CN114854033A - Preparation and application of Eu metal-organic framework material based on non-planar porphyrin ligand - Google Patents

Preparation and application of Eu metal-organic framework material based on non-planar porphyrin ligand Download PDF

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CN114854033A
CN114854033A CN202210583752.XA CN202210583752A CN114854033A CN 114854033 A CN114854033 A CN 114854033A CN 202210583752 A CN202210583752 A CN 202210583752A CN 114854033 A CN114854033 A CN 114854033A
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谢亚勃
吴伟
吕修亮
司广锐
李建荣
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Abstract

Preparation and application of a metal-organic framework material of Eu based on non-planar porphyrin ligand, belonging to the technical field of crystalline materials. The material is made of Eu 6 Cluster, o-fluorobenzoic acid molecule, DMF and porphyrin ligand 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]4,4' -dicarboxylic acid porphyrin-Co (II) (Co-BBCPPP-Ph), and the chemical formula is [ C 170 H 114 CoEu 6 F 2 N 12 O 34 ]. The synthesis of the metal-organic framework is carried out by taking Co-BBCPPP-Ph and europium nitrate hexahydrate as mixed solution of DMF and o-fluorobenzoic acid and carrying out solvothermal reactionObtaining crystals of the metal organic framework material; the material shows the application in the aspect of degrading the mustard gas simulant 2-chloroethyl ethyl sulfide by high-efficiency photocatalytic oxidation.

Description

Preparation and application of Eu metal-organic framework material based on non-planar porphyrin ligand
Technical Field
The invention belongs to the technical field of crystalline materials, and relates to a metal-organic coordination polymer material, which is characterized by a synthetic method and application research of a Eu metal-organic framework material of a non-planar porphyrin ligand.
Background
Porphyrin compounds are widely existed in living bodies in the nature, for example, heme is a porphyrin compound containing iron, chlorophyll is a porphyrin compound containing magnesium, and the porphyrin compounds have the characteristics of oxygen transmission, light capture, catalysis and the like. They act with varying degrees of distortion of the porphyrin planes, which, of course, give rise to many unique functions with rather unique effects. For example, the macrocyclic contorted conformation of heme can alter its affinity for oxygen, can activate inactive C-H bonds, stabilize the oxidation state of the central fe (ii) and produce a highly oxidized fe (iv) O complex, and the like. Therefore, the study on the synthesis, structure and performance of the non-planar porphyrin is widely concerned.
Metal organic framework Materials (MOFs) assembled from organic ligands and metal cations or metal clusters have attracted considerable attention over the last two decades. They show excellent potential application prospects in many fields such as gas storage/separation, catalysis, sensing and proton conduction. The excellent application properties of MOFs benefit from their high porosity and structural tunability, and a variety of organic ligands can be combined into MOFs, allowing the generation of an almost unlimited number of new materials. Porphyrin MOFs have gained wide attention as one of the special MOFs in the biomedical and chemical fields. However, in the porphyrin MOFs, the configuration of the porphyrin ring is relatively single, and most of the porphyrin ring is in a planar configuration. Therefore, it is of great significance to explore the diversity of porphyrin ligand configurations and the diversity of porphyrin MOFs structures so as to endow more performances.
Disclosure of Invention
The invention aims to provide a metal-organic framework material of Eu of a non-planar porphyrin ligand, a preparation method and application thereof.
