CN116239784B - Photosensitive MOF and preparation method and application thereof - Google Patents

Photosensitive MOF and preparation method and application thereof Download PDF

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CN116239784B
CN116239784B CN202310159667.5A CN202310159667A CN116239784B CN 116239784 B CN116239784 B CN 116239784B CN 202310159667 A CN202310159667 A CN 202310159667A CN 116239784 B CN116239784 B CN 116239784B
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mof
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CN116239784A (en
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唐晓亮
白东杰
陈小芬
章万超
王维欢
胡广寿
刘伟生
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Gansu Rare Earth New Material LLC
Lanzhou University
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Lanzhou University
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    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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Abstract

The invention belongs to the technical field of photocatalytic organic conversion. The invention provides a photosensitive MOF, a preparation method and application thereof. The preparation method comprises the following steps: the ligands H 3LRu, N-dimethylacetamide, zrCl 4 and anhydrous formic acid are reacted to obtain the photosensitive MOF. The photosensitive MOF material prepared by the invention has higher catalytic activity, good thermal stability and permanent porosity, has the advantage of wide substrate universality range in the photocatalytic oxidation C-C coupling reaction, has a simple preparation method and high yield, and can realize industrial preparation.

Description

Photosensitive MOF and preparation method and application thereof
Technical Field
The invention relates to the technical field of photocatalytic organic conversion, in particular to a photosensitive MOF, a preparation method and application thereof.
Background
The one-step formation of tetrahydroquinoline products from N, N-dimethylaniline and N-phenylmaleimide is a common structural motif in many biologically active natural products and pharmacologically relevant therapeutic agents. Whereas conventional non-photochemical synthetic methods often require the simultaneous addition of a catalyst and an oxidant at elevated temperatures. Although the photochemical synthesis of tetrahydroquinoline products has been carried out using organic dyes as photocatalysts in the prior art, the homogeneity of the photocatalysts can lead to unavoidable pollution to the environment. There are also disadvantages when the hot Ru/Ir complexes are used as photocatalysts. For example, there are problems that the homogeneous photocatalyst is not recyclable, noble metals such as Ru/Ir are wasted, and the reaction time is long.
Many heterogeneous photocatalysts have been used for photocatalytic oxidation of C-C coupling reactions (e.g., COF materials and inorganic semiconductor materials) to solve the homogeneous catalysis problems that exist during the reaction, but soluble Ru/Ir complexes have their unique advantages in terms of photocatalytic organic conversion, and thus how to solve the problems that exist with soluble Ru/Ir complexes remains a great challenge. The main influence is that the modification of Ru/Ir complex is difficult, and the ligand size after modification is large, so that other heterogeneous photocatalytic materials are not easy to synthesize. However, the synthetic method and structural characteristics of MOFs materials can exactly and perfectly solve the problems. Therefore, the Ru/Ir complex is modified and synthesized to be used for constructing ligands of MOFs materials to solve the problems of unrecoverable Ru/Ir complex, resource waste and long reaction time, and has good application prospect.
Disclosure of Invention
The invention aims to provide a photosensitive MOF, a preparation method and application thereof, and aims to overcome the defects in the prior art, wherein the prepared photosensitive MOF has high photocatalytic activity in a photocatalytic oxidation C-C coupling reaction, and the technical problems of irrecoverability, long reaction time and the like of the conventional Ru/Ir complex in the photocatalytic oxidation C-C coupling reaction can be effectively solved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a photosensitive MOF, which comprises the following steps:
The ligands H 3LRu, N-dimethylacetamide, zrCl 4 and anhydrous formic acid are reacted to obtain the photosensitive MOF.
Preferably, the ligand H 3LRu has the structural formula
Preferably, the mass volume ratio of the ligand H 3LRu、ZrCl4, N-dimethylacetamide and anhydrous formic acid is 8-12 mg: 18-22 mg: 1-2 mL: 0.5-1 mL.
Preferably, the temperature of the reaction is 110 to 130 ℃.
Preferably, the reaction time is 70 to 74 hours.
The invention also provides the photosensitive MOF prepared by the preparation method.
The invention also provides application of the photosensitive MOF in photocatalytic oxidation C-C coupling reaction, wherein the photosensitive MOF is used as a catalyst to carry out the photocatalytic oxidation C-C coupling reaction on a substrate in an organic solvent.
