CN113896897A - Metal organic framework material for photocatalytic aerobic reaction and preparation method thereof - Google Patents
Metal organic framework material for photocatalytic aerobic reaction and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of environmental protection, and particularly discloses a metal organic framework material for a photocatalytic aerobic reaction and a preparation method thereof. The general formula of the metal organic framework material is { [ M (PBT) ]]·Gx}nBelonging to the tetragonal system, space group I4122, wherein M is Zn or Co, PBT is 4, 7-di (pyrazolyl) benzothiadiazole, G is a guest molecule, and x is a positive integer. The metal organic framework material provided by the invention has good chemical stability and thermal stability, good repeatability, simple synthesis process flow and strong operability. Importantly, the metal organic framework material requires only 1% of photocatalyst to catalyze five different aerobic reactions. Therefore, the metal organic framework material prepared by the method can be used as a metal organic framework material for carrying out the aerobic reaction through the cheap and efficient selective heterogeneous catalysis, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a metal organic framework material for a photocatalytic aerobic reaction and a preparation method thereof.
Background
Visible light driven organic conversion of solar energy to chemical energy provides a sustainable approach to the synthesis of valuable organic compounds. In the past decades, visible light driven photo-redox catalysis techniques have been significantly developed, particularly with ru (ii) and ir (iii) complexes as homogeneous photocatalysts that catalyze various organic reactions via a Single Electron Transfer (SET) mechanism. In recent years, compared with noble metal photocatalysts, inexpensive metal organic catalysts have been widely studied because of their advantages such as good practicability and low cost. Further, such a homogeneous catalyst is also limited by low utilization efficiency, poor recyclability, and the like. To address these drawbacks, researchers have developed a variety of strategies including integrating donors and acceptors into the same system for efficient use of visible light, and modifying photosensitizers into solid materials as heterogeneous catalysts.
Metal-organic frameworks (MOFs) are a class of crystalline porous materials due to their (1) large surface area and adjustable porosity; (2) easy functionalization; (3) the active sites are uniformly distributed; (4) the circulation can be carried out; (5) fast charge separation; (6) high photon absorption and other excellent characteristics, and may find wide application in magnetic, separating, storing, conducting, sensing, medicine transferring, especially heterogeneous catalysis and other fields. In addition, organic photosensitizers can act as building blocks, building into the framework of MOFs, forming photosensitizer complexes in the solid state. Because The Diazosulfide (BTD) unit has excellent light absorption efficiency, strong electron-withdrawing ability and photochemical activity, the BTD unit has been applied to the preparation of various heterogeneous photocatalytic complex materials. Meanwhile, it has been demonstrated in the previous literature that photosensitizers of donor-acceptor-donor (D-a-D) type can improve charge transfer efficiency. However, only the use of a single derivative of benzothiadiazole for the photocatalytic reaction has been reported, which does not reveal the excellent optical properties of the benzothiadiazole unit. Importantly, few of the previously reported MOF materials utilize ligands of the D-A-D type to effect photocatalytic aerobic type reactions. Thus, we envision that combining electron donating pyrazole groups and electron accepting benzothiophenediazole groups into D-a-D type organic ligands for the construction of MOF materials may provide a recoverable, inexpensive platform for heterogeneous photocatalysts with superior photocatalytic performance.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a metal organic framework material for visible light catalytic aerobic reactions under mild conditions and a method for preparing the same.
In order to achieve the purpose, the invention provides the following technical scheme:
a metal organic framework material for photocatalytic aerobic reaction has a structural general formula { [ M (PBT) ]]·Gx}nWherein M is Zn or Co, PBT is 4, 7-di (pyrazolyl) benzothiadiazole, and G is a guest molecule, such as DMF or water; x is a positive integer and n is a positive infinite natural number.
Preferably, when M is Zn, the structural formula is { [ Zn (PBT) ]]·Gx}n(ii) a When M is Co, the structural general formula is { [ Co (PBT)]·Gx}n. G is a guest molecule, such as DMF or water; x is a positive integer and n is a positive infinite natural number.
The metal organic framework material belongs to a tetragonal system, and the space group is I41When M ═ Zn, the unit cell parameters are:
α＝β＝γ＝90°，
when M is equal to Co, the composition,
α＝β＝γ＝90°，
a method for preparing the metal organic framework material for photocatalytic aerobic reactions described above, obtained:
(1) the ligand 4, 7-di (pyrazolyl) benzothiadiazole and zincDissolving salt in organic solvent, adding H after completely dissolving2O/HNO3Obtaining a mixed solution from the solution;
(2) and heating the mixed solution for reaction, and activating the obtained crystal after the reaction is finished to obtain the metal organic framework material.
Further, the organic solvent in the step (1) is N, N-dimethylacetamide or N, N-diethylacetamide.
Further, the mass ratio of the organic ligand 4, 7-bis (pyrazolyl) benzothiadiazole and the metal zinc salt in the step (1) is 1: 0.6-1.5.
Further, the metal zinc salt in the step (1) is Zn (NO)3)2·6H2O, cobalt salts being Co (NO)3)2·6H2O。
The molar concentration of the zinc salt in the organic solvent is 3.6 mmol/L-10 mmol/L.
