阅读说明：本技术 3,4-乙撑二氧基噻吩-2,5-二羧酸锌配合物及其制备方法 (3, 4-ethylenedioxy group thiophene-2, 5-dicarboxylic acid zinc complex and preparation method thereof ) 是由 刘峥 韦文厂 梁楚欣 梁秋群 陈则胜 艾慧婷 于 2019-09-19 设计创作，主要内容包括：本发明公开了一种3,4-乙撑二氧基噻吩-2,5-二羧酸锌配合物及其制备方法。以3,4-乙撑二氧基噻吩-2,5-二羧酸为配体,4,4-联吡啶为辅配,和氯化锌盐通过溶剂热法获得3,4-乙撑二氧基