Preferably, the photosensitive MOF comprises 0.5 to 1.5% of the total molar amount of substrate and photosensitive MOF.
Preferably, the substrate is an aniline compound or an imide compound; the organic solvent is N, N-dimethylformamide; the proportion of the aniline compound, the imide compound and the organic solvent is 1.9-2.1 mmol:1mmol: 7-9 mL.
Preferably, the temperature of the photocatalytic oxidation C-C coupling reaction is 20-30 ℃, the time of the photocatalytic oxidation C-C coupling reaction is 11-13 h when the photocatalytic oxidation C-C coupling reaction is irradiated with light and the time of the photocatalytic oxidation C-C coupling reaction is oxidized with oxygen, and the photocatalytic oxidation C-C coupling reaction is carried out in the atmosphere of light and oxygen.
The beneficial effects of the invention include the following points:
1) The photosensitive MOF material prepared by the invention has higher catalytic activity, good thermal stability and permanent porosity, and has the advantage of wide substrate universality range in the photocatalytic oxidation C-C coupling reaction.
2) The preparation method of the photosensitive MOF material is simple, has high yield and can realize industrial preparation.
Drawings
FIG. 1 is a TGA graph of a photosensitive MOF of example 1;
FIG. 2 is a FT-IR diagram of a photosensitive MOF of example 1;
FIG. 3 is an N 2 adsorption/desorption isotherm plot of the photosensitive MOF of example 1;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the product of application example 1;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the product of application example 2;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of the product of application example 3;
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of the product of application example 4;
FIG. 8 is a nuclear magnetic resonance hydrogen spectrum of the product of application example 5;
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of the product of application example 6;
FIG. 10 is a nuclear magnetic resonance hydrogen spectrum of the product of application example 7.
Detailed Description
The invention provides a preparation method of a photosensitive MOF, which comprises the following steps:
The ligands H 3LRu, N-dimethylacetamide, zrCl 4 and anhydrous formic acid are reacted to obtain the photosensitive MOF.
In the present invention, the ligand H 3LRu is preferably of the formula
In the present invention, the preparation method of the ligand H 3LRu preferably comprises the following steps:
(1) Reacting 1, 10-phenanthroline-5, 6-dione, 4-formylbenzoic acid methyl ester, ammonium acetate and glacial acetic acid to obtain a solid L;
(2) Reacting the solid L, ruCl 3·3H2 O with ethylene glycol to obtain solid powder;
(3) The solid powder, methanol, tetrahydrofuran and sodium hydroxide solution are reacted to obtain ligand H 3LRu.
In the invention, the mass volume ratio of the 1, 10-phenanthroline-5, 6-diketone, the 4-formylbenzoic acid methyl ester, the ammonium acetate and the glacial acetic acid in the step (1) is preferably 2-2.5 g:1.5 g to 2g: 6-7 g:80 to 100mL, more preferably 2.2 to 2.4g:1.6 to 1.8g:6.4 to 6.6g:85 to 95mL, more preferably 2.3g:1.7g:6.5g:90mL; the reaction temperature is preferably 120 to 140 ℃, more preferably 125 to 135 ℃, and even more preferably 130 ℃; the reaction time is preferably 20 to 30 hours, more preferably 22 to 28 hours, and still more preferably 24 to 26 hours.
After the reaction in the step (1) is finished, the reaction system is naturally cooled to room temperature, the cooled system is poured into ice water, the pH value is regulated by ammonia water, solids are filtered after the solids are separated out, and the solids are sequentially washed by deionized water and dried to obtain a solid L; the concentration of the aqueous ammonia is preferably 10 to 12mol/L, more preferably 10.5 to 11.5mol/L, still more preferably 11mol/L; when the pH is adjusted with ammonia, the pH is preferably adjusted to 6 to 7, more preferably 6.5; the temperature of the drying treatment is preferably 60 to 80 ℃, more preferably 65 to 75 ℃, still more preferably 70 ℃, and the time of the drying treatment is preferably 22 to 26 hours, more preferably 23 to 25 hours, still more preferably 24 hours.
In the present invention, the solid L in the step (1) is a light pink solid.