Further, step (1) said H2O/HNO3H in solution2O and HNO3The volume ratio of (a) to (b) is 50: 8-15, preferably 50: 12.
said H2O/HNO3The volume ratio of the solution to the organic solvent is 1.5-5.5 mL: 100 to 180 μ L.
And (3) heating to react at the temperature of 115-135 ℃ for 48-96 h in the step (2).
After the heating reaction in step (2) is completed, the obtained crystals are preferably washed with an organic solvent, and the organic solvent is more preferably at least one of methanol and ethanol.
The activation in the step (2) is carried out for 12-36 h at 80-150 ℃, preferably 24h at 120 ℃.
The metal organic framework material for the high-efficiency photocatalytic reaction is applied as a photocatalyst.
The metal-organic framework material for photocatalytic aerobic reactions prepared by the process of the invention (denominated JNU-204-M) comprises an asymmetric unit comprising a crystallographically independent Zn (II) or Co (II) tetradentally with four pyrazoles having the same coordination environment. The zinc atom and the pyrazole coordinate to form one-dimensional (1D) rod-like secondary building blocks (SBUs). The SBU extends infinitely in the form of a common edge tetrahedron forming a strip 4 in its centre1A screw shaft; they are connected into a three-dimensional (3D) framework by organic ligands and are present in [001 ]]The direction has a square pore passage structure. The rod-shaped SBUs formed by the zinc atoms and the pyrazoles occupy the top points of the square pore channels, and the benzothiazole units in the organic ligand are uniformly distributed on four sides, so that the contact area with a guest molecule can be increased to the greatest extent. The metal organic framework has specific photosensitive groups, so that the metal organic framework can catalyze various aerobic reactions in the presence of a small amount of photocatalyst JNU-204-Zn (1%), and can be recycled for at least 3 times under the same reaction conditions, and the reaction yield is not reduced. Importantly, powder X-ray diffraction showed that the crystalline phase of JNU-204-Zn remained stable after three cycles.
Compared with the prior art, the invention has the following beneficial effects:
1. according to single crystal diffraction, the successfully synthesized metal organic framework material has a crystallographically independent Zn or Co atom in JNU-204-M, Zn or Co is coordinated with pyrazole from four ligands to form a chain-shaped secondary construction unit, and the secondary construction unit is further connected with organic ligand 4, 7-bis (pyrazolyl) benzothiadiazole to form a three-dimensional framework; in addition, along [001 ]]In the orientation, there was only one near square hole in the frame, calculated using PLATON, with a porosity of 34.3% or 33.8%. JNU-204-M can be simplified to a 6-c grid with point codes of 36.44.62.7.82}。
2. According to the experimental values, only 1% of photocatalyst is required to achieve catalysis of five aerobic reactions. Therefore, the metal organic framework material prepared by the method can be used as a metal organic framework material for selectively catalyzing aerobic type reaction with low cost and high efficiency.
3. The catalyst washed after centrifugation can be continuously used for at least 3 times after being dried, and the yield of the obtained corresponding product is not reduced. Importantly, JNU-204-Zn has good chemical stability and thermal stability, good repeatability, simple synthesis process flow, strong operability and wide application prospect.
Drawings
FIG. 1 is a high resolution desktop scanning electron micrograph of JNU-204-Zn prepared in example 1;
FIG. 2 is a powder XRD diffractogram of JNU-204-Zn prepared in example 1;
FIG. 3 is an infrared spectrum of JNU-204-Zn prepared in example 1;
FIG. 4 is a thermogram of JNU-204-Zn prepared in example 1;
FIG. 5 is a powder XRD diffractogram for JNU-204-Zn prepared in example 1 in different solvents;
FIG. 6 is a powder XRD diffractogram at various pHs for JNU-204-Zn prepared in example 1;
FIG. 7 is a diagram of the asymmetric unit of JNU-204-Zn prepared in example 1;
FIG. 8 is a c-axis pattern of the framework of JNU-204-Zn prepared in example 1;
FIG. 9 is the JNU-204-Zn nitrogen adsorption isotherm prepared in example 1;
FIG. 10 is a solid state UV-Vis diffuse emission plot of JNU-204-Zn prepared in example 1;
FIG. 11 is a graph of the Eg of JNU-204-Zn prepared in example 1, calculated by Tauc plot from the solid state UV-Vis diffuse emission data;
FIG. 12 is a graph of the solid state emission spectrum of JNU-204-Zn prepared in example 1;
FIG. 13 is an electromagnetic paramagnetic resonance spectrum of JNU-204-Zn prepared in example 1 showing superoxide radical anion generation;
FIG. 14 is a singlet oxygen generating electromagnetic paramagnetic resonance spectrum of JNU-204-Zn prepared in example 1;
FIG. 15 is a comparative powder XRD diffractogram of JNU-204-Zn and JNU-204-Co prepared in example 2
FIG. 16 is a graph of the visible light catalyzed arylphenylboronic acid reaction of JNU-204-Zn prepared in example 3;
FIG. 17 is a graph of the visible light catalyzed enamine reaction of JNU-204-Zn prepared in example 4;
FIG. 18 is a reaction diagram of JNU-204-Zn prepared in example 5 in visible light catalysis of sulfide to prepare beta-ketosulfone;
FIG. 19 is a graph of the visible photocatalytic oxidation/[ 3+2] cycloaddition/oxidative aromatization reaction of JNU-204-Zn prepared in example 6;
FIG. 20 is a powder XRD diffractogram of JNU-204-Zn prepared in example 1 after three cycles of photocatalytic aerobic reaction;
Detailed Description
The process of the present invention will be described in detail with reference to specific examples. The chemical name of DMF in the invention is N, N-dimethylformamide. In the invention, JNU-204-M represents a metal organic framework obtained by synthesis, wherein M is Zn or Co. The invention utilizes nuclear magnetic resonance hydrogen spectroscopy to determine the yield of the obtained organic product.
