CN113512203B - Preparation method of chiral photosensitive metal organic framework material - Google Patents
Preparation method of chiral photosensitive metal organic framework material Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013110 organic ligand Substances 0.000 claims abstract description 106
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 68
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 80
- 150000001875 compounds Chemical class 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 16
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 11
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 11
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- QMVMDYSTJSUDKC-UHFFFAOYSA-N [4-[(2-methylpropan-2-yl)oxycarbonyl]phenyl]boronic acid Chemical compound CC(C)(C)OC(=O)C1=CC=C(B(O)O)C=C1 QMVMDYSTJSUDKC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical compound C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004485 2-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])C1([H])* 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 7
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
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- 230000001699 photocatalysis Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- KPBSWMXCQKQBOQ-UHFFFAOYSA-N 4,7-dibromo-2H-thiadiazolo[4,5-b]pyridine Chemical compound BrC(C=C1)=C2SNN=C2N1Br KPBSWMXCQKQBOQ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
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- ZQEBQGAAWMOMAI-ZETCQYMHSA-N (2s)-1-[(2-methylpropan-2-yl)oxycarbonyl]pyrrolidine-2-carboxylic acid Chemical compound CC(C)(C)OC(=O)N1CCC[C@H]1C(O)=O ZQEBQGAAWMOMAI-ZETCQYMHSA-N 0.000 description 2
- RUTZCCVYFMZGIK-UHFFFAOYSA-N 1h-benzimidazole;pyrrolidine Chemical group C1CCNC1.C1=CC=C2NC=NC2=C1 RUTZCCVYFMZGIK-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- VPMJBJSLTPBZLR-UHFFFAOYSA-N 3,6-dibromobenzene-1,2-diamine Chemical compound NC1=C(N)C(Br)=CC=C1Br VPMJBJSLTPBZLR-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
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- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013336 microporous metal-organic framework Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
A preparation method of a chiral photosensitive metal organic framework material comprises the following steps: adding an organic ligand I shown in a formula (1) and an organic ligand II shown in a formula (2) into N, N-dimethylformamide to dissolve to obtain a reaction solution; adding zirconium tetrachloride and trifluoroacetic acid, dissolving, reacting at 90-120 deg.C for 48-72h, cooling to room temperature, centrifuging, and collecting precipitate; washing the precipitate with N, N-dimethylformamide and ethanol to obtain chiral photosensitive metal organic framework material with a structural formula of Zr 6 O 4 (OH) 8 (L 2 ) n (L 1 ) m In the formula, L 1 Are organic ligands I, L 2 The organic ligand II, m and n are the number of the organic ligand I and the organic ligand II, and m + n is 6. The method is simple and easy to operate, and the prepared metal organic framework material can have a large specific surface area and a regular pore channel structure, and is favorable for the reaction of substrate molecules and a functional framework.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method of a chiral photosensitive metal organic framework material.
Background
Chirality is related to the origin of universe and life, and organisms assembled from specific chiral units have a clear selective response to external enantiomers. Molecules with different chiral configurations may have significantly different biological activities, for example, one isomer of a particular compound may be effective in treating a disease, while another isomer may be harmful to the human body. The preparation of single isomer compounds is therefore of great importance.
The visible light induced asymmetric photocatalysis has the characteristics of environmental protection, energy sustainability and low cost. A great progress of asymmetric photocatalysis is that a light active group and a chiral center are combined to form a molecular catalyst, which has the advantages of effective light-induced charge transfer and convenient separation of products and the catalyst. However, the above homogeneous catalysts have the disadvantage of being difficult to separate from the product, which limits their wide industrial application. Heterogenising homogeneous chiral catalysts is a major approach to this problem.
The chiral metal organic framework material has a chiral organic ligand capable of being functionally modified, a diversified framework structure and larger porosity, is convenient for regulating and controlling the structure and performance of the chiral metal organic framework material and accelerating the transmission of reaction raw materials and products, and has great application prospects in the fields of separation and identification and asymmetric photocatalysis. However, the amount of chiral metal organic framework materials available for photocatalytic asymmetric reactions has been still small to date because chiral organic ligands are complicated in synthesis process, high in cost, and complicated in product separation and purification. Although some progress has been made in asymmetric photocatalytic reactions based on chiral metal organic framework materials, they still have some challenges, such as small pore size and specific surface area, which are not favorable for the reaction substrate molecules to act on the functional framework, and in addition, have problems of poor chemical stability, thermal stability and crystallinity.