In the invention, the mass-volume ratio of the solid L, ruCl 3·3H2 O and the ethylene glycol in the step (2) is preferably 2.5-3 g:0.5g:50 to 100mL, more preferably 2.6 to 2.8g:0.5g:60 to 90mL, more preferably 2.7g:0.5g: 70-80 mL; the reaction temperature is preferably 180 to 200 ℃, more preferably 185 to 195 ℃, and even more preferably 190 ℃; the reaction time is preferably 24 to 35 hours, more preferably 26 to 32 hours, and still more preferably 28 to 30 hours; the reaction is preferably carried out in a protective atmosphere.
In the present invention, the protective atmosphere is preferably nitrogen, argon, helium or neon.
In the invention, after the reaction in the step (2) is finished, the reaction system is preferably naturally cooled to room temperature, then ammonium hexafluorophosphate solution is dropwise added under the condition of stirring to obtain orange-red solid, then stirring is continued to obtain precipitate, and the precipitate is sequentially filtered, washed by deionized water and dried to obtain solid powder; the ammonium hexafluorophosphate solution is preferably a saturated ammonium hexafluorophosphate solution, and the volume-mass ratio of the ammonium hexafluorophosphate solution to the solid L in the step (2) is preferably 90-110 mL:2.5 to 3g, more preferably 95 to 105mL:2.6 to 2.8g, more preferably 100mL:2.7g; the stirring time is preferably 25 to 35 minutes, more preferably 28 to 32 minutes, and still more preferably 30 minutes; the temperature of the drying treatment is preferably 60 to 80 ℃, more preferably 65 to 75 ℃, still more preferably 70 ℃, and the time of the drying treatment is preferably 22 to 26 hours, more preferably 23 to 25 hours, still more preferably 24 hours.
In the invention, the solid powder in the step (2) is reddish brown solid powder.
In the present invention, the concentration of the sodium hydroxide solution in the step (3) is preferably 5 to 7mol/L, more preferably 5.5 to 6.5mol/L, and still more preferably 6mol/L; the mass volume ratio of the solid powder, the methanol, the tetrahydrofuran and the sodium hydroxide solution is preferably 2-3 g: 40-60 mL: 40-60 mL:40 to 60mL, more preferably 2.2 to 2.8g: 45-55 mL: 45-55 mL:45 to 55mL, more preferably 2.4 to 2.6g: 48-52 mL: 48-52 mL: 48-52 mL; the reaction temperature is preferably 70 to 90 ℃, more preferably 75 to 85 ℃, and even more preferably 80 ℃; the reaction time is preferably 12 to 24 hours, more preferably 14 to 22 hours, and still more preferably 16 to 20 hours.
In the invention, after the reaction in the step (3) is finished, the solution is naturally cooled to room temperature, the organic solvent is dried by spin drying, deionized water is added to completely dissolve the organic solvent, the pH value of the system is regulated by hydrochloric acid solution, solids are separated out, and the solids are sequentially washed by deionized water and dried to obtain a ligand H 3LRu; the concentration of the hydrochloric acid solution is preferably 11 to 13mol/L, more preferably 12mol/L; when the pH of the system is adjusted with a hydrochloric acid solution, the pH is preferably adjusted to 0.5 to 1.5, more preferably 1; the temperature of the drying treatment is preferably 60 to 80 ℃, more preferably 65 to 75 ℃, still more preferably 70 ℃, and the time of the drying treatment is preferably 22 to 26 hours, more preferably 23 to 25 hours, still more preferably 24 hours.
In the invention, the mass volume ratio of the ligand H 3LRu、ZrCl4, N-dimethylacetamide and anhydrous formic acid is preferably 8-12 mg: 18-22 mg: 1-2 mL:0.5 to 1mL, more preferably 9 to 11mg: 19-21 mg: 1.2-1.8 mL:0.7 to 0.9mL, more preferably 10mg:20mg:1.4 to 1.6mL:0.8mL.
In the present invention, the temperature of the reaction is preferably 110 to 130 ℃, more preferably 115 to 125 ℃, and still more preferably 120 ℃.
In the present invention, the reaction time is preferably 70 to 74 hours, more preferably 71 to 73 hours, and still more preferably 72 hours;
In the invention, after reacting ligands H 3LRu, N-dimethylacetamide, zrCl 4 and anhydrous formic acid, preferably filtering out mother liquor to obtain crystals, and washing and drying the crystals to obtain the photosensitive MOF; the washing reagent is preferably absolute ethanol, and the washing times are preferably 2 to 4 times, and more preferably 3 times; the drying is preferably in air.