Example 1 preparation of a Metal-organic framework Material for reactions of the visible photocatalytic aerobic type
JNU-204-Zn preparation:
(1) the organic ligand 4, 7-bis (pyrazolyl) benzothiadiazole (5.7mg,0.02mmol) and Zn (NO)3)2·6H2O (6.0mg,0.02mmol) was dissolved in 3mL of DMF and after complete dissolution by sonication, 180. mu.L of H was added to the solution2O/HNO3(50/12mL) of the mixed solution, and ultrasonic treatment; adding the mixed solvent into a 10mL hard glass tube, placing the glass tube into an oven, heating to 120 ℃, preserving heat for 72 hours, cooling to room temperature, soaking the glass tube with absolute methanol or ethanol for multiple times, and filtering to obtain yellow columnar crystals; and exchanging the yellow crystal with anhydrous methanol or ethanol for multiple times, then putting the yellow crystal into a vacuum drying oven with the temperature of 120 ℃ for activation for 24 hours, and removing solvent molecules to obtain the metal organic framework material, which is JNU-204-Zn for short.
The crystal shape of the metal organic framework material prepared by the invention is shown in figure 1, figure 1 is a high-resolution desktop scanning electron microscope image of prepared JNU-204-Zn, as can be seen from the figure, the particle size of JNU-204-Zn crystal is about 100 μm, and the crystal quality and size can be characterized by a single crystal X-ray diffractometer.
The JNU-204-Zn obtained by the preparation is characterized as follows
(1) Powder X-ray diffraction characterization purity
Powder diffraction data collection was done on a bruker D8 advance diffractometer operating at 40KV and 40mA current using X-rays of a graphite monochromatized copper target (Cu ka,
) And continuous scanning is completed within the range of 3-40 degrees. Single crystal structure powder diffraction spectrum simulated transformation Mercury software was used. FIG. 2 is a powder XRD diffraction pattern of JNU-204-Zn, and from FIG. 2, it can be seen that synthesized JNU-204-Zn is identical with simulated JNU-204-Zn peak position, which proves that JNU-204-Zn has been successfully synthesized by the application.
(2) Infrared spectroscopy, thermal stability and chemical stability analysis
FIG. 3 is an infrared spectrum of JNU-204-Zn prepared using a Nicolet Impact 410FTIR spectrometer with KBr as the base at 400-4000cm-1Measured in the range, FT-IR (Potassium bromide tablet, cm)-1)：3119(w),1670(w),1590(m),1551(w),1409(w),1391(m),1306(w),1297(w),1255(s),1172(m),1099(m),1063(s),1017(m),924(w),882(m),865(w),831(m),611(m),543(m),505(w),464(m)cm-1。
In order to verify that JNU-204-Zn prepared by the invention has good chemical stability and thermal stability, thermogravimetric analysis is carried out, as shown in figure 4, JNU-204-Zn starts to decompose after 510 ℃, which shows that JNU-204-Zn has higher thermal stability; FIG. 5 shows XRD diffraction patterns of JNU-204-Zn prepared by the invention after being soaked for 2d in different solvents, and FIG. 6 shows XRD diffraction patterns of JNU-204-Zn prepared by the invention after being soaked for 2d in different pH conditions. As can be seen from the figure, the material has good solvent stability and acid-base stability.
(3) Determination of the Crystal Structure
Single crystals of appropriate size were selected under a microscope and subjected to X-ray diffractometry on XtaLab PRO single crystal (Cu K alpha,
) The radiation is monochromated by a graphite monochromator. Data processing program CrysAlis Using diffractometerPro.1(ii) a The structure was solved using the direct method to the initial model, then using F-based2And (4) refining the structure by using a least square method. All non-hydrogen atoms are processed by anisotropic refinement, and the position of the hydrogen atom is determined by a theoretical hydrogenation method. The guest molecules were in a highly disordered state and were processed using the SQEEZE program of PLATON software.