The invention relates to a three-dimensional porphyrin-based metal-organic framework material, which is characterized in that Eu is used as a raw material 6 Metal-organic framework material composed of cluster, o-fluorobenzoic acid molecule, N-Dimethylformamide (DMF) molecule and non-planar porphyrin ligandMaterial with chemical formula of [ C 170 H 114 CoEu 6 F 2 N 12 O 34 ]Wherein the porphyrin ligand is 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]-4,4 "-dicarboxylic acid) porphyrin-Co (II) Co-BBCPPP-Ph, having the formula:
Figure BDA0003662788330000021
the metal-organic framework material has a three-dimensional framework structure, and from the angle of the connection and construction of the framework, the crystal structure of the metal-organic framework belongs to a monoclinic system, the space group is C2/m, and the unit cell parameters are as follows:
Figure BDA0003662788330000022
Figure BDA0003662788330000023
α＝γ＝90°,β＝101.169(3)°。
in the metal-organic framework, the Co-BBCPPP-Ph ligand presents a tetrahedral configuration, porphyrin rings in the ligand are in a non-coplanar state, the ligand belongs to a saddle-type non-planar distortion mode, and the connected metal cluster is Eu 6 Cluster and Eu 6 The clusters coordinate with the carboxyl oxygen from eight different Co-BBCPPP-Ph ligands; generally, the carboxyl group from the ligand is bound to the Eu 6 The O-Eu-Eu-O planes in the cluster are coplanar. However, in this metal-organic framework, four of the carboxyl groups from the Co-BBCPPP-Ph ligands were severely distorted from the O-Eu-O plane by 39 degrees from their normal in-plane position, while the carboxyl groups of the remaining four ligands were also bent by 14 degrees from their normal in-plane position; further, each Eu 6 Two o-fluorobenzoic acid molecules and four DMF molecules are coordinated on the cluster; each porphyrin ligand is bound to Eu 6 The clusters are interconnected to form a hexagonal channel in the direction of the a-axis.
From a topological point of view, each Co-BBCPPP-Ph ligand can be regarded as a 4-connected node with a tetrahedral configuration, and at the same time Eu is 6 The cluster canViewed as 8-connected vertices, these two types of building blocks are alternately connected to form a classical (4, 8) -connected flu topology network.
The ligand comprises a porphyrin ring and four carboxylic acid groups, and the included angle between two adjacent carboxylic acid groups in the ligand is 115 degrees.
The invention relates to a synthesis method of novel organic ligand 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) double ([1,1 ': 3', 1 '-terphenyl ] -4,4' -dicarboxylic acid) porphyrin-Co (II), which comprises the following steps:
(a) formation of bis (1H-pyrrol-2-yl) methane (3): adding trifluoroacetic acid into a solution of paraformaldehyde and freshly distilled pyrrole, sealing, protecting with inert gas, reacting at room temperature for 3 hours, adding sodium hydroxide, and purifying to obtain bis (1H-pyrrol-2-yl) methane (3);
(b)5 '-formyl- [1, 1': 3', 1' -terphenyl]Preparation of dimethyl 4,4' -dicarboxylate (6): 3, 5-dibromobenzaldehyde, 4-methoxycarbonyl phenylboronic acid, sodium carbonate and Pd (PPh) 3 ) 4 Putting the mixture into a methanol solution, heating the mixture at the temperature of 80 ℃ for reaction for 12 hours under the protection of inert gas, and purifying to obtain the required aldehyde;
(c) synthesis of 5', 5 "- (5, 15-disubstituted) bis ([1, 1': 3', 1" -terphenyl ] -4,4' -dicarboxylic acid) tetramethylester porphyrin (7): reacting bis (1H-pyrrol-2-yl) methane (3) and 5 '-formyl- [1, 1': dissolving 3', 1' -terphenyl ] -4,4' -dicarboxylic acid dimethyl ester (6) in dichloromethane, adding trifluoroacetic acid under the protection of inert gas, reacting for 10 hours at room temperature in the dark, adding dichlorodicyano benzoquinone, continuing to react for 4 hours, and purifying to obtain a product;
preferably, the amount of 5 '-formyl- [1, 1': dimethyl 3', 1' -terphenyl ] -4,4' -dicarboxylate (6) corresponded to 13.68mmol of bis (1H-pyrrol-2-yl) methane (3), 10.00mmol of trifluoroacetic acid, 13.22mmol of dichlorodicyanobenzoquinone;