The invention also provides the photosensitive MOF prepared by the preparation method.
The invention also provides application of the photosensitive MOF in photocatalytic oxidation C-C coupling reaction, wherein the photosensitive MOF is used as a catalyst to carry out the photocatalytic oxidation C-C coupling reaction on a substrate in an organic solvent.
In the present invention, the photosensitive MOF preferably occupies 0.5 to 1.5%, more preferably 0.8 to 1.2%, and still more preferably 1% of the total molar amount of the substrate and the photosensitive MOF.
In the invention, the substrate is preferably an aniline compound and an imide compound; the organic solvent is preferably N, N-dimethylformamide; the ratio of the aniline compound, the imide compound and the organic solvent is preferably 1.9 to 2.1mmol:1mmol:7 to 9mL, more preferably 2mmol:1mmol:8mL.
In the invention, the aniline compound is preferably N, N-dimethylaniline, 4-methyl-N, N-dimethylaniline, 4-methoxy-N, N-dimethylaniline or 3-methoxy-N, N-dimethylaniline; the imide compound is preferably N-phenylmaleimide, N-cyclohexylmaleimide, N-biphenylmaleimide or N-naphthylmaleimide.
In the invention, the temperature of the photocatalytic oxidation C-C coupling reaction is preferably 20-30 ℃, more preferably 22-28 ℃, and even more preferably 24-26 ℃; the time of the photocatalytic oxidation C-C coupling reaction is preferably 11 to 13 hours, more preferably 11.5 to 12.5 hours, and still more preferably 12 hours; the photocatalytic oxidation C-C coupling reaction is preferably carried out in an atmosphere of oxygen under irradiation with light.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
2G of 1, 10-phenanthroline-5, 6-dione, 1.87g of methyl 4-formylbenzoate, 6.23g of ammonium acetate and 80mL of glacial acetic acid are reacted at 130 ℃ for 24 hours, after the reaction is finished, the reaction system is naturally cooled to room temperature, the cooled system is poured into ice water, the pH value is regulated to 6 by 11mol/L of ammonia water, solids are precipitated, the solids are washed by deionized water, and the solids are dried in a vacuum drying oven at 70 ℃ for 24 hours, so that light pink solid L is obtained.
2.82G of solid L, 0.5gRuCl 3·3H2 O and 100mL of ethylene glycol are added into a 250mL round bottom flask, then the mixture is reacted for 24 hours in a nitrogen atmosphere with the temperature of 190 ℃, after the reaction is finished, the reaction system is naturally cooled to room temperature, then 100mL of saturated ammonium hexafluorophosphate solution is added dropwise under the condition of stirring, a large amount of orange-red solid is obtained, stirring is continued for 30 minutes, the precipitate is filtered and washed by deionized water, and then the precipitate is placed into a vacuum drying oven with the temperature of 70 ℃ for drying for 24 hours, so as to obtain reddish brown solid powder.
2G of solid powder, 40mL of methanol, 40mL of tetrahydrofuran and 40mL of sodium hydroxide solution with the concentration of 6mol/L are reacted for 20H at 80 ℃, after the reaction is finished, the solution is naturally cooled to room temperature, an organic solvent is dried by spin drying through a rotary evaporator, deionized water is added to dissolve the organic solvent completely, the pH is adjusted to 1 by using hydrochloric acid solution with the concentration of 12mol/L, a solid is separated out, the solid is washed by deionized water, and the solid is dried for 24H in a vacuum drying oven with the temperature of 70 ℃ to obtain the ligand H 3LRu.
10Mg of ligand H 3LRu and 20mg of ZrCl 4 are placed in a polytetrafluoroethylene high-pressure reaction kettle with 25mL, 2mLN, N-dimethylacetamide and 0.65mL of anhydrous formic acid are added, the mixture is taken out after being reacted in an oven with 120 ℃ for 72 hours, mother liquor is filtered out, rectangular flaky orange-red crystals are obtained, and after washing the crystals with absolute ethyl alcohol for 2 times, the crystals are dried in air, so that the photosensitive MOF is obtained.
This example produced 0.013g of photosensitive MOF, which was calculated to be: the yield of photosensitive MOF was 58.7%.