The crystal of the metal organic framework material prepared in example 1 belongs to the tetragonal system, and the space group is I4122. According to SXRD analysis and the coordination environment diagram of JNU-204-Zn, the frames of FIGS. 7 and JNU-204-Zn are along the c-axis direction. As can be seen from FIG. 8, the asymmetric unit contains a crystallographically independent Zn (II) which is tetrahedrally coordinated with four pyrazoles having the same coordination environment. The zinc atom and the pyrazole coordinate to form one-dimensional (1D) rod-like secondary building blocks (SBUs). The SBU extends infinitely in the form of a common edge tetrahedron, forming a strip 4 in its centre1A screw shaft; they are connected by organic ligands into a three-dimensional (3D) framework. The rod-shaped SBUs formed by the zinc atoms and the pyrazoles occupy the top points of the square pore channels, and the benzothiazole units in the organic ligand are uniformly distributed on four sides, so that the contact area with a guest molecule can be increased to the greatest extent. In addition, along [001 ]]In the orientation, there was only one near square hole in the frame, calculated using PLATON, with a porosity of 34.3%. JNU-204-Zn can be simplified into a 6-c grid with a point code number of 36.44.62.7.82}. JNU-204-Zn some of the parameters for crystallographic diffraction point data collection and structure refinement are shown in Table 1.
TABLE 1 crystallographic data for 1 JNU-204-Zn
aR1＝∑(||F0|-|Fc||)/∑|F0|；bwR2＝[∑w(F0 2-Fc 2)2/∑w(F0 2)2]1/2
FIG. 9 shows the nitrogen adsorption isotherms of JNU-204-Zn, from which it is clear that JNU-204-Zn has a large specific surface area (BET 804.9 m)2g-1) And porosity.
(4) Solid ultraviolet-visible diffuse reflection characterization light absorption range and band gap width
And (3) completing ultraviolet-visible diffuse reflection data collection on an Shimadzu UV3600 Plus, and completing continuous scanning within the range of 200-800 nm. The optical band gap of JNU-204-Zn was estimated based on the Tauc graphic method. FIG. 10 shows the UV-visible diffuse reflection of JNU-204-Zn, and FIGS. 10 and 11 show that the synthesized JNU-204-Zn has a light absorption range of 200-600 nm and an optical band gap of 2.35 eV.
(5) Characterization of the luminescence Range by solid emission Spectroscopy
Solid state luminescence spectra were measured on a Horiba FluoroMax-4 fluorometer. And continuously scanning within the range of 500-700 nm. FIG. 12 shows the solid state luminescence spectrum of JNU-204-Zn, and it can be seen from FIG. 12 that the synthesized JNU-204-Zn has a maximum emission wavelength of 585nm under 365nm excitation.
(6) Electromagnetic resonance spectrum characterization JNU-204-Zn can generate active oxygen under visible light
Electron Paramagnetic Resonance (EPR) signals were recorded on a Bruker A300 spectrometer (Germany), the tests were carried out at room temperature and under visible light irradiation with blue LEDs (400-470 nm). As can be seen from FIGS. 13 and 14, JNU-204-Zn can generate singlet oxygen under visible light irradiation ((S))1O2) And superoxide radical anion (O)2 ·-)。
Example 2
JNU-204-Co preparation:
(1) the organic ligand 4, 7-bis (pyrazolyl) benzothiadiazole (5.7mg,0.02mmol) and Co (NO)3)2·6H2O (5.7mg,0.02mmol) was dissolved in 3mL of DMF and after complete dissolution by sonication, 130. mu.L of H was added to the solution2O/HNO3(50/12mL) of the mixed solution, and ultrasonic treatment; the mixed solvent is added into a 10mL hard glass tubeHeating to 120 deg.C in oven, keeping the temperature for 72h, cooling to room temperature, soaking in anhydrous methanol or ethanol for several times, and filtering to obtain yellow columnar crystal; and exchanging the yellow crystal with anhydrous methanol or ethanol for multiple times, then putting the yellow crystal into a vacuum drying oven with the temperature of 120 ℃ for activation for 24 hours, and removing solvent molecules to obtain the metal organic framework material, which is JNU-204-Co for short.
(2) Determination of the Crystal Structure
Single crystals of appropriate size were selected under a microscope and subjected to X-ray diffractometry on XtaLab PRO single crystal (Cu K alpha,
) The radiation is monochromated by a graphite monochromator. Data processing program CrysAlis Using diffractometerPro.1(ii) a The structure was solved using the direct method to the initial model, then using F-based2And (4) refining the structure by using a least square method. All non-hydrogen atoms are processed by anisotropic refinement, and the position of the hydrogen atom is determined by a theoretical hydrogenation method. The guest molecules were in a highly disordered state and were processed using the SQEEZE program of PLATON software.
The crystal of the metal organic framework material prepared in example 2 belongs to the tetragonal system, and the space group is I4122. As shown in FIG. 15, XRD showed JNU-204-Zn and JNU-204-Co were of the same configuration. JNU-204-Co, some of the parameters for crystallographic diffraction point data collection and structure refinement are shown in Table 2.
TABLE 2 crystallographic data 2 JNU-204-Co
aR1＝∑(||F0|-|Fc||)/∑|F0|；bwR2＝[∑w(F0 2-Fc 2)2/∑w(F0 2)2]1/2
Example 3
JNU-204-Zn used for visible light catalysis of arylboronic acidsHydroxylation reaction of (2): aryl boronic acid (1) (0.501mmol), Et under a 30W blue LED3N (139.3. mu.L, 1.002mmol), JNU-204(1.0mg, 0.005mmol) in CH3CN/H2The mixed solution of O (4:1, 5mL) was stirred at room temperature for 48 h. The solvent was distilled under reduced pressure, and the crude residue was purified by column chromatography on a silica gel column (petroleum ether: ethyl acetate 8:1) to obtain product 2 as shown in fig. 16.