(d) synthesis of 5', 5 "- (10, 20-dibromo-5, 15-disubstituted) bis ([1,1 ': 3', 1" -terphenyl ] -4,4 "-dicarboxylic acid) tetramethylester porphyrin (8): dissolving 5', 5' - (5, 15-disubstituted) bis ([1,1 ': 3', 1 '-terphenyl ] -4,4' -dicarboxylic acid) tetramethyl porphyrin (7) and N-bromosuccinimide in trichloromethane, and reacting for four days at room temperature;
(e)5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]-synthesis of 4,4 "-dicarboxylic acid) tetramethylporphyrin (9): reacting 5', 5' - (10, 20-dibromo-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]4,4' -dicarboxylic acid) tetramethylporphyrin (8) and phenylboronic acid, potassium carbonate, Pd (PPh) 3 ) 4 Dissolving in a mixed solution of dioxane and water, heating and reacting for 12 hours at 100 ℃ under the protection of inert gas, and purifying to obtain a product;
(f)5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]Synthesis of 4,4' -dicarboxylic acid tetramethylporphyrin-Co (II) (10): reacting 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]4,4' -dicarboxylic acid) tetramethylporphyrin (9) and CoCl 2 ·6H 2 Dissolving O in N, N-Dimethylformamide (DMF), heating and refluxing at 150 ℃ for reaction for 12 hours to obtain a Co (II) porphyrin compound (10);
(g) preparation of 5', 5 "- (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1" -terphenyl ] -4,4 "-dicarboxylic acid) porphyrin-co (ii) (11): 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1 '-terphenyl ] -4,4' -dicarboxylic acid) tetramethylporphyrin-Co (II) (10) and sodium hydroxide in a mixed solution of tetrahydrofuran/methanol/water at 70 ℃ under heating and refluxing for 12 hours, removing the organic solvent by rotary evaporation, adjusting the pH of the solution to 3 with hydrochloric acid, and finally filtering to obtain the final product Co-BBCPPP-Ph (11).
The invention discloses a synthesis method of a novel metal-organic framework material, which comprises the following steps:
5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl) under sealed conditions]4,4' -dicarboxylic acid porphyrin-Co (II) Co-BBCPPP-Ph with europium nitrate hexahydrate (Eu (NO) 3 ) 3 ·6H 2 O) obtaining crystals of the metal-organic framework by solvothermal reaction in a mixed solution of N, N-Dimethylformamide (DMF) and O-fluorobenzoic acid;
further preferred are the organic ligands 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]-4,4' -dicarboxylic acid) pornquinoline-Co (II), i.e., Co-BBCPPP-Ph, with europium nitrate hexahydrate (Eu (NO) 3 ) 3 ·6H 2 O) is 1 (1-5), each 0.05mmol of europium nitrate corresponds to 1 mL-4 mL of DMF and 0.05 g-4 g of O-fluorobenzoic acid, the temperature of the thermal reaction is 80-160 ℃, and the reaction time is 12-168 hours.
The Eu metal-organic framework material of the non-planar porphyrin ligand can rapidly oxidize 2-chloroethyl ethyl sulfide (CEES, a chemical warfare agent mustard gas simulant) into a non-toxic product 2-chloroethyl ethyl sulfoxide (CEESO) within 20 minutes under the irradiation of an LED lamp.
The organic ligand synthesized by the invention belongs to a novel porphyrin carboxylic acid ligand. The metal-organic frame material constructed by the invention belongs to a novel organic frame material, and the material has a larger one-dimensional channel and is beneficial to the diffusion of reactants. And the porphyrin ring in the material is in a non-planar state, which is beneficial to the generation of singlet oxygen. The characteristics of the material enable the MOFs to have good catalytic performance in photocatalytic rapid oxidative degradation of mustard gas simulant 2-chloroethyl ethyl sulfide.
Drawings
FIG. 1 is a synthesis scheme for the synthesis of carboxylic porphyrin ligands of the metal-organic framework.
FIG. 2 shows a diagram of a secondary building block of the metal-organic framework, wherein (a) shows a coordination environment of Eu, and (b) and (c) show non-planar porphyrin ligands.
Fig. 3 is a schematic three-dimensional structure of the metal-organic framework.