Example 1 the TGA profile, FT-IR profile and N 2 adsorption/desorption isotherms of a photosensitive MOF are shown in figures 1-3. As can be seen from fig. 1 to 3: the photosensitive MOF has not only good thermal stability but also permanent porosity.
Example 2
2.5G of 1, 10-phenanthroline-5, 6-diketone, 2g of 4-formylbenzoic acid methyl ester, 7g of ammonium acetate and 100mL of glacial acetic acid are reacted for 30 hours at 140 ℃, after the reaction is finished, the reaction system is naturally cooled to room temperature, the cooled system is poured into ice water, the pH value is regulated to 6.5 by using 10mol/L ammonia water, solids are separated out, the solids are washed by deionized water and then are dried for 26 hours in a vacuum drying oven at 80 ℃ to obtain light pink solid L; adding 2.82g of solid L,0.5 g of RuCl 3·3H2 O and 80mL of ethylene glycol into a 250mL round-bottomed flask, then reacting for 30h in an argon atmosphere at 200 ℃, naturally cooling the reaction system to room temperature after the reaction is finished, then dropwise adding 110mL of saturated ammonium hexafluorophosphate solution under stirring to obtain a large amount of orange-red solid, continuing stirring for 35min, filtering the precipitate and washing with deionized water, and then placing the precipitate into a vacuum drying oven at 60 ℃ for drying for 26h to obtain brownish red solid powder; 3g of solid powder, 60mL of methanol, 50mL of tetrahydrofuran and 60mL of sodium hydroxide solution with the concentration of 7mol/L are reacted for 24 hours at the temperature of 90 ℃, after the reaction is finished, the solution is naturally cooled to the room temperature, an organic solvent is dried by spin drying through a rotary evaporator, deionized water is added to dissolve all the organic solvent, the pH is adjusted to 1.5 by using hydrochloric acid solution with the concentration of 11mol/L, a solid is separated out, the solid is washed by deionized water, and the solid is dried in a vacuum drying oven at the temperature of 60 ℃ for 26 hours to obtain the ligand H 3LRu.
12Mg of ligand H 3LRu and 22mg of ZrCl 4 are placed in a polytetrafluoroethylene high-pressure reaction kettle with 25mL, 1.8mLN, N-dimethylacetamide and 1mL anhydrous formic acid are added, the mixture is taken out after being reacted in an oven with 110 ℃ for 74 hours, mother liquor is filtered out, rectangular flaky orange-red crystals are obtained, and after washing the crystals with absolute ethyl alcohol for 3 times, the crystals are dried in air, so that the photosensitive MOF is obtained.
Example 3
2.1G of 1, 10-phenanthroline-5, 6-diketone, 1.6g of 4-formylbenzoic acid methyl ester, 6g of ammonium acetate and 90mL of glacial acetic acid are reacted for 20 hours at 120 ℃, after the reaction is finished, the reaction system is naturally cooled to room temperature, the cooled system is poured into ice water, the pH value is regulated to 7 by using 12mol/L ammonia water, solids are separated out, the solids are washed by deionized water and then are dried for 22 hours in a vacuum drying oven at 75 ℃ to obtain light pink solid L; adding 2.82g of solid L, 0.5g of RuCl 3·3H2 O and 50mL of ethylene glycol into a 250mL round-bottom flask, then reacting for 35h in a helium atmosphere at 180 ℃, naturally cooling the reaction system to room temperature after the reaction is finished, then dropwise adding 90mL of saturated ammonium hexafluorophosphate solution under stirring to obtain a large amount of orange-red solid, continuing stirring for 25min, filtering the precipitate and washing with deionized water, and then placing the precipitate into a vacuum drying oven at 80 ℃ for drying for 22h to obtain brownish red solid powder; 2.5g of solid powder, 50mL of methanol, 60mL of tetrahydrofuran and 50mL of sodium hydroxide solution with the concentration of 5mol/L are reacted for 12H at 70 ℃, after the reaction is finished, the solution is naturally cooled to room temperature, an organic solvent is dried by spin drying through a rotary evaporator, deionized water is added to dissolve the organic solvent completely, the pH value is adjusted to 0.5 by using hydrochloric acid solution with the concentration of 13mol/L, a solid is separated out, the solid is washed by deionized water, and the solid is dried in a vacuum drying box at 80 ℃ for 22H to obtain the ligand H 3LRu.
