0094] Preparation of compound 4: The steps are as follows:

[0095] Under a nitrogen atmosphere, 0.3 mmol of p-fluoroiodobenzene, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, and 3 mL of anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the mixture was stirred and reacted for 24 hours at room temperature under 3 W, 415 nm blue LED illumination. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 4, which was a white solid with a yield of 87%.

[0096] 1 H NMR (400MHz, CDCl3) δ (ppm) 7.72–7.60 (m, 6H), 7.60–7.52 (m, 2H), 7.53–7.45 (m, 4H), 7.18–7.13 (m, 2H); 1 H NMR such as Figure 18 As shown.

[0097] Application Example 5

[0098] Preparation of compound 5: The steps are as follows:

[0099] Under a nitrogen atmosphere, 0.3 mmol of p-chloroiodobenzene, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, and 3 mL of anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the mixture was stirred and reacted for 24 hours at room temperature under 3 W, 415 nm blue LED illumination. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 5, which was a white solid with a yield of 85%.

[0100] 1 H NMR (400MHz, CDCl3) δ (ppm) 7.72–7.52 (m, 8H), 7.50–7.43 (m, 6H); 1 H NMR such as Figure 19 As shown.

[0101] Application Example 6

[0102] Preparation of compound 6: The steps are as follows:

[0103] Under a nitrogen atmosphere, 0.3 mmol of p-bromoiodobenzene, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, and 3 mL of anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the mixture was stirred and reacted for 24 hours at room temperature under 3 W, 415 nm blue LED illumination. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 6, which was a white solid with a yield of 80%.

[0104] 1 H NMR (400MHz, CDCl3) δ (ppm) 7.72–7.59 (m, 6H), 7.58–7.52 (m, 4H), 7.49–7.46 (m, 4H); 1 HNMR such as Figure 20 As shown.

[0105] Application Example 7

[0106] Preparation of compound 7: The steps are as follows:

[0107] Under a nitrogen atmosphere, 0.3 mmol of 4-iodotrifluorotoluene, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, and 3 mL of anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the reaction was stirred for 24 hours at room temperature under 3W, 415 nm blue LED irradiation. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 7, which was a white solid with a yield of 74%.

[0108] 1 H NMR (400MHz, CDCl3) δ (ppm) = 7.88–7.77 (m, 2H), 7.72 (d, 2H), 7.69–7.61 (m, 4H), 7.58 (t, 2H), 7.49 (d, 4H); 1 H NMR such as Figure 21 As shown.

[0109] Application Example 8

[0110] Preparation of compound 8: The steps are as follows:

[0111] Under a nitrogen atmosphere, 0.3 mmol iodobenzene, 0.6 mmol diphenylphosphine oxide, 5 mg POP2-Ni, 0.6 mmol Cs2CO3, and 3 mL anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the reaction was stirred for 24 hours at room temperature under 3W, 415 nm blue LED irradiation. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 8, which was a white solid with a yield of 91%.

[0112] 1 H NMR (400MHz, CDCl3) δ (ppm) 7.78–7.60 (m, 6H), 7.60–7.52 (m, 3H), 7.49–7.44 (m, 6H); 1 HNMR such as Figure 22 As shown.

[0113] Application Example 9

[0114] Preparation of compound 9: The steps are as follows:

[0115] Under a nitrogen atmosphere, 0.3 mmol of 4-iodobiphenyl, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, 2 mL of anhydrous methanol, and 1 mL of anhydrous DMF were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the reaction was stirred for 24 hours at room temperature under 3W, 415 nm blue LED illumination. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 9, which was a white solid with a yield of 89%.

[0116] 1 H NMR (400MHz, CDCl3) δ (ppm) = 7.72 (dd, 8H), 7.57 (dd, 4H), 7.46 (dd, 6H), 7.41–7.34 (m, 1H); 1 HNMR such as Figure 23 As shown.

[0117] Application Example 10

[0118] Preparation of compound 10: The steps are as follows:

[0119] Under a nitrogen atmosphere, 0.3 mmol of 3-iodotoluene, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, and 3 mL of anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the reaction was stirred for 24 hours at room temperature under 3W, 415 nm blue LED illumination. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 10, which was a white solid with a yield of 91%.

[0120] 1 H NMR (400MHz, CDCl3) δ (ppm) = 7.64-7.71 (m, 4H), 7.52-7.61 (m, 3H), 7.43-7.50 (m, 4H), 7.31-7.41 (m, 3H), 2.37 (s, 3H); 1 H NMR such as Figure 24 As shown.