Disclosure of Invention
The invention aims to provide a preparation method of a chiral photosensitive metal organic framework material, which is simple and easy to operate, and the prepared metal organic framework material can have a larger specific surface area and a regular pore channel structure on the one hand, thereby being beneficial to enhancing the adsorption effect on reactant molecules and the smooth frame entry and exit of substrates and products in asymmetric photocatalysis, being beneficial to the reaction of the substrate molecules and a functional frame, and further improving the catalytic activity; on the other hand, the material can have better chemical stability, thermal stability and higher crystallinity.
In order to realize the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a chiral photosensitive metal organic framework material comprises the following steps:
a. synthesis of organic ligand i: (S) -4,4' - (2- (pyrrolidin-2-yl) -1H-benzo [ d ] imidazole-4, 7-diyl) dibenzoic acid represented by formula (1); synthesizing an organic ligand II: 4,4' - ([ [1,2,5] thiadiazole [3,4-c ] pyridine-4, 7-diyl) dibenzoic acid represented by formula (2);
b. sequentially adding an organic ligand I and an organic ligand II into a reaction bottle containing N, N-dimethylformamide to dissolve to obtain a reaction solution; the mass ratio of the organic ligand I to the organic ligand II is (1-2): 1; the adding amount of the N, N-dimethylformamide is 1.33-1.67mL/mg of the organic ligand II;
c. Adding zirconium tetrachloride and trifluoroacetic acid into the reaction solution, placing the reaction bottle at the temperature of 90-120 ℃ for reacting for 48-72h after dissolving, cooling to room temperature after the reaction is finished, placing the reaction bottle into a centrifuge, and collecting the precipitate; the mass ratio of the zirconium tetrachloride to the organic ligand II is (1-3): 1; the addition amount of trifluoroacetic acid is 1.44-8.89 mu L/mg of organic ligand II;
d. c, respectively washing the precipitate collected in the step c with N, N-dimethylformamide and ethanol for three times to obtain yellow powder, namely the chiral photosensitive metal organic framework material with the structural formula of Zr 6 O 4 (OH) 8 (L 2 ) n (L 1 ) m In the formula, L 1 Are organic ligands I, L 2 And m and n are the numbers of the organic ligand I and the organic ligand II respectively, and m + n is 6.
Preferably, in step b, the mass ratio between the organic ligand I and the organic ligand II is 2: 1; the adding amount of the N, N-dimethylformamide is 1.33mL/mg of organic ligand II; in the step c, the reaction flask is placed at the temperature of 100 ℃ for reaction for 72 hours, and the mass ratio of the zirconium tetrachloride to the organic ligand II is 1: 1; trifluoroacetic acid was added in an amount of 4.45. mu.L/mg of organic ligand II.
Further, the specific steps of synthesizing the organic ligand I are as follows:
a. weighing cesium carbonate and cesium fluoride in a reaction bottle, adding water to dissolve, adding toluene, removing air in the reaction bottle and a solvent, adding a compound shown as a formula (3) and 4-tert-butoxycarbonylphenylboronic acid, fully stirring and dissolving, adding catalysts [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and tetrakis (triphenylphosphine) palladium, reacting for 24-48h at 90-110 ℃ under the protection of nitrogen, cooling, extracting, drying, standing, spin-drying, and finally separating and purifying by column chromatography to obtain a compound shown as a formula (4);
b. Dissolving the compound shown in the formula (4) by using dichloromethane, then adding trifluoroacetic acid, stirring at room temperature overnight, and after the reaction is finished, carrying out suction filtration to obtain a white solid, namely the organic ligand I.
Preferably, in step a, the mass ratio between cesium carbonate and cesium fluoride is 6: 1, in a molar ratio of the compound represented by the formula (3) to 4-tert-butoxycarbonylphenylboronic acid of 1: 2.4 the molar ratio between [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium and tetrakis (triphenylphosphine) palladium is 1: 1.2; the molar ratio of cesium carbonate, [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium to the compound represented by the formula (3) is 3: 1 and 0.1: 1.
preferably, in the step a, after the reaction is finished, cooling to room temperature, extracting the reaction system by using dichloromethane, adding an organic phase and anhydrous sodium sulfate, drying, standing for 6 hours, adding a proper amount of silica gel, performing vacuum spin drying, and separating out a white solid by using a column chromatography to obtain the compound shown in the formula (4); the mobile phase composition in the column chromatography is 50: 1, a mixed solvent of dichloromethane and ethyl acetate.