8Mg of ligand H 3LRu and 18mg of ZrCl 4 are placed in a polytetrafluoroethylene high-pressure reaction kettle with 25mL, 1mLN, N-dimethylacetamide and 0.5mL anhydrous formic acid are added, the mixture is taken out after being reacted in an oven with 130 ℃ for 70 hours, mother liquor is filtered out, rectangular flaky orange-red crystals are obtained, and after washing the crystals with absolute ethyl alcohol for 4 times, the crystals are dried in air, so that the photosensitive MOF is obtained.
Example 4
2G of 1, 10-phenanthroline-5, 6-diketone, 1.87g of 4-formylbenzoic acid methyl ester, 6.58g of ammonium acetate and 85mL of glacial acetic acid are reacted for 22 hours at the temperature of 125 ℃, after the reaction is finished, the reaction system is naturally cooled to room temperature, the cooled system is poured into ice water, the pH value is regulated to 6 by 11mol/L of ammonia water, solids are separated out, the solids are washed by deionized water and then are dried for 25 hours in a vacuum drying oven at the temperature of 75 ℃, and light pink solid L is obtained; adding 2.82g of solid L, 0.5gRuCl 3·3H2 O and 85mL of ethylene glycol into a 250mL round-bottom flask, then reacting for 32 hours in a neon atmosphere at the temperature of 195 ℃, naturally cooling the reaction system to room temperature after the reaction is finished, then dropwise adding 105mL of saturated ammonium hexafluorophosphate solution under stirring to obtain a large amount of orange-red solid, continuing stirring for 26 minutes, filtering precipitate and washing the precipitate with deionized water, and then putting the precipitate into a vacuum drying oven at the temperature of 65 ℃ for drying for 23 hours to obtain reddish brown solid powder; 2.2g of solid powder, 45mL of methanol, 45mL of tetrahydrofuran and 45mL of sodium hydroxide solution with the concentration of 6.5mol/L are reacted for 18H at the temperature of 75 ℃, after the reaction is finished, the solution is naturally cooled to room temperature, an organic solvent is dried by spin drying through a rotary evaporator, deionized water is added to dissolve the organic solvent completely, the pH is adjusted to be 1 by using hydrochloric acid solution with the concentration of 12mol/L, a solid is separated out, the solid is washed by the deionized water, and the solid is dried for 26H in a vacuum drying box at the temperature of 75 ℃ to obtain the ligand H 3LRu.
10Mg of ligand H 3LRu and 20mg of ZrCl 4 are placed in a polytetrafluoroethylene high-pressure reaction kettle with 25mL, 2mLN, N-dimethylacetamide and 0.85mL of anhydrous formic acid are added, the mixture is taken out after being reacted in an oven with the temperature of 125 ℃ for 72 hours, mother liquor is filtered out, rectangular flaky orange-red crystals are obtained, and after washing the crystals with absolute ethyl alcohol for 4 times, the crystals are dried in air, so that the photosensitive MOF is obtained.
Application example 1
Under the conditions that the temperature is 25 ℃ and the xenon lamp with a 420nm cut-off filter 300W is irradiated and oxygen is continuously introduced, the photosensitive MOF obtained in the example 1 is used as a catalyst, the photocatalytic oxidation C-C coupling reaction is carried out on N, N-dimethylaniline and N-phenylmaleimide in N, N-dimethylformamide for 12 hours (the mass-volume ratio of the N, N-dimethylaniline, the N-phenylmaleimide to the N, N-dimethylformamide is 2 mmol/1 mmol/8 mL; the photosensitive MOF accounts for 1% of the total molar amount of the N, N-dimethylaniline, the N-phenylmaleimide and the photosensitive MOF), after the reaction is finished, the catalyst is filtered, the solvent in the filtrate is dried by a rotary evaporator, the obtained mixture is separated by silica gel column chromatography, the target product is obtained, and the yield is determined by hydrogen spectrogram analysis.