FIG. 4 is a PXRD pattern for stability testing of the metal-organic framework material.
FIG. 5 shows MOF catalysts of the metal-organic framework material under LED illumination and O 2 Chemical expression of photo-oxidation CEES under atmosphere, (b, c) nuclear magnetic resonance hydrogen spectrum at reaction time 0 and 20 minutes.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
paraformaldehyde (100.00mmol), trifluoroacetic acid (5mL) and pyrrole (1000mL) were added to a 2L round bottom flask under nitrogen and the reaction was stirred at room temperature for 3 hours. After completion of the reaction, sodium hydroxide (50mmol) was added and the excess pyrrole was spun off. The crude product was purified by column chromatography to give, after concentration, 5.9g of bis (1H-pyrrol-2-yl) methane (3) as a white solid (62% yield).
Example 2:
3, 5-dibromobenzaldehyde (22.36mmol), 4-methoxycarbonylphenylboronic acid (38.53mmol), sodium carbonate (24.36mmol), Pd (PPh) 3 ) 4 (0.75mmol) and 600mL of methanol were added to a 1L round bottom flask, and the mixture was reacted at 80 ℃ for 12 hours under nitrogen. After the reaction, the reaction system was filtered, washed with ethanol (200mL × 2), and the solid obtained by the filtration was dissolved in chloroform (500mL), washed with water (500mL × 2) and saturated brine (500mL) in this order, and spin-dried to obtain 7.6g of a white product, 5 '-formyl- [1, 1': 3', 1' -terphenyl]Dimethyl (6) -4,4' -dicarboxylate (91% yield).
Example 3:
bis (1H-pyrrol-2-yl) methane (3) (13.68mmol), 5 '-formyl- [1, 1': 3', 1' -terphenyl]Dimethyl (6) (13.68mmol) of (E) -4,4' -dicarboxylate was dissolved in 2L of dichloromethane, trifluoroacetic acid (10.00mmol) was added under nitrogen protection, reaction was carried out at room temperature for 10 hours in the dark, dichlorodicyanobenzoquinone (13.22mmol) was added, the reaction system was spun off after 4 hours, the residue was dissolved in chloroform (500mL), washed with water (500 mL. times.3) and saturated brine (500mL) in this order, and washed with anhydrous Na 2 SO 4 Drying, filtering and concentrating. The crude product is purified by column chromatography (SiO) 2 Dichloromethane/ethyl acetate ═ 40:1 to 20:1) and concentrated to give 1.8g of a violet solid 5', 5 "- (5, 15-disubstituted) bis ([1, 1': 3', 1' -terphenyl]4,4' -dicarboxylic acid) tetramethylporphyrin (7) (yield 13%). 1 H NMR(CDCl 3 ,400MHz):δ＝10.38(s,2H),9.46(d,J＝4.64Hz,4H),9.21(d,J＝4.64Hz,4H),8.60(d,J＝1.64Hz,4H),8.34(m,2H),8.21(d,J＝8.52Hz,8H),8.01(d,J＝8.52Hz,8H),3.96(s,12H),-3.06(s,2H)。
Example 4:
by reacting 5', 5 "- (5, 15)-disubstituted) bis ([1, 1': 3', 1' -terphenyl]-4,4' -dicarboxylic acid) tetramethylporphyrin (7) (1.5mmol) was dissolved in 500mL of chloroform, N-bromosuccinimide (3.65mmol) was added to the reaction system in small amounts several times, and after four days of reaction at room temperature, the crude product was purified by column chromatography to obtain 1.6g of a violet solid 5', 5 "- (10, 20-dibromo-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl]4,4 "-dicarboxylic acid) tetramethylporphyrin (8) (yield 92%). 1 H NMR(CDCl 3 ,400MHz):δ＝9.68(d,J＝4.84Hz,4H),8.98(d,J＝4.32Hz,4H),8.48(d,J＝1.64Hz,4H),8.33(m,2H),8.21(d,J＝8.52Hz,8H),7.98(d,J＝8.52Hz,8H),3.96(s,12H),-2.64(s,2H)。