Preferably, step b specifically comprises: dissolving the compound shown in the formula (4) by using dichloromethane, then adding trifluoroacetic acid, wherein the addition amount of the trifluoroacetic acid is 3mL/mmol, stirring at room temperature overnight, after the reaction is finished, adding dichloromethane, continuously stirring, washing off the trifluoroacetic acid, then standing, and carrying out suction filtration to obtain a white solid, namely the organic ligand I.
Further, the specific steps of synthesizing the organic ligand II are as follows:
a. weighing cesium carbonate and cesium fluoride in a reaction bottle, adding water to dissolve, adding toluene, removing air in the reaction bottle and a solvent, adding 4, 7-dibromo-pyridylthiodiazole and 4-tert-butoxycarbonylphenylboronic acid, fully stirring to dissolve, adding catalysts [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and tetrakis (triphenylphosphine) palladium, reacting for 24-48h at 90-110 ℃ under the protection of nitrogen, cooling, extracting, drying, standing, spin-drying, and finally separating and purifying by column chromatography to obtain the compound shown in the formula (5);
b. dissolving the compound shown in the formula (5) by using dichloromethane, then adding trifluoroacetic acid, stirring at room temperature overnight, and after the reaction is finished, performing suction filtration to obtain a white solid, namely the organic ligand II.
Preferably, in step a, the mass ratio between cesium carbonate and cesium fluoride is 6: the molar ratio between 1, 4, 7-dibromo-pyridothiadiazole and 4-tert-butoxycarbonylphenylboronic acid was 3.3: 1, [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium and tetrakis (triphenylphosphine) palladium in a molar ratio of 1: 1; the molar ratio of cesium carbonate, [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium to 4, 7-dibromo-pyridothiadiazole was 3: 1 and 0.1: 1.
Preferably, in the step a, after the reaction is finished, cooling to room temperature, extracting the reaction system by using dichloromethane, adding an organic phase and anhydrous sodium sulfate, drying, standing for 6 hours, adding a proper amount of silica gel, performing vacuum spin drying, and separating out a white solid by using a column chromatography to obtain the compound shown in the formula (5); the mobile phase composition in the column chromatography is 50: 1, a mixed solvent of dichloromethane and ethyl acetate.
Preferably, step b specifically comprises: dissolving the compound shown in the formula (5) by using dichloromethane, then adding trifluoroacetic acid, wherein the addition amount of the trifluoroacetic acid is 1mL/3mmol, stirring at room temperature overnight, after the reaction is finished, adding dichloromethane, continuously stirring, washing off the trifluoroacetic acid, then standing, and carrying out suction filtration to obtain a white solid, namely the organic ligand II.
Compared with the prior art, the invention adopts two new organic ligands to prepare the organic framework material, and the preparation method is simple and convenient to separate and purify; on one hand, the metal organic framework material prepared by the invention has larger specific surface area and regular pore channel structure, is beneficial to enhancing the adsorption effect on reactant molecules and the smooth frame entry and exit of substrates and products in asymmetric photocatalysis, and is beneficial to reacting the substrate molecules with the function frame, thereby improving the catalytic activity; on the other hand, the material has very good chemical stability, thermal stability and higher crystallinity.
Drawings
FIG. 1 shows the NMR spectrum of a compound represented by formula (4) synthesized in the example;
FIG. 2 shows the NMR spectra of organic ligand I synthesized in the example;
FIG. 3 shows the NMR spectrum of a compound represented by formula (5) synthesized in the example;
FIG. 4 is a nuclear magnetic resonance spectrum of organic ligand II synthesized in the example;
FIG. 5 is a schematic structural framework diagram of a chiral photosensitive metal organic framework material MOF UiO-68-cs prepared by an example;
FIG. 6 is the nuclear magnetic resonance spectrum of chiral photosensitive metal organic framework MOF UiO-68-cs after hydrofluoric acid cracking;
FIG. 7 is an X-ray diffraction pattern of an example synthesized chiral photosensitive metal organic framework material MOF UiO-68-cs;
FIG. 8 shows the nitrogen desorption isotherms and pore size distribution curves of the chiral photosensitive metal organic framework material MOF UiO-68-cs synthesized in the examples.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The starting materials and reagents used in the following examples were all those conventionally commercially available unless otherwise specified.
