CN110551293A - 3, 4-ethylenedioxy group thiophene-2, 5-dicarboxylic acid zinc complex and preparation method thereof - Google Patents
3, 4-ethylenedioxy group thiophene-2, 5-dicarboxylic acid zinc complex and preparation method thereof Download PDFInfo
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- CN110551293A CN110551293A CN201910888925.7A CN201910888925A CN110551293A CN 110551293 A CN110551293 A CN 110551293A CN 201910888925 A CN201910888925 A CN 201910888925A CN 110551293 A CN110551293 A CN 110551293A
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- ethylenedioxythiophene
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Abstract
The invention discloses a 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid zinc complex and a preparation method thereof.A 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid is taken as a ligand, 4, 4-bipyridine is taken as an auxiliary ligand, and a zinc chloride salt is used for obtaining the 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid zinc complex by a solvothermal method, wherein the complex belongs to a monoclinic system, a space group is C 2 /c, unit cell parameters are a =18.5781(15) Å, b =10.0613(5) Å, c =17.9916(11) Å, beta =107.314(8) DEG, V =3210.6(4) Å 3 and Z = 8.
Description
Technical Field
the invention belongs to the technical field of metal organic complex synthesis, and particularly relates to a structure of a 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid zinc complex and a preparation method thereof.
Background
The metal organic complex is an organic-inorganic hybrid material with intramolecular pores, which is assembled by an organic ligand and metal ions or metal clusters through coordination bonds. The arrangement of organic ligand, metal ion and metal cluster has obvious directivity, so that it can form several frame structures, and has the characteristics of both organic matter and inorganic matter. And the MOFs material also has the advantages of very high specific surface area and high porosity, and also has the structural characteristics of controllability, decorativeness and the like. The material has excellent performances in the aspects of light, electricity, magnetism, adsorption, catalysis, ion exchange and the like, and attracts the attention of scientific researchers. The metal ions are easy to coordinate with lone pair electron atoms such as N, S, O, P and the like to form a complex with one-dimensional, two-dimensional and three-dimensional structures. The nitrogen heterocyclic carboxyl ligand combines the characteristics of nitrogen heterocycles and carboxyl groups, and the carboxylic acid groups can show various coordination modes such as monodentate coordination, bidentate coordination, asymmetric coordination, tridentate coordination, tetradentate coordination and the like when being coordinated with metal ions, so that the complex with complex and various configurations, novel structure and different functions can be derived. The current methods commonly used for synthesizing the complex are as follows: normal temperature solution method, hydrothermal method, solvothermal method, evaporation method, diffusion method, electrochemical method, and the like.
The metal ions are important factors influencing the complex structure, and different metal ions have different coordination numbers, so that the properties of the formed complexes are different. The transition metal complex has wide application in the aspects of magnetism, catalysis, luminescence, gas adsorption and the like. The application provides a method for synthesizing a compound with a chemical formula of [ C ] by taking 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid and transition metal salt as raw materials through a solvothermal method13H12ZnN2O9S]nA zinc complex structure and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a structure of a 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid zinc complex and a preparation method thereof.
The idea of the invention is as follows: 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid is used as a ligand, 4, 4-bipyridyl is used as an auxiliary ligand, and zinc chloride salt is used for obtaining the 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid zinc complex by a solvothermal method.
The molecular formula of the complex is as follows: c13H12ZnN2O9S, molecular weight is: 423.67, the complex belongs to monoclinic system, space group is C2/C, unit cell parameter is β＝107.314(8)°，The crystallographic data of Z-8 are shown in Table 1, and the partial bond lengths and bond angles are shown in Table 2.
TABLE 1 crystallographic data for zinc 3, 4-ethylenedioxythiophene-2, 5-dicarboxylate complexes
The preparation method of the 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid zinc complex comprises the following specific steps:
(1) 0.25mmol (0.0340g) of ZnCl was weighed2The resulting solution was dissolved in 6mL of distilled water to prepare a zinc chloride solution.