Application example 2
Under the conditions that the temperature is 20 ℃ and a xenon lamp with a 420nm cut-off filter 300W is irradiated and oxygen is continuously introduced, the photosensitive MOF obtained in the example 1 is used as a catalyst, the 4-methyl-N, N-dimethylaniline and N-phenylmaleimide are subjected to photocatalytic oxidation C-C coupling reaction for 11 hours in N, N-dimethylformamide (the mass volume ratio of the 4-methyl-N, N-dimethylaniline, N-phenylmaleimide and N, N-dimethylformamide is 2mmol:1mmol:7mL; the photosensitive MOF accounts for 0.5 percent of the total molar weight of the 4-methyl-N, N-dimethylaniline, N-phenylmaleimide and the photosensitive MOF), after the reaction is finished, the catalyst is filtered, the solvent in the filtrate is dried by a rotary evaporator, the obtained mixture is separated by a silica gel column chromatography, and a target product is obtained, and the nuclear magnetic resonance hydrogen spectrum of the target product is measured.
Application example 3
Under the conditions that the temperature is 30 ℃ and the xenon lamp with a 420nm cut-off filter 300W is irradiated and oxygen is continuously introduced, the photosensitive MOF obtained in the example 1 is used as a catalyst, the photocatalytic oxidation C-C coupling reaction is carried out on N, N-dimethylaniline and N-cyclohexylmaleimide in N, N-dimethylformamide for 13 hours (the mass-volume ratio of the N, N-dimethylaniline, the N-cyclohexylmaleimide to the N, N-dimethylformamide is 2mmol:1mmol:9mL, the photosensitive MOF accounts for 1.5 percent of the total mol of the N, N-dimethylaniline, the N-cyclohexylmaleimide and the photosensitive MOF), after the reaction is finished, the catalyst is filtered, the solvent in the filtrate is dried by a rotary evaporator, the obtained mixture is separated by a silica gel column chromatography, and a target product is obtained, and a hydrogen nuclear magnetic resonance spectrum of the target product is measured.
Application example 4
The N, N-dimethylaniline in application example 1 was replaced with an equimolar amount of 4-methoxy-N, N-dimethylaniline, the reaction time was modified to 11.5 hours, the reaction temperature was modified to 20℃and the other conditions were unchanged, and the nuclear magnetic resonance hydrogen spectrum was measured.
Application example 5
The N, N-dimethylaniline in application example 1 was replaced with an equimolar amount of 3-methoxy-N, N-dimethylaniline, the reaction temperature was changed to 28℃and the total molar amount of the photosensitive MOF to the substrate and the photosensitive MOF was changed to 1.2%, and the reaction was carried out under the other conditions, and the nuclear magnetic resonance hydrogen spectrum thereof was measured.
Application example 6
The N, N-dimethylaniline in application example 1 was replaced with an equimolar amount of 3-methoxy-N, N-dimethylaniline, N-phenylmaleimide was replaced with an equimolar amount of N-biphenylmaleimide, the reaction time was modified to 12.5 hours, the reaction temperature was modified to 30℃and the other conditions were unchanged, and the nuclear magnetic resonance hydrogen spectrum thereof was measured.
Application example 7
N-biphenylmaleimide in application example 6 was replaced with N-naphthylmaleimide in an equimolar amount, the reaction time was modified to 12 hours, the reaction temperature was modified to 25 ℃, the volume of N, N-dimethylformamide was modified to 7.5mL, and the reaction was carried out under the same conditions, and the nuclear magnetic resonance hydrogen spectrum thereof was measured.
The nuclear magnetic resonance hydrogen spectra of the products of application examples 1 to 7 are shown in fig. 4 to 10, respectively. As can be seen from fig. 4 to 10: the photosensitive MOF obtained in example 1 has the advantage of wide substrate universality in the photocatalytic oxidation C-C coupling reaction.
Comparative application example 1
The N, N-dimethylformamide in application example 1 was replaced with an equivalent amount of acetonitrile, the reaction was performed under the other conditions unchanged, and the yield was determined by nuclear magnetic resonance hydrogen spectrogram analysis.
Comparative application example 2
The N, N-dimethylformamide in application example 1 was replaced with an equal amount of methanol, the reaction was performed under the other conditions unchanged, and the yield was determined by nuclear magnetic resonance hydrogen spectrogram analysis.
Comparative application example 3
The N, N-dimethylformamide in application example 1 was replaced with an equal amount of methylene chloride, the reaction was performed under the other conditions unchanged, and the yield was determined by nuclear magnetic resonance hydrogen spectrogram analysis.