Example one
A preparation method of a chiral photosensitive metal organic framework material comprises the following steps:
The synthesis steps of the organic ligand I are as follows:
the synthesis of the compound represented by formula (3) is as follows:
adding a measured 30mL of anhydrous dichloromethane into a 100mL eggplant-shaped bottle, weighing Boc-L-proline (2.66g,12.36mmol) and adding the Boc-L-proline into a solvent, stirring and dissolving at 0 ℃, standing for 5min, then dropwise adding ethyl chloroformate (1.14mL,11.66mmol) and anhydrous triethylamine (3.3mL,23.33mol) into the bottle, continuing to stir for 10min, then adding 3, 6-dibromo-1, 2-phenylenediamine (2.585g,9.72mmol) into the reaction system at one time, continuing to stir, removing ice water at the moment, continuing to react for 36h after the reaction system returns to the room temperature, and slowly turning yellow turbid liquid into white. After the reaction is finished, dichloromethane and prepared saturated NaCl aqueous solution are used for extraction, and then the organic phases are combined and added with anhydrous Na 2 SO 4 And (5) drying. The dried organic phase was then spin dried and concentrated to a brown yellow oil to which glacial acetic acid (12.5mL,0.22mmol) was added and the temperature was maintained at 65 ℃ for 12 h. After the reaction is finished, pouring the reaction system cooled to room temperature into a beaker, and then adding a proper amount of saturated NaHCO 3 Making the solution alkaline, extracting with ethyl acetate and saturated aqueous NaCl solution, washing the organic phase, and adding anhydrous Na 2 SO 4 Drying for 24 h. Adding silica gel, vacuum drying, and separating and purifying by column chromatography, wherein the polarity is approximately in dichloromethane: petroleum ether 2:1, and the compound represented by formula (3) (2.8g,6.29mmol, 65% yield) was obtained as a white solid.
The synthesis of the compound represented by formula (4) is as follows:
cesium carbonate (4.4g,13.50 m) was weighed outmol) and cesium fluoride (0.34g,2.24mmol) were added to a 250mL two-necked round bottom flask, dissolved in water with the appropriate amount of water, followed by 150mL of toluene, added to the reaction flask, degassed for 3h (with N) 2 The air in the reaction flask and the solvent was removed), followed by adding the compound represented by the formula (3) (2g,4.49mmol) and 4-tert-butoxycarbonylphenylboronic acid (2.4g,10.81mmol) to the flask, sufficiently stirring to dissolve them, and adding the catalyst [1, 1' -bis (diphenylphosphino) ferrocene ] to the flask]Palladium dichloride (165mg,0.26mmol) and tetrakis (triphenylphosphine) palladium (0.36g,0.31mmol), the round-bottomed flask was evacuated of air using a vacuum pump, and N was bubbled through 2 (vacuum evacuation and N filling) 2 5 cycles) and finally the temperature is kept at 90 ℃ for 24 h. After the reaction is finished, cooling to room temperature, extracting the reaction system by using dichloromethane, adding an organic phase, drying by using anhydrous sodium sulfate, standing for 6 hours, adding a proper amount of silica gel, carrying out vacuum spin drying, and separating a product by using a column chromatography method, wherein the polarity is approximately within the range of dichloromethane: ethyl acetate 50:1, and finally a white solid was obtained as the compound represented by formula (4) (2.2g,3.44mmol, yield 77%).
The compound shown as the formula (4) is detected by a hydrogen spectrum, a carbon spectrum and a high-resolution mass spectrum, the spectrogram is shown as a figure 1, and analytical data are as follows: 1 H NMR(400MHz,CDCl 3 )δ＝8.13(d,J＝7.8,4H),7.93(s,4H),7.50(s,2H),5.18(s,1H),3.44(s,2H),2.32–1.97(m,4H),1.63(s,18H),1.53(s,9H). 13 C NMR(101MHz,CDCl 3 )δ166.06,156.87,155.88,142.52,130.46,129.55,129.09,127.49,80.96,77.16,54.94,47.47,28.51,27.93,24.97.EI-MS:m/z calcd.for C 38 H 45 N 3 O 6 :639.33,found:639.32[M] + these parameters correspond to the chemical structure of the inventive compounds.