(2) 0.15mmol (0.0345g) of 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid and 0.15mmol (0.0234g) of 4, 4-bipyridine were weighed into a 25mL beaker, 4mL of DMF was added, followed by stirring to dissolve, to prepare a mixed solution containing 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid and 4, 4-bipyridine.
(3) dropwise adding the zinc chloride solution prepared in the step (1) into the mixed solution prepared in the step (2), magnetically stirring for 30min at room temperature, adjusting the pH value to 5-7 with ammonia water to clarify the solution, continuously stirring for 20min, transferring the obtained solution into a 25mL reaction kettle with a polytetrafluoroethylene bottle, putting the reaction kettle into an oven, heating to 85 ℃, reacting for 72h, cooling to 60 ℃ at the speed of 5 ℃/h, keeping the temperature for 12h, closing the oven, naturally cooling to room temperature, taking out the reaction kettle, generating block-shaped light yellow crystals, alternately washing for 3 times with DMF and distilled water, wherein the amount of DMF is 5mL each time, the amount of distilled water is 5mL, then putting the reaction kettle into a 50 ℃ vacuum drying oven, and drying for 12h to obtain the 3, 4-ethylenedioxythiophene-2, 5-zinc dicarboxylate complex.
The preparation method has the advantages of simple process, good repeatability, environmental protection and the like, successfully synthesizes the 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid zinc complex, and provides a certain basis for synthesizing the nitrogen heterocyclic carboxylic acid transition metal complex.
Drawings
FIG. 1 shows an example of the present invention in which the chemical formula is [ C ]13H12ZnN2O9S]nThe crystal structure of the zinc complex of (1).
FIG. 2 shows an example of the present invention in which the chemical formula is [ C ]13H12ZnN2O9S]nThe crystal three-dimensional stacking diagram (a direction) of the zinc complex of (a).
Detailed Description
Example (b):
(1) 0.25mmol (0.0340g) of ZnCl was weighed2The resulting solution was dissolved in 6mL of distilled water to prepare a zinc chloride solution.
(2) 0.15mmol (0.0345g) of 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid and 0.15mmol (0.0234g) of 4, 4-bipyridine were weighed into a 25mL beaker, and 4mL of DMF was added and then stirred to dissolve to prepare a mixed solution containing 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid and 4, 4-bipyridine.
(3) Dropwise adding the solution prepared in the step (1) into the mixed solution prepared in the step (2), magnetically stirring for 30min at room temperature, adjusting the pH value to 6 by using ammonia water to clarify the solution, and continuously stirring for 20 min; the obtained solution is transferred into a 25mL reaction kettle with a polytetrafluoroethylene bottle and is put into an oven to be heated to 5 ℃ for reaction for 72 hours. Cooling to 60 deg.C at a rate of 5 deg.C/h after 72 hr, maintaining for 12 hr, closing oven, naturally cooling to room temperature, taking out the reaction kettle, generating yellowish blocky crystal, washing with DMF and distilled water for 3 times, each time of DMF5mL of distilled water and 5mL of distilled water are put into a vacuum drying oven at 50 ℃ and dried for 12 hours to obtain the product with the chemical formula of [ C ]13H12ZnN2O9S]nzinc complex, yield 69%. Theoretical value of elemental analysis (%): c, 36.82; n, 6.61; h, 2.83; test value (%) C, 36.53; n, 6.43; h, 2.97.
The obtained chemical formula is [ C ]13H12ZnN2O9S]nAnd (3) analyzing the crystal structure of the zinc complex: selecting crystals with proper size, and using an Agilent Cni surface-detecting monocrystal diffractometer in America at 293(2) K, and adopting Mo-Ka raysDiffraction points were collected in an omega scan fashion. All crystal data are subjected to Lp factor correction and empirical absorption correction by adopting an SADABS program, non-hydrogen atoms are corrected by using a full matrix least square method, and hydrogen atom coordinates are given by theoretical values. Structural analysis was performed with Olex2, structural refinement and all calculations were performed with Olex 2. All hydrogen atoms are theoretically hydrogenated. The relevant crystallographic data are listed in table 1, and the main bond lengths and bond angles are listed in table 2.