Example 5:
under the protection of nitrogen, 5'- (10, 20-dibromo-5, 15-disubstituted) double ([1, 1': 3', 1' -terphenyl)]4,4' -dicarboxylic acid) tetramethylporphyrin (8) (1.30mmol), phenylboronic acid (2.85mmol), K 2 CO 3 (5.06mmol)，Pd(PPh 3 ) 4 (0.62mmol) and dioxane (250mL) and water (50mL) were added to a 500mL round bottom flask and the reaction was stirred at 100 ℃ for 12 hours. After the reaction is finished, the organic solvent is removed by rotary evaporation, and the crude product is purified by column chromatography to obtain 1.4g of purple solid 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]-4,4 "-dicarboxylic acid) tetramethylporphyrin (9) (yield 93.63%). 1 H NMR(CDCl 3 ,400MHz):δ＝8.99(d,J＝4.72,4H),8.91(d,J＝4.68,4H),8.55(d,J＝1.56,4H),8.31(s,2H),8.22-8.24(m,4H),8.19(d,J＝8.44,8H),7.98(d,J＝8.44,8H),7.75-7.79(m,6H),3.95(s,12H),-2.71(s,2H)。
Example 6:
reacting 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]4,4' -dicarboxylic acid) tetramethylporphyrin (9) (1.0mmol) and CoCl 2 ·6H 2 O (12.6mmol) was dissolved in N, N-dimethylformamide (100mL), and the reaction was heated under reflux for 12 hours. After cooling to room temperature, 200mL of H was added to the mixture 2 And O. The resulting suspension was filtered and the solid dissolved in CHCl 3 And washed with water (100 mL. times.3). The organic layer was dried over anhydrous MgSO 4 Dried and evaporated, i.e.The purple solid 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bi ([1,1 ': 3', 1' -terphenyl) can be obtained]4,4 "-dicarboxylic acid tetramethylester porphyrin-Co (II) (10) (89.89% yield).
Example 7:
the resulting solid 5', 5 "- (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1" -terphenyl ] -4,4 "-dicarboxylic acid) tetramethylporphyrin-Co (II) (10) (0.87mmol) and sodium hydroxide (25mmol) were dissolved in a tetrahydrofuran (50 mL)/methanol (50 mL)/water (50mL) solution, stirred at 70 ℃ for 12 hours under reflux, and after the reaction was completed, the organic solvent was removed by rotary evaporation. The remaining solid was dispersed in 200mL of water, and then a 2M aqueous hydrochloric acid solution was added dropwise to adjust the pH to 3. The resulting suspension was filtered and the solid was washed with water (100 mL. times.3) and dried under vacuum at 60 ℃ to give the final product 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1 '-terphenyl ] -4,4' -dicarboxylic acid) porphyrin-Co (II) (Co-BBCPPP-Ph) (11) (90% yield).
Example 8:
the ligands Co-BBCPPP-Ph (0.06mmol) and Eu (NO) were weighed 3 ) 3 ·6H 2 O (0.12mmol) was placed in a 4mL glass vial, 1mL of DMF solution and 200mg of O-fluorobenzoic acid were added, and the vial was sealed and placed in an sonicator and sonicated at room temperature for 5 minutes. The sealed vial was placed in a 100 ℃ oven for reaction for 48 hours. After the reaction was complete, the oven was turned off, and after cooling to room temperature, the solid particles obtained in the vial were collected by filtration and then washed with DMF and EtOH in sequence (5 mL. times.3) to obtain purple blocky crystals (yield: 68% based on Co-BBCPPP-Ph ligand) as observed under the microscope.