The synthesis of organic ligands I represented by formula (1) is as follows:
a compound represented by the formula (4) (2.2g,3.44mmol) was put into a 100mL eggplant-shaped bottle, dissolved in a small amount of methylene chloride, and then 10mL of trifluoroacetic acid was added thereto and the mixture was stirred at room temperature overnight. After the reaction is finished, adding 50mL of dichloromethane into the bottle, continuing stirring for 30min, washing out trifluoroacetic acid, standing for 5min, and performing suction filtration to obtain a white solid, namely the organic ligand I (1.6g,3.74mmol, yield 97%).
By detecting the organic ligand I through hydrogen spectrum, carbon spectrum and high-resolution mass spectrum, the spectrogram is shown as figure 2, and the analytical data are as follows: 1 H NMR(400MHz,DMSO-d 6 )δ13.04(s,2H),9.69(s,1H),9.06(s,1H),8.11(d,J＝7.4Hz,4H),7.60(s,2H),5.01(s,1H),3.43(d,J＝40.3Hz,2H),2.28(s,3H). 13 C NMR(101MHz,DMSO-d 6 )δ167.25,158.72,158.37,151.58,141.83,129.85,129.79,128.76,55.64,45.40,39.52,30.11,23.30.EI-MS:m/z calcd.for C 25 H 21 N 3 O 4 :427.15,found:427.16[M] + these parameters correspond to the chemical structure of the inventive compounds.
The synthesis steps of the organic ligand II are as follows:
the synthesis of the compound represented by formula (5) is as follows:
cesium carbonate (20g,61.38mmol) and cesium fluoride (1.56g,10.27mmol) were weighed into a 250mL two-necked round bottom flask and dissolved with 3mL of water, followed by 80mL of toluene, added to the reaction flask and degassed for 3h (with N) 2 The flask and the solvent were purged of air), followed by addition of 4, 7-dibromo-pyridothiadiazole (3g,10.24mmol) and 4-tert-butoxycarbonylphenylboronic acid (6.83g,3.08mmol) to the flask, well stirred to dissolve, and addition of [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (740mg,1.02mmol) and tetrakis (triphenylphosphine) palladium (1.18g,1.02mmol) as two palladium catalysts, the air in the round-bottom flask was evacuated using a vacuum pump and N was bubbled through 2 (vacuum pumping and N filling) 2 And 5 times of circulation), setting the temperature at 90 ℃, and reacting for 48 hours at constant temperature. After the reaction is finished, cooling the reaction system to room temperature, extracting by using dichloromethane, combining organic phases and adding anhydrous NaSO 4 Drying, standing for 6 hr, adding silica gel, vacuum spin drying, and separating by column chromatography to obtain product with polarity substantially in dichloromethane: ethyl acetate 50:1, and finally a white solid was obtained as the compound represented by formula (5) (4g,8.17mmol, yield 80%).
By making a pair withThe compound shown in the formula (5) is subjected to hydrogen spectrum detection, the spectrogram is shown in figure 3, and the analytical data are as follows: 1 H NMR(400MHz,CDCl 3 ) δ 8.91(s,1H),8.72(d, J ═ 8.6Hz,2H),8.20(dd, J ═ 8.5,2.0Hz,4H),8.09(d, J ═ 8.5Hz,2H),1.64(d, J ═ 2.6Hz,18H) these parameters correspond to the chemical structure of the invented compounds.
The synthesis process of the organic ligand II shown in the formula (2) is as follows:
a compound represented by the formula (5) (1.45g,2.97mmol) was added to a 100mL eggplant-shaped bottle, followed by adding 20mL dichloromethane to the bottle, ultrasonic dispersion was performed, 1mL trifluoroacetic acid was measured with a measuring cylinder, and the mixture was added thereto and stirred at room temperature overnight. After the reaction is finished, 50mL of dichloromethane is added into the eggplant-shaped bottle, the mixture is stirred for 1 hour, trifluoroacetic acid is washed away, then the mixture is kept stand and filtered, and finally white solid, namely the organic ligand II (1.1g,2.91mmol, the yield is 98%) is obtained.
By carrying out hydrogen spectrum detection on the organic ligand II, a spectrogram is shown in FIG. 4, and analytical data are as follows: 1 H NMR(400MHz,DMSO-d 6 ) δ 9.05(s,1H),8.73(d, J ═ 8.4Hz,2H),8.25(d, J ═ 8.3Hz,2H),8.16(dd, J ═ 13.5,8.4Hz,4H).