(2a)1H NMR(400MHz,CDCl3)δ6.91(2H,d,J＝8.0Hz),7.55(2H,d,J＝8.0Hz)；13C NMR(100MHz,CDCl3)δ＝108.3,116.3,119.2,134.3,159.0。
(2b)1H NMR(400MHz,CDCl3)δ＝4.95(1H,br),6.82-6.84(1H,m),6.91-6.95(2H,m),7.22-7.27(2H,m)；13C NMR(100MHz,CDCl3)δ＝115.3,120.8,129.7,155.4.
(2c)1H NMR(400MHz,CDCl3)δ＝3.09(3H,s),6.08(1H,br),6.88(2H,ddd,J＝2.0,2.8,8.8Hz),7.96(2H,ddd,J＝2.0,2.8,8.8Hz)；13C NMR(100MHz,CDCl3)δ＝52.1,115.2,122.4,131.9,160.0,167.2.
(2d)1H NMR(400MHz,CDCl3)δ＝5.06(1H,br),6.72(2H,ddd,J＝2.0,2.8,8.8Hz),7.33(2H,ddd,J＝2.0,2.8,8.8Hz)；13C NMR(100MHz,CDCl3)δ＝112.8,117.2,132.4,154.6.
(2e)1H NMR(400MHz,CDCl3)δ＝7.17(1H,d,J＝7.2Hz),7.39(1H,s),7.43-7.49(2H,m),9.98(1H,s)；13C NMR(100MHz,CDCl3)δ＝114.7,122.0,123.5,130.4,137.8,156.3,192.3.
(2f)1H NMR(400MHz,CDCl3)δ＝3.76(3H,s),6.76-6.81(4H,m)；13CNMR(100MHz,CDCl3)δ＝55.8,114.8,116.0,149.4,153.7.
(2g)1H NMR(400MHz,CD3SOCD3)δ＝6.56(4H,s),8.62(2H,s)；13C NMR(100MHz,CD3SOCD3)δ＝116.1,150.2。
(2h)1H NMR(400MHz,CDCl3)δ＝7.28-7.34(2H,m),8.09(1H,d,J＝8.0Hz),8.28(1H,d,J＝1.6Hz)；13C NMR(100MHz,CDCl3)δ＝125.3,136.3,139.1,155.3.
Example 4
Enamine derivative (3) (0.501mmol), JNU-204-Zn (1.0mg,0.005mmol) were dissolved in MeOH (5mL) and stirred under a 30W blue LED at room temperature for 8 h. The solvent was distilled under reduced pressure, and the crude residue was purified by column chromatography on a silica gel column (petroleum ether: ethyl acetate ═ 20:1) to give product 4 as shown in fig. 17.
(4a)1H NMR(400MHz,CD3Cl)δ＝1.69(3H,s),2.20(3H,s),3.79(3H,s),5.29(1H,s),6.52(2H,dd,J＝0.8,8.8Hz),6.74(1H,t,J＝7.2Hz),7.20(2H,dd,J＝7.2,8.8Hz)；13C NMR(100MHz,CD3Cl)δ＝18.6,24.6,53.5,69.5,114.1,118.3,129.3,143.8,171.7,203.4.
(4b)1H NMR(400MHz,CD3Cl)δ＝1.62(3H,s),2.21(3H,s),3.73(3H,s),3.78(3H,s),4.96(1H,s),6.50(2H,ddd,J＝2.4,3.6,9.2Hz),6.74(2H,ddd,J＝2.4,3.6,9.2Hz)；13C NMR(100MHz,CD3Cl)δ＝18.7,24.8,53.4,55.6,70.1,114.8,116.4,137.7,152.9,171.9,203.9.
(4c)1H NMR(400MHz,CD3Cl)δ＝1.66(3H,s),2.19(3H,s),3.78(3H,s),5.33(1H,s),6.45(2H,d,J＝8.4Hz),7.09(2H,d,J＝8.4Hz)；13C NMR(100MHz,CD3Cl)δ＝18.5,24.6,53.6,69.5,115.2,123.1,129.2,142.4,171.4,202.8.
(4d)1H NMR(400MHz,CD3Cl)δ＝1.68(3H,s),2.20(3H,s),2.25(3H,s),3.79(3H,s),5.23(1H,s),6.30(1H,dd,J＝2.0,8.0Hz),6.37(1H,s),6.56(1H,d,J＝7.6Hz),7.03(1H,dd,J＝7.6,8.0Hz)；13C NMR(100MHz,CD3Cl)δ＝18.6,21.6,24.7,53.5,69.5,111.0,115.1,119.3,129.2,139.3,143.8,171.7,203.7.