Example 9:
the ligands Co-BBCPPP-Ph (0.05mmol) and Eu (NO) were weighed 3 ) 3 ·6H 2 O (0.20mmoL) was put into a 4mL glass vial, 2mL of DMF solution and 400mg of O-fluorobenzoic acid were added, and then the vial was sealed and put into an ultrasonic device and sonicated at room temperature for 5 minutes. The sealed vial was placed in a 120 ℃ oven for 72 hours. After the reaction was complete, the oven was turned off, after cooling to room temperature, the solid particles obtained in the vial were collected by filtration, then washed with DMF and EtOH in sequence (5mL × 3),observation under a microscope gave purple blocky crystals (yield: 75%, based on Co-BBCPPP-Ph ligand).
The test results of the products obtained in the above examples are the same, and specifically the following are shown:
(1) determination of crystal structure:
the powder with the proper size is selected, and data are collected by using a PANalytical X' Pert PRO high-resolution powder diffractometer at 298K. Data Collection Using Cu-Ka monochromatized by graphite monochromator
Figure BDA0003662788330000092
A target ray. Data absorption correction was done using SCALE3 absack software. The crystal structure was resolved by direct methods using the program SHELXTL-97. Firstly, determining all non-hydrogen atom coordinates by using a difference function method and a least square method, obtaining the hydrogen atom position by using a theoretical hydrogenation method, and then refining the crystal structure by using SHELXTL-97. See figures 2 to 3 for a block diagram. The crystallographic data are shown in table 1.
TABLE 1 crystallography data for Metal-organic framework materials
Figure BDA0003662788330000091
The carboxylic porphyrin ligand synthesis scheme of figure 1 shows: and (2) adding trifluoroacetic acid into the paraformaldehyde and the newly-distilled pyrrole solution, sealing, protecting with inert gas, adding sodium hydroxide after the room-temperature reaction is finished, and purifying to obtain the dipyrrole (3). 3, 5-dibromobenzaldehyde, 4-methoxycarbonyl phenylboronic acid, sodium carbonate and Pd (PPh) 3 ) 4 Putting the mixture into a methanol solution, heating and reacting under the protection of inert gas, and then carrying out suction filtration to obtain aldehyde (6); dissolving the dipyrrole (3) and the aldehyde (6) in dichloromethane, adding trifluoroacetic acid under the protection of inert gas, reacting for 10 hours at room temperature in the dark, adding dichlorodicyanobenzoquinone, and continuing to react for 4 hours to obtain a crude product (7). Dissolving porphyrin compound (7) and N-bromosuccinimide in chloroform, and reacting at room temperature for four days to obtain bromoporphyrin (8). Bromoporphyrin (8) and phenylboronic acid, potassium carbonate, Pd (PPh) 3 ) 4 Dissolved in dioxane and waterUnder the protection of inert gas, reacting at 100 ℃ for 12 hours to obtain the benzoporphyrin (9). Benzoporphyrin (9) and CoCl 2 ·6H 2 Dissolving O in DMF, heating and refluxing for reaction for 12 hours to obtain the cobalt porphyrin compound (10). Heating and refluxing a mixed solution of a cobalt porphyrin compound (10) and sodium hydroxide in tetrahydrofuran/methanol/water (preferably in a volume ratio of 1:1:1) for 12 hours, removing the organic solvent by rotary evaporation, adjusting the pH value of the solution to 3, and finally filtering to obtain a final carboxylic acid porphyrin ligand (11).
The block diagram of fig. 2 shows: the inorganic node contained in the frame structure is Eu 6 The porphyrin ligands present a tetrahedral configuration and the porphyrin rings are in a non-planar state.
The block diagram of fig. 3 shows: a three-dimensional stacking diagram in the metal-organic framework.
(2) The stability of the material and the photocatalytic oxidation degradation of the 2-chloroethyl ethyl sulfide.