Sequentially adding 10.2mg of organic ligand I and 9mg of organic ligand II which are synthesized by the above process into a reaction bottle containing 12mL of N, N-dimethylformamide to dissolve to obtain a reaction solution; the mass ratio between the organic ligand I and the organic ligand II is 1: 1; the adding amount of the N, N-dimethylformamide is 1.33mL/mg of organic ligand II;
adding 16.7mg of zirconium tetrachloride and 14.4 mu L of trifluoroacetic acid into the reaction solution, placing the reaction bottle at the temperature of 90 ℃ for reaction for 72 hours after dissolution, cooling to room temperature after the reaction is finished, placing the reaction bottle into a centrifuge, and collecting precipitates; the mass ratio of the zirconium tetrachloride to the organic ligand II is 3: 1; the addition amount of trifluoroacetic acid is 1.44 mu L/mg of organic ligand II;
Washing the collected precipitate with N, N-dimethylformamide and ethanol respectively for three times to obtain yellow powder, i.e. chiral photosensitive metal organic framework MOF UiO-68-cs, with yield of 68%, and structural framework diagram thereof as shown in figure5 is shown in the structural formula of Zr 6 O 4 (OH) 8 (L 2 ) n (L 1 ) m In the formula, L 1 Are organic ligands I, L 2 And m and n are the numbers of the organic ligand I and the organic ligand II respectively, and m + n is 6.
The chiral photosensitive metal organic framework UiO-68-cs is cracked by hydrofluoric acid to determine the ratio of the two ligands and the structural integrity, and the result is characterized by nuclear magnetic hydrogen spectrum, as shown in FIG. 6, and it can be seen from the figure that the two ligands can still maintain better structural integrity and the ratio is 1: 1, which is less than the charge ratio of two ligands in the synthesis of MOF 2: this is probably because the benzimidazole pyrrolidine functional group of the newly synthesized chiral ligand i has a large structure, which makes it less prone to incorporation into the framework structure during synthesis of MOFs. In addition, from the comparison of the nuclear magnetism of MOF UiO-68-cs after cracking with ligand I, it was found that the nuclear magnetism is slightly different from the pure ligand I, which is probably caused by the process of the chiral ligand in the synthesis of MOF or in the hydrofluoric acid cracking process. On the other hand, the main characteristic peaks of the chiral functional group part of the chiral ligand are all in the same, which indicates that the chiral ligand has certain stability.
In order to determine the crystallinity degree of the obtained MOF UO-68-cs and whether the MOF UO-68-cs has a UO-68 type topological structure, powder X-ray diffraction experiments are carried out on the MOF UO-68-cs within a scanning angle of 3-50 degrees, the characterization result is shown in figure 7, and as can be seen from the figure, the MOF UO-68-cs has the same diffraction peak position with the UO-68 data fitted to a single crystal, and the MOF material is proved to have a topological parent framework structure of the UO-68; meanwhile, the diffraction peak of the synthesized MOF UiO-68-cs is observed to be very sharp and is highly matched with the fitted UiO-68 data, which indicates that the MOF material has better crystallinity.
In order to explore the porous property of the MOF UiO-68-cs, a sample is pretreated, high-boiling-point DMF solvent molecules adsorbed in the pore channels of the MOF material are exchanged by using solvents such as ethanol, DCM and the like, and N is carried out after vacuum drying 2 The adsorption test characterizes the specific surface area size and pore size distribution, and from FIG. 8, it can be seen that the curve is a typical type I reversible isothermal adsorption curve, so to speakThe MOF UiO-68-cs is a microporous metal organic framework, and the BET specific surface area of the MOF UiO-68-cs is calculated to be 2326m by theoretical simulation 2 ·g -1 This is smaller than the specific surface area of the general UiO-68 MOF, probably because the large group benzimidazole pyrrolidine blocks part of the pore channels to reduce the specific surface area, and the pore diameter is calculated to be about 1.4nm by the theory of non-local density functional. The large specific surface and pore size of the MOF UiO-68-cs are beneficial to enhancing the adsorption effect on reactant molecules and smoothly entering and exiting a framework of a substrate and a product in asymmetric photocatalysis, thereby improving the catalytic activity.