(4e)1H NMR(400MHz,CD3Cl)δ＝0.88(3H,t,J＝7.6Hz),1.24-1.33(2H,m),1.54-1.62(2H,m),1.68(3H,s),2.19(3H,s),4.19(2H,t,J＝6.4Hz),5.3(1H,s),6.52(2H,dd,J＝0.8,8.4Hz),6.73(1H,dd,J＝7.6,8.0Hz),7.14(2H,dd,J＝7.6,8.0Hz)；13C NMR(100MHz,CD3Cl)δ＝13.5,18.5,18.8,24.7,30.3,66.5,69.6,114.1,118.3,129.3,143.9,171.2,203.7.
(4f)1H NMR(400MHz,CD3Cl)δ＝1.19(3H,d,J＝6.0Hz),1.27(3H,d,J＝6.4Hz),1.68(3H,s),2.21(3H,s),5.12(1H,m),5.31(1H,s),6.55(2H,d,J＝8.0Hz),6.75(1H,t,J＝7.2Hz),7.16(2H,dd,J＝7.6,8.0Hz)；13C NMR(100MHz,CD3Cl)δ＝18.4,21.3,21.4,24.6,69.6,70.5,114.1,118.2,129.3,144.1,170.5,205.8.
(4g)1H NMR(400MHz,CD3Cl)δ＝1.43(9H,s),1.63(3H,s),2.18(3H,s),5.25(1H,s),6.52(2H,d,J＝8.4Hz),6.72(1H,t,J＝7.2Hz),7.14(1H,2H,dd,J＝7.2,8.4Hz)；13C NMR(100MHz,CD3Cl)δ＝18.4,24.6,27.6,70.0,76.7,83.6,114.1,118.2,129.3,144.2,170.0,204.1.
Example 5
JNU-204-Zn for visible light catalysis of sulfides to produce beta-ketosulfones: under a 30W blue LED, acetylene derivative (6) (0.500mmol), JNU-204-Zn (1.0mg,0.005mmol), aryl-substituted benzenesulfonylhydrazide (5) (1.100mmol), KI (83.7mg, 0.504mmol) and NaOAc.3H2O (149.7mg, 1.100mmol) in DMF/H2O (5:1, 6mL) was stirred at room temperature for 24 h. After the reaction was completed, the reaction was quenched with water and extracted with ethyl acetate. The organic layer was washed with brine and Na2SO4Drying, filtering and concentrating. The crude residue was purified by flash column chromatography on silica gel (petroleum ether: ethyl acetate: 8:1) to give product 7 as shown in fig. 18.
(7a)1H NMR(400MHz,CD3Cl)δ＝2.47(3H,s),4.74(2H,s),7.36(2H,d,J＝8.4Hz),7.51(2H,dd,J＝7.6,8.0Hz),7.65(1H,t,J＝7.6Hz),7.79(2H,d,J＝8.4Hz),7.97(2H,d,J＝8.4Hz)；13C NMR(100MHz,CD3Cl)δ＝21.7,63.5,128.6,128.8,129.3,129.8,134.3,135.6,135.7,145.4,188.1。
(7b)1H NMR(400MHz,CD3Cl)δ＝2.45(3H,s),4.68(2H,s),7.34(2H,d,J＝8.0Hz),7.46(2H,ddd,J＝2.0,2.4,8.0Hz),7.59(2H,d,J＝8.0Hz),7.90(2H,ddd,J＝2.0,2.4,8.0Hz)；13C NMR(100MHz,CD3Cl)δ＝26.4,42.1,58.2,78.7,115.1,119.4,126.7,127.0,128.1,129.2,129.5,132.9,135.2,148.4
(7c)1H NMR(400MHz,CD3Cl)δ＝2.45(3H,s),4.68(2H,s),7.16(2H,tdd,J＝2.0,3.2,8.4Hz),7.34(2H,d,J＝8.0Hz),7.74(2H,d,J＝8.0Hz),7.98-8.02(2H,m)；13C NMR(100MHz,CD3Cl)δ＝21.7,63.7,116.1(d,J＝22.0Hz),128.5,128.9,132.2,132.3,135.5,145.5,166.4(d,J＝256.1Hz),186.6；19F NMR(396MHz,CD3Cl)δ＝102.35(1F,s).
(7d)1H NMR(400MHz,CD3Cl)δ＝2.47(3H,s),3.87(3H,s),4.73(2H,s),7.19(1H,dd,J＝2.4,8.0Hz),7.34(2H,d,J＝8.4Hz),7.39(1H,dd,J＝7.6,8.4Hz),7.44(1H,dd,J＝2.4,2.4Hz),7.52(1H,d,J＝7.6Hz),7.77(2H,d,J＝8.4Hz)；13CNMR(100MHz,CD3Cl)δ＝21.7,55.5,63.6,112.9,121.2,122.2,128.6,129.8,135.7,137.0,145.4,159.9,188.0.
(7e)1H NMR(400MHz,CD3Cl)δ＝2.455(3H,s),2.461(3H,s),4.71(2H,s),7.27(1H,d,J＝7.6Hz),7.30(1H,dd,J＝4.4,8.0Hz),7.35(2H,d,J＝8.0Hz),7.44(1H,dd,J＝7.2,7.6Hz),7.74-7.78(3H,m)；13C NMR(100MHz,CD3Cl)δ＝21.5,21.7,65.5,125.9,128.5,129.8,130.4,132.2,132.7,135.7,135.9,140.0,145.2,190.5.