[0121] Application Example 11

[0122] Preparation of compound 11: The steps are as follows:

[0123] Under a nitrogen atmosphere, 0.3 mmol of 3-iodoanisole, 0.6 mmol of diphenylphosphine oxide, 5 mg of POP2-Ni, 0.6 mmol of Cs2CO3, and 3 mL of anhydrous methanol were added to a 10 mL reaction tube. The mixture was degassed three times using a refrigeration pump. Then, the reaction was stirred for 24 hours at room temperature under 3W, 415 nm blue LED irradiation. The catalyst was then recovered by filtration. The filtrate was extracted with ethyl acetate and water, and the organic phase was collected. The organic phase was subjected to vacuum decompression to remove the solvent. The crude product was separated by rapid column chromatography with PE:EA = 2:1 as the eluent to obtain compound 11, which was a white solid with a yield of 92%.

[0124] 1 H NMR (400MHz, CDCl3): δ (ppm) = 7.64-7.70 (m, 4H), 7.50-7.54 (m, 2H), 7.42-7.46 ( m,4H),7.28-7.37(m,2H),7.12-7.17(m,1H),7.06(dd,J=2.6,1H),3.77(s,3H); 1 H NMR such as Figure 25 As shown.

[0125] The above detailed description of a dihydrophenazine porous organic polymer photocatalyst, its preparation method, and its application, with reference to the embodiments, is illustrative rather than limiting. Several embodiments may be listed within the defined scope. Therefore, variations and modifications without departing from the overall concept of the present invention should be within the protection scope of the present invention.

Claims

1. A dihydrophenazine-based porous organic polymer photocatalyst, characterized in that, The dihydrophenazine porous organic polymer photocatalyst is obtained by free radical polymerization of dihydrophenazine vinyl monomers and bipyridine vinyl monomers, followed by coordination with nickel salts. The structural formula of the dihydrophenazine vinyl monomer is: R1, R2, and R3 are hydrogen, phenyl, substituted phenyl, straight-chain or branched alkyl with 6 or fewer carbons, or straight-chain or branched alkoxy with 6 or fewer carbons. The structural formula of the bipyridine vinyl monomer is: R4 is hydrogen, phenyl, substituted phenyl, straight-chain or branched alkyl with 6 or fewer carbons, or straight-chain or branched alkoxy with 6 or fewer carbons.

2. The dihydrophenazine-based porous organic polymer photocatalyst according to claim 1, characterized in that, The dihydrophenazine vinyl monomer is The dipyridine vinyl monomer is .

3. The method for preparing the dihydrophenazine-based porous organic polymer photocatalyst as described in claim 1 or 2, characterized in that, The preparation method includes the following steps: (1) Dihydrophenazine vinyl monomers, bipyridine vinyl monomers and catalysts are dissolved in a polar solvent and reacted at 70-100°C for 6-24 hours in a nitrogen atmosphere. The reaction solution is centrifuged, washed and dried to prepare polymer POP2. (2) Disperse polymer POP2 in alcohol solvent, add nickel salt alcohol solution to it, stir the reaction at room temperature for 10-14 h, and then centrifuge, wash and dry to prepare dihydrophenazine porous organic polymer photocatalyst. In step (1), the molar ratio of the dihydrophenazine vinyl monomer, the bipyridine vinyl monomer, and the catalyst is 1:1~1.2:45~60; the catalyst is azobisisobutyronitrile; and the polar solvent is any one of THF, DMF, DMA, and DMSO. In step (2), the mass ratio of polymer POP2 to nickel salt is 1:3~5; the nickel salt is any one of nickel chloride, nickel sulfate, and nickel bromide; the alcohol solvent used for the alcohol solvent and the alcohol solution of the nickel salt is any one of methanol, ethanol, and isopropanol.

4. The application of the dihydrophenazine porous organic polymer photocatalyst as described in claim 1 or 2 as a photocatalyst.

5. A method for a CP bond coupling reaction, characterized in that, Under nitrogen protection, , The catalyst and carbonate are added to the solvent, and the mixture is stirred at room temperature under blue light for 20-24 hours. After filtration, the filtrate is extracted, concentrated, and purified to obtain the desired product. Wherein, M1 and M2 are any one of aryl and alkoxy groups with 6 or fewer carbons; R is any one of hydrogen, straight-chain or branched alkoxy groups with 6 or fewer carbons, straight-chain or branched alkyl groups with 6 or fewer carbons, haloalkyl groups, halogroups, and phenyl groups. The catalyst is the dihydrophenazine porous organic polymer photocatalyst according to claim 1 or 2, or the dihydrophenazine porous organic polymer photocatalyst prepared by the preparation method according to claim 3.

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