Example two
A preparation method of a chiral photosensitive metal organic framework material comprises the following steps:
sequentially adding 15.3mg of the organic ligand I and 9mg of the organic ligand II which are synthesized in the first embodiment into a reaction bottle containing 15mL of N, N-dimethylformamide to dissolve to obtain a reaction solution; the mass ratio between the organic ligand I and the organic ligand II is 3: 2; the adding amount of the N, N-dimethylformamide is 1.67mL/mg of the organic ligand II;
adding 5.6mg of zirconium tetrachloride and 46.5 mu L of trifluoroacetic acid into the reaction solution, placing the reaction bottle at the temperature of 110 ℃ for reacting for 60 hours after dissolving, cooling to room temperature after the reaction is finished, placing the reaction bottle into a centrifuge, and collecting precipitates; the mass ratio of the zirconium tetrachloride to the organic ligand II is 1: 1; the addition amount of trifluoroacetic acid is 5.165 mu L/mg of organic ligand II;
washing the collected precipitate with N, N-dimethylformamide and ethanol for three times respectively to obtain yellow powder, namely chiral photosensitive metal organic framework MOF UiO-68-cs with a yield of 56%, and a structural framework diagram is shown in FIG. 5, wherein the structural formula is Zr 6 O 4 (OH) 8 (L 2 ) n (L 1 ) m In the formula, L 1 Are organic ligands I, L 2 And m and n are the numbers of the organic ligand I and the organic ligand II respectively, and m + n is 6.
EXAMPLE III
A preparation method of a chiral photosensitive metal organic framework material comprises the following steps:
sequentially adding 20.4mg of the organic ligand I and 9mg of the organic ligand II which are synthesized in the first embodiment into a reaction bottle containing 13.5mL of N, N-dimethylformamide to dissolve to obtain a reaction solution; the mass ratio of the organic ligand I to the organic ligand II is 2: 1; the adding amount of the N, N-dimethylformamide is 1.5mL/mg of the organic ligand II;
adding 11.1mg of zirconium tetrachloride and 80 mu L of trifluoroacetic acid into the reaction solution, placing the reaction bottle at the temperature of 120 ℃ for reaction for 48h after dissolution, cooling to room temperature after the reaction is finished, placing the reaction bottle into a centrifuge, and collecting precipitates; the mass ratio of the zirconium tetrachloride to the organic ligand II is 2: 1; the addition amount of trifluoroacetic acid is 8.89 mu L/mg of organic ligand II;
washing the collected precipitate with N, N-dimethylformamide and ethanol for three times respectively to obtain yellow powder, i.e. chiral photosensitive metal organic framework MOF UiO-68-cs, with yield of 45%, and structural framework diagram shown in FIG. 5, with structural formula of Zr 6 O 4 (OH) 8 (L 2 ) n (L 1 ) m In the formula, L 1 Are organic ligands I, L 2 And m and n are the numbers of the organic ligand I and the organic ligand II respectively, and m + n is 6.
Example four
A preparation method of a chiral photosensitive metal organic framework material comprises the following steps:
sequentially adding 20.4mg of the organic ligand I and 9mg of the organic ligand II which are synthesized in the first embodiment into a reaction bottle containing 12mL of N, N-dimethylformamide to dissolve to obtain a reaction solution; the mass ratio between the organic ligand I and the organic ligand II is 2: 1; the adding amount of the N, N-dimethylformamide is 1.33mL/mg of organic ligand II;
adding 5.6mg of zirconium tetrachloride and 40 mu L of trifluoroacetic acid into the reaction solution, placing the reaction bottle at the temperature of 100 ℃ for reaction for 72 hours after dissolution, cooling to room temperature after the reaction is finished, placing the reaction bottle into a centrifuge, and collecting precipitates; the mass ratio of the zirconium tetrachloride to the organic ligand II is 1: 1; the addition amount of trifluoroacetic acid is 4.45 mu L/mg of organic ligand II;
washing the collected precipitate with N, N-dimethylformamide and ethanol for three times respectively to obtain yellow powder, namely chiral photosensitive metal organic framework MOF UiO-68-cs, with yield of 80%, and structural framework diagram shown in FIG. 5, with structural formula of Zr 6 O 4 (OH) 8 (L 2 ) n (L 1 ) m In the formula, L 1 Are organic ligands I, L 2 And m and n are the numbers of the organic ligand I and the organic ligand II respectively, and m + n is 6.