(7f)1H NMR(400MHz,CD3Cl)δ＝2.43(3H,s),4.71(2H,s),7.24-7.29(2H,m),7.42(1H,dd,J＝7.2,7.6Hz),7.54(2H,t,J＝7.6Hz),7.66(1H,dd,J＝7.2,7.6Hz),7.71(1H,d,J＝8.0Hz),7.86-7.89(2H,m)；13C NMR(100MHz,CD3Cl)δ＝21.5,65.4,125.9,128.5,129.2,130.3,132.3,132.8,134.1,135.6,138.9,140.1,190.3.
(7g)1H NMR(400MHz,CD3Cl)δ＝2.40(3H,s),4.85(2H,s),7.30(2H,d,J＝8.0Hz),7.58(1H,ddd,J＝1.2,7.2,8.4Hz),7.64(1H,ddd,J＝1.6,7.2,8.0Hz),7.77(2H,d,J＝8.4Hz),7.87(1H,dd,J＝2.4,8.0Hz),7.89(1H,s),7.95(2H,d,J＝8.4Hz),8.4(1H,s)；13C NMR(100MHz,CD3Cl)δ＝21.6,63.7,123.9,127.1,127.7,128.6,128.8,129.3,129.8,129.9,132.16,132.20,133.0,135.6,135.9,145.4,188.0.
Example 6
JNU-204-Zn for visible light catalytic oxidation/[ 3+2]Cycloaddition/oxidative aromatization reaction: dissolving N-substituted tetrahydroisoquinoline ethyl acetate derivative (8) (132.7mg,0.605mmol), JNU-204-Zn (1.0mg,0.005mmol), and pyrroledione (9) (55.6mg, 0.500mmol) in CH3CN (5mL), stirred at room temperature for 12h under 30W blue LED. The blue LED was removed and N-bromo succinimide (97.9mg, 0.550mmol) was added. The solvent was distilled under reduced pressure, and flash column chromatography was performed on silica gel (petroleum ether: ethyl acetate: 10:1) to obtain product 10 as shown in fig. 19.
(10a)1H NMR(400MHz,CD3Cl)δ＝1.49(3H,t,J＝7.2Hz),3.13(3H,s),3.16(2H,t,J＝6.8Hz),4.43(2H,q,J＝7.2Hz),4.73(1H,t,J＝6.8Hz),7.28(1H,d,J＝8.4Hz),7.37(1H,ddd,J＝1.6,7.2,7.6Hz),7.42(2H,dd,J＝6.4,8.4Hz),8.52(1H,d,J＝6.8Hz)；13C NMR(100MHz,CD3Cl)δ＝14.1,24.1,28.2,43.1,61.4,116.5,118.0,125.5,125.7,127.5,127.7,127.9,130.1,132.3,132.7,159.6,162.7,164.0.
(10b)1H NMR(400MHz,CD3Cl)δ＝1.25-1.43(4H,m),1.49(3H,t,J＝7.2Hz),1.72(2H,d,J＝12.8Hz),1.85(2H,d,J＝13.2Hz),2.23(2H,ddd,J＝3.2,12.4,12.4Hz),3.14(1H,t,J＝6.8Hz),4.03-4.11(1H,m),4.43(2H,q,J＝6.8Hz),4.72(2H,t,J＝6.8Hz),7.27(1H,d,J＝4.4Hz),7.36(1H,ddd,J＝1.6,7.2,7.2Hz),7.41(1H,ddd,J＝1.2,7.2,8.0Hz)8.54(1H,dd,J＝1.6,8.0Hz)；13C NMR(100MHz,CD3Cl)δ＝14.3,25.3,26.2,28.4,29.9,43.3,51.1,61.5,116.8,117.9,125.7,125.8,127.6,127.89,127.94,130.1,132.4,132.8,159.9,162.8,164.4.
(10c)1H NMR(400MHz,CD3Cl)δ＝1.49(3H,t,J＝6.8Hz),3.19(2H,t,J＝6.8Hz),4.44(2H,q,J＝6.8Hz),4.78(2H,t,J＝6.8Hz),7.29(1H,d,J＝6.8Hz),7.36-7.43(5H,m),7.49(2H,t,J＝8.0Hz),8.59(1H,dd,J＝1.6,7.2Hz)；13C NMR(100MHz,CD3Cl)δ＝14.2,28.3,43.4,61.6,116.2,118.7,125.2,125.6,127.2,127.7,127.8,127.98,128.01,128.9,130.3,132.4,132.6,133.5,159.7,161.6,163.1.
(10d)1H NMR(400MHz,CD3Cl)δ＝1.47(3H,t,J＝6.8Hz),3.19(2H,t,J＝6.8Hz),3.84(3H,s),4.43(2H,q,J＝6.8Hz),4.78(2H,t,J＝6.8Hz),7.00(2H,d,J＝8.8Hz),7.28-7.32(3H,m),7.39(2H,ddd,J＝5.6,7.2,14.0Hz),8.58(1H,dd,J＝1.6,7.2Hz)；13C NMR(100MHz,CD3Cl)δ＝14.2,28.4,43.4,55.5,61.6,114.3,116.3,118.6,125.28,125.31,125.6,127.7,128.0,128.5,130.3,132.4,133.4,159.0,159.7,162.0,163.4.