As shown in Table 1, the complex belongs to the monoclinic system, space group is C2/C, unit cell parameter isβ＝107.314(8)°， and Z is 8. The basic unit of the complex comprises a 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid anion, a 4, 4-bipyridyl anion, a Zn ion and three water molecules (one of which is free water molecule) and a DMF molecule. In the complex, the coordination mode of Zn metal central ion is penta-coordination, which is respectively connected with two oxygen atoms of carboxyl on two 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid ligands and twoOne water molecule and one 4, 4-bipyridine molecule are coordinated. The Zn-O bond is grown atIn the meantime. The crystal structure diagram of the complex is shown in figure 1, and the direction a stacking diagram is shown in figure 2.
Claims (2)
1. A3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid zinc complex is characterized in that the molecular formula of the complex is as follows: c13H12ZnN2O9S, molecular weight is: 423.67, the complex belongs to monoclinic system, space group is C2/C, unit cell parameter isβ＝107.314(8)°，Z ═ 8, the crystallographic data are shown in table 1, and the parts and bond angles are shown in table 2;
TABLE 1 crystallographic data for zinc 3, 4-ethylenedioxythiophene-2, 5-dicarboxylate complexes
TABLE 2 partial bond length of zinc 3, 4-ethylenedioxythiophene-2, 5-dicarboxylate complexesAngle of harmony key (°)
2. A method for preparing a 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid zinc complex as claimed in claim 1, characterized by comprising the specific steps of:
(1) 0.25mmol (0.0340g) of ZnCl was weighed2Dissolving in 6mL of distilled water to prepare a zinc chloride solution;
(2) Weighing 0.15mmol (0.0345g) of 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid and 0.15mmol (0.0234g) of 4, 4-bipyridine into a 25mL beaker, adding 4mLN, N-Dimethylformamide (DMF), and stirring until dissolving to obtain a mixed solution containing 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid and 4, 4-bipyridine;
(3) dropwise adding the zinc chloride solution prepared in the step (1) into the mixed solution prepared in the step (2), magnetically stirring for 30min at room temperature, adjusting the pH value to 5-7 with ammonia water to clarify the solution, continuously stirring for 20min, transferring the obtained solution into a 25mL reaction kettle with a polytetrafluoroethylene bottle, putting the reaction kettle into an oven, heating to 85 ℃, reacting for 72h, cooling to 60 ℃ at the speed of 5 ℃/h, keeping the temperature for 12h, closing the oven, naturally cooling to room temperature, taking out the reaction kettle, generating block-shaped light yellow crystals, alternately washing for 3 times with DMF and distilled water, wherein the amount of DMF is 5mL each time, the amount of distilled water is 5mL, then putting the reaction kettle into a 50 ℃ vacuum drying oven, and drying for 12h to obtain the 3, 4-ethylenedioxythiophene-2, 5-zinc dicarboxylate complex.
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| CN110981894A (en) * | 2019-12-20 | 2020-04-10 | 山西大学 | Two-dimensional Cu functional complex and preparation method and application thereof |
| CN112409249A (en) * | 2020-10-28 | 2021-02-26 | 桂林理工大学 | 6-methylpyridine-2, 3-dicarboxylic acid zinc complex and preparation method thereof |
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| CN110981894A (en) * | 2019-12-20 | 2020-04-10 | 山西大学 | Two-dimensional Cu functional complex and preparation method and application thereof |
| CN110981894B (en) * | 2019-12-20 | 2021-07-27 | 山西大学 | Two-dimensional Cu functional complex and preparation method and application thereof |
| CN112409249A (en) * | 2020-10-28 | 2021-02-26 | 桂林理工大学 | 6-methylpyridine-2, 3-dicarboxylic acid zinc complex and preparation method thereof |
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Application publication date: 20191210 |