Claims (5)
1. A preparation method of a chiral photosensitive metal organic framework material is characterized by comprising the following steps:
a. synthesis of organic ligand i: (S) -4,4' - (2- (pyrrolidin-2-yl) -1H-benzo [ d ] imidazole-4, 7-diyl) dibenzoic acid represented by formula (1); synthesizing an organic ligand II: 4,4' - ([ [1,2,5] thiadiazole [3,4-c ] pyridine-4, 7-diyl) dibenzoic acid represented by formula (2);
the organic ligand I is synthesized by the following specific steps:
weighing cesium carbonate and cesium fluoride in a reaction bottle, adding water to dissolve, adding toluene, removing air in the reaction bottle and a solvent, adding a compound shown as a formula (3) and 4-tert-butoxycarbonylphenylboronic acid, fully stirring and dissolving, adding catalysts [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and tetrakis (triphenylphosphine) palladium, reacting for 24-48 h at 90-110 ℃ under the protection of nitrogen, cooling, extracting, drying, standing, spin-drying, and finally separating and purifying by column chromatography to obtain a compound shown as a formula (4);
dissolving a compound shown as a formula (4) by using dichloromethane, adding trifluoroacetic acid, stirring at room temperature overnight, and after the reaction is finished, carrying out suction filtration to obtain a white solid, namely the organic ligand I;
b. Sequentially adding organic ligand I and organic ligand II into the containerN,NDissolving dimethylformamide in a reaction bottle to obtain a reaction solution; the mass ratio of the organic ligand I to the organic ligand II is (1-2): 1;N,N-dimethylformamide is added in an amount of 1.33-1.67mL/mg of organic ligand ii;
c. adding zirconium tetrachloride and trifluoroacetic acid into the reaction solution, placing the reaction bottle at the temperature of 90-120 ℃ for reacting for 48-72h after dissolving, cooling to room temperature after the reaction is finished, placing the reaction bottle into a centrifuge, and collecting the precipitate; the mass ratio of the zirconium tetrachloride to the organic ligand II is (1-3): 1; the addition amount of trifluoroacetic acid is 1.44-8.89 mu L/mg of organic ligand II;
d. collecting the precipitate from step cN,NWashing with dimethylformamide and ethanol for three times respectively to obtain yellow powder, which is the chiral photosensitive metal organic framework material with the structural formula of Zr 6 O 4 (OH) 8 (L 2 ) n (L 1 ) m In the formula, L 1 Are organic ligands I, L 2 Is organic ligand II, m and n are the numbers of the organic ligand I and the organic ligand II respectively, and m + n = 6.
2. The method of claim 1, wherein in step b, the mass ratio of the organic ligand I to the organic ligand II is 2: 1; N,N-dimethylformamide is added in an amount of 1.33mL/mg of organic ligand ii; in the step c, the reaction bottle is placed at the temperature of 100 ℃ for reaction for 72 hours, and the mass ratio of the zirconium tetrachloride to the organic ligand II is 1: 1; trifluoroacetic acid is added in an amount of4.45. mu.L/mg of organic ligand II.
3. The method of claim 1, wherein in the step of synthesizing the organic ligand I, the mass ratio of cesium carbonate to cesium fluoride is 6: 1, in a molar ratio of the compound represented by the formula (3) to 4-tert-butoxycarbonylphenylboronic acid of 1: 2.4 the molar ratio between [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium and tetrakis (triphenylphosphine) palladium is 1: 1.2; the molar ratio of cesium carbonate, [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium to the compound represented by the formula (3) is 3: 1 and 0.1: 1.
4. the method for preparing the chiral photosensitive metal organic framework material according to claim 1, wherein in the specific step of synthesizing the organic ligand I, after the reaction is finished, the reaction system is cooled to room temperature, dichloromethane is used for extracting the reaction system, the organic phase is dried by adding anhydrous sodium sulfate, after the reaction system is kept stand for 6 hours, a proper amount of silica gel is added for vacuum spin drying, and a white solid is separated by a column chromatography method, so that the compound shown in the formula (4) is obtained; the mobile phase composition in the column chromatography is 50: 1, a mixed solvent of dichloromethane and ethyl acetate.
5. The method for preparing a chiral photosensitive metal organic framework material according to claim 1, wherein the step of synthesizing the organic ligand I comprises: dissolving the compound shown in the formula (4) by using dichloromethane, then adding trifluoroacetic acid, wherein the addition amount of the trifluoroacetic acid is 3mL/mmol, stirring at room temperature overnight, after the reaction is finished, adding dichloromethane, continuously stirring, washing off the trifluoroacetic acid, then standing, and carrying out suction filtration to obtain a white solid, namely the organic ligand I.
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