Comparative application example 4
The N, N-dimethylformamide in application example 1 was replaced with an equal amount of absolute ethanol, the reaction was performed under the other conditions unchanged, and the yield was determined by nuclear magnetic resonance hydrogen spectrogram analysis.
Comparative application example 5
The photosensitive MOF catalyst in application example 1 was replaced with an equal amount of H 3LRu catalyst, the reaction was performed under other conditions, and the yield was determined by nmr hydrogen spectrogram analysis.
Comparative application example 6
The photosensitive MOF catalyst in application example 1 was replaced with an equivalent amount of ZrCl 4 catalyst, the reaction was performed under other conditions, and the yield was determined by nmr hydrogen spectrogram analysis.
Comparative application example 7
The photosensitive MOF catalyst in application example 1 was omitted, the reaction was performed under other conditions, and the yield was determined by nmr hydrogen spectrogram analysis.
Comparative application example 8
The time of the photocatalytic oxidation c—c coupling reaction in application example 1 was modified to 6 hours, the reaction was performed under other conditions, and the yield was determined by nmr hydrogen spectrogram analysis.
Comparative application example 9
The conditions for irradiation with the xenon lamp with the 420nm cutoff filter 300W in application example 1 were omitted, the other conditions were unchanged for the reaction, and the yield was determined by nmr hydrogen spectrogram analysis.
Comparative application example 10
The conditions for continuously introducing oxygen in application example 1 were omitted, the reaction was performed under the other conditions, and the yield was determined by nmr hydrogen spectrum analysis.
Comparative application example 11
The conditions of irradiation with a xenon lamp with a 420nm cutoff filter 300W and continuous introduction of oxygen in application example 1 were omitted, the other conditions were unchanged, the reaction was performed, and the yield was determined by nmr hydrogen spectrogram analysis.
The reaction procedure of application example 1 and comparative application examples 1 to 11 is as follows:
the yields of the products obtained in application example 1 and comparative application examples 1 to 11 were determined by nuclear magnetic resonance hydrogen spectrogram analysis, and the results of the yields are shown in table 1.
TABLE 1 yield results
Sequence number Yield/%
Application example 1 85
Comparative application example 1 0
Comparative application example 2 0
Comparative application example 3 0
Comparative application example 4 0
Comparative application example 5 27
Comparative application example 6 0
Comparative application example 7 0
Comparative application example 8 51
Comparative application example 9 0
Comparative application example 10 0
Comparative application example 11 0
As can be seen from table 1: the photosensitive MOF prepared in example 1 has higher photocatalytic activity.
The photosensitive MOF material prepared by the invention has higher catalytic activity, good thermal stability and permanent porosity, has the advantage of wide substrate universality range in the photocatalytic oxidation C-C coupling reaction, has a simple preparation method and high yield, and can realize industrial preparation.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The application of the photosensitive MOF in the photocatalytic oxidation C-C coupling reaction is characterized in that the photosensitive MOF is used as a catalyst to carry out the photocatalytic oxidation C-C coupling reaction on a substrate in an organic solvent; the substrate is an aniline compound and an imide compound; the organic solvent is N, N-dimethylformamide;
the preparation method of the photosensitive MOF comprises the following steps:
reacting the ligands H 3LRu, N-dimethylacetamide, zrCl 4 and anhydrous formic acid to obtain a photosensitive MOF;
The structural formula of the ligand H 3LRu is
2. The use according to claim 1, wherein the mass to volume ratio of the ligands H 3LRu、ZrCl4, N-dimethylacetamide and anhydrous formic acid is 8-12 mg: 18-22 mg: 1-2 mL: 0.5-1 mL.
3. The use according to claim 2, wherein the temperature of the reaction is 110-130 ℃.
4. The method according to claim 3, wherein the reaction time is 70 to 74 hours.
5. The use according to claim 1, wherein the photosensitive MOF comprises 0.5 to 1.5% of the total molar amount of substrate and photosensitive MOF.
6. The use according to claim 1, wherein the ratio of aniline compound, imide compound and organic solvent is 1.9-2.1 mmol:1mmol: 7-9 mL.
7. The use according to claim 6, wherein the temperature of the photocatalytic oxidation C-C coupling reaction is 20-30 ℃, the time of the photocatalytic oxidation C-C coupling reaction is 11-13 hours, and the photocatalytic oxidation C-C coupling reaction is carried out in an atmosphere of oxygen under irradiation of light.
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