FIG. 4 is a graph of powder diffraction data of the material of the present invention, which can be seen to be stable in methanol, acetonitrile, dichloromethane, and water. FIG. 5(a) MOF catalyst on LED illumination and O 2 Chemical expression of photooxidative degradation of CEES under atmosphere. FIG. 5(b, c) is the NMR spectra at 0 and 20 minutes, and it can be seen that the material can rapidly oxidize CEES to non-toxic CEESO with selectivity>99％。

Claims (8)

1. The Eu metal-organic framework material of the non-planar porphyrin ligand is characterized in that Eu is used as a metal-organic framework material 6 Cluster, o-fluorobenzoic acid molecule, N-Dimethylformamide Molecule (DMF) and porphyrin ligand 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]A metal-organic framework material consisting of (E) -4,4' -dicarboxylic acid porphyrin-Co (II) Co-BBCPPP-Ph and a chemical molecular formula of [ C 170 H 114 CoEu 6 F 2 N 12 O 34 ]。
2. A metal-organic framework material of Eu based on non-planar porphyrin ligands according to claim 1, characterized in that the metal-organic framework material hasThe three-dimensional frame structure is formed by connecting and constructing frames, the crystal structure of the metal-organic frame belongs to a monoclinic system, the space group is C2/m, and the unit cell parameters are as follows:
Figure FDA0003662788320000011
Figure FDA0003662788320000012
α＝γ＝90°,β＝101.169(3)°。
3. a metal-organic framework material of Eu based on non-planar porphyrin ligands, according to claim 1, wherein in the metal-organic framework the Co-BBCPPP-Ph porphyrin ligands assume a tetrahedral configuration with the porphyrin rings in a non-planar state, Eu 6 The clusters coordinate with the carboxyl oxygen from eight different Co-BBCPPP-Ph ligands, and, in addition, Eu 6 Two o-fluorobenzoic acid molecules and four DMF molecules are coordinated on the cluster; generally, the carboxyl group from the ligand is bound to the Eu 6 The O-Eu-Eu-O planes in the cluster are coplanar; however, in this metal-organic framework, four of the carboxyl groups from the Co-BBCPPP-Ph ligands are severely twisted with the O-Eu-O plane, bending 39 degrees from their normal in-plane position, while the remaining four ligands also bend 14 degrees from their normal in-plane position; porphyrin ligand and Eu 6 The clusters are interconnected to form a hexagonal channel in the direction of the a-axis.
4. A Eu metal-organic framework material based on non-planar porphyrin ligands, according to claim 1, wherein each of the Co-BBCPPP-Ph ligands in tetrahedral configuration can be considered as a 4-connected node from a topological point of view, and Eu is at the same time 6 Clusters can be regarded as 8-linked vertices, and these two types of building blocks are alternately linked to form a (4, 8) -linked flu network, i.e., a porphyrin MOF with flu topology.
5. A non-planar porphyrin ligand Eu-based metal-organic framework material according to claim 1, wherein said organic ligand is 5', 5 "- (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1" -terphenyl ] -4,4 "-dicarboxylic acid) porphyrin-Co (ii) (Co-BBCPPP-Ph) having the following structural formula:
Figure FDA0003662788320000021
the ligand comprises a porphyrin ring and four carboxylic acid groups; the included angle between two adjacent carboxyl groups in the ligand is 115 degrees.
6. A non-planar porphyrin ligand Eu-based metal-organic framework material according to claim 5, wherein the Co-BBCPPP-Ph ligand synthesis method comprises the following seven steps:
(a) formation of bis (1H-pyrrol-2-yl) methane (3): adding trifluoroacetic acid into paraformaldehyde and freshly distilled pyrrole, sealing, protecting by inert gas, reacting at room temperature for 3 hours, adding sodium hydroxide, and purifying to obtain di (1H-pyrrol-2-yl) methane (3);
(b)5 '-formyl- [1, 1': 3', 1' -terphenyl]Preparation of dimethyl 4,4' -dicarboxylate (6): 3, 5-dibromobenzaldehyde, 4-methoxycarbonyl phenylboronic acid, sodium carbonate and Pd (PPh) 3 ) 4 Putting the mixture into a methanol solution, heating the mixture for reaction for 12 hours at the temperature of 80 ℃ under the protection of inert gas, and purifying to obtain the required aldehyde.