(10e)1H NMR(400MHz,CD3Cl)δ＝1.47(3H,t,J＝7.2Hz),3.19(2H,t,J＝6.8Hz),4.44(2H,q,J＝6.8Hz),4.78(2H,t,J＝6.8Hz),7.30(1H,d,J＝6.0Hz),7.31-7.47(6H,m),8.56(1H,dd,J＝1.6,7.6Hz)；13C NMR(100MHz,CD3Cl)δ＝14.2,28.3,43.4,61.7,116.0,118.9,125.0,125.5,127.7,128.0,128.1,128.3,129.1,130.5,131.1,132.4,133.4,133.7,159.6,161.3,162.8.
(10f)1H NMR(400MHz,CD3Cl)δ＝1.47(3H,t,J＝6.8Hz),2.41(3H,s),3.19(2H,t,J＝6.8Hz),4.43(2H,q,J＝7.2Hz),4.78(2H,t,J＝6.8Hz),7.18-7.20(3H,m),7.29(1H,d,J＝6.4Hz),7.35-7.43(3H,m),8.59(1H,dd,J＝2.0,7.6Hz)；13C NMR(100MHz,CD3Cl)δ＝14.2,21.4,28.4,43.4,61.7,116.3,118.7,124.3,125.3,125.6,127.7,127.9,128.0,128.1,128.8,130.4,132.4,133.5,138.9,159.8,161.8,163.3.
Example 7
JNU-204-Zn cycling experiment: after carrying out the catalysis of examples 3, 4 and 5, the suspension after the reaction was centrifuged and, in turn, centrifuged several times with the corresponding reaction solvent. The obtained solid was dried and the same proportions of reactants were added, and the operation was repeated three times after the reaction was completed. The solids obtained after the third reaction was completed by centrifugation were tested for XRD as shown in fig. 20.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A metal organic framework material for photocatalytic reaction is characterized in that,the general formula of the metal organic framework material is { [ M (PBT) ]]·Gx}nWherein M is Zn or Co, PBT is 4, 7-di (pyrazolyl) benzothiadiazole, G is guest molecule, x is positive integer, and n is positive infinite natural number.
2. The metal-organic framework material for photocatalytic reaction according to claim 1, characterized in that,
when M is Zn, the general structural formula is { [ Zn (PBT)]·Gx}n(ii) a When M is Co, the structural general formula is { [ Co (PBT)]·Gx}n(ii) a PBT is 4, 7-di (pyrazolyl) benzothiadiazole, G is guest molecule, x is positive integer, and n is positive infinite natural number.
3. The metal-organic framework material for photocatalytic reaction according to claim 1, wherein the metal-organic framework material belongs to the tetragonal system and has space group I41When M ═ Zn, the unit cell parameters are:
α＝β＝γ＝90°，
when M ═ Co, unit cell parameters are:
α＝β＝γ＝90°，
4. a method for preparing a metal organic framework material for photocatalytic reactions as defined in any one of claims 1 to 3, comprising the steps of:
(1) the ligand isDissolving 4, 7-di (pyrazolyl) benzothiadiazole and zinc salt or cobalt salt in organic solvent, adding H after completely dissolving2O/HNO3Obtaining a mixed solution from the solution;
(2) and heating the mixed solution for reaction, and activating the obtained crystal after the reaction is finished to obtain two metal organic framework materials.
5. The method of claim 4, wherein the Zn salt used in step (1) is Zn (NO)3)2·6H2O, cobalt salts being Co (NO)3)2·6H2The O organic solvent is N, N-dimethylformamide or N, N-diethylacetamide; the molar concentration of the zinc salt and the cobalt salt in the organic solvent is 3.6 mmol/L-10 mmol/L.
6. The process for the preparation of a metal-organic framework material for photocatalysis according to claim 4, characterized in that, in step (1), the ratio of the amounts of said ligand 4, 7-bis (pyrazolyl) benzothiadiazole and metal zinc or cobalt salt species is 1:0.6 to 1.5.
7. The method for preparing a metal-organic framework material for photocatalysis according to claim 4, wherein the H in step (1)2O/HNO3H in solution2O and HNO3The volume ratio of (A) to (B) is 50: 8-15.
8. The method for preparing a metal organic framework material for photocatalysis according to claim 4, wherein the heating reaction temperature in the step (2) is 115-135 ℃, and the reaction time is 48-96 h; the activation in the step (2) is carried out for 12-36 h at 80-150 ℃.
9. Use of the metal organic framework material for high efficiency photocatalytic reactions according to claim 1 or 2 or 3 as a photocatalyst.
10. The use according to claim 9, wherein the metal organic framework material is used for visible light catalysis of sulfide to prepare beta-ketosulfone, visible light catalysis of oxidation/[ 3+2] cycloaddition/oxidative aromatization reaction, visible light catalysis of hydroxylation reaction of arylboronic acid or visible light catalysis of enamine reaction.
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