(c) Synthesis of 5', 5 "- (5, 15-disubstituted) bis ([1, 1': 3', 1" -terphenyl ] -4,4' -dicarboxylic acid) tetramethylester porphyrin (7): reacting bis (1H-pyrrol-2-yl) methane (3) and 5 '-formyl- [1, 1': dissolving 3', 1' -terphenyl ] -4,4' -dicarboxylic acid dimethyl ester (6) in dichloromethane, adding trifluoroacetic acid under the protection of inert gas, reacting for 10 hours at room temperature in the dark, then adding dichlorodicyanobenzoquinone, continuing to react for 4 hours, and purifying to obtain a product;
preferably, the amount of 5 '-formyl- [1, 1': dimethyl 3', 1' -terphenyl ] -4,4' -dicarboxylate (6) corresponded to 13.68mmol of bis (1H-pyrrol-2-yl) methane (3), 10.00mmol of trifluoroacetic acid, 13.22mmol of dichlorodicyanobenzoquinone;
(d) synthesis of 5', 5 "- (10, 20-dibromo-5, 15-disubstituted) bis ([1,1 ': 3', 1" -terphenyl ] -4,4 "-dicarboxylic acid) tetramethylester porphyrin (8): dissolving 1.5mmol of 5', 5' - (5, 15-disubstituted) bis ([1,1 ': 3', 1 '-terphenyl ] -4,4' -dicarboxylic acid) tetramethyl porphyrin (7) and 3.65mmol of N-bromosuccinimide in 500mL of trichloromethane, and reacting at room temperature for four days to obtain (8);
(e)5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]-synthesis of 4,4 "-dicarboxylic acid) tetramethylporphyrin (9): reacting 5', 5' - (10, 20-dibromo-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]4,4' -dicarboxylic acid) tetramethylporphyrin (8) and phenylboronic acid, potassium carbonate, Pd (PPh) 3 ) 4 Dissolving in a mixed solution of dioxane and water, and heating and reacting for 12 hours at 100 ℃ under the protection of inert gas;
(f)5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]Synthesis of 4,4' -dicarboxylic acid tetramethylporphyrin-Co (II) (10): reacting 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1' -terphenyl)]4,4' -dicarboxylic acid) tetramethylporphyrin (9) and CoCl 2 ·6H 2 Dissolving O in N, N-Dimethylformamide (DMF), heating and refluxing at 150 ℃ for reaction for 12 hours to obtain a Co (II) porphyrin compound (10);
(g) preparation of 5', 5 "- (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1" -terphenyl ] -4,4 "-dicarboxylic acid) porphyrin-co (ii) (11): 5', 5' - (10, 20-diphenyl-5, 15-disubstituted) bis ([1,1 ': 3', 1 '-terphenyl ] -4,4' -dicarboxylic acid) tetramethylporphyrin-Co (II) (10) and sodium hydroxide in a mixed solution of tetrahydrofuran/methanol/water at 70 ℃ under heating and refluxing for 12 hours, removing the organic solvent by rotary evaporation, adjusting the pH of the solution to 3 with hydrochloric acid, and finally filtering to obtain the final product Co-BBCPPP-Ph (11).
7. Method for the preparation of Eu metal-organic framework material based on non-planar porphyrin ligands according to any of claims 1-6, characterized in that it comprises the following steps:
under the sealing condition, the Co-BBCPPP-Ph and the europium nitrate hexahydrate are in the N state,obtaining crystals of the metal-organic framework through solvothermal reaction in a mixed solution of N-Dimethylformamide (DMF) and o-fluorobenzoic acid; organic ligand Co-BBCPPP-Ph and europium nitrate hexahydrate (Eu (NO) 3 ) 3 ·6H 2 O) is 1 (1-5), each 0.05mmol of europium nitrate corresponds to 1 mL-4 mL of DMF and 0.05 g-4 g of O-fluorobenzoic acid, the temperature of the thermal reaction is 80-160 ℃, and the reaction time is 12-168 hours.
8. Use of the Eu-based metal-organic framework material of any one of claims 1-6 for photocatalytic oxidative degradation of mustard gas simulant 2-chloroethyl ethyl sulfide (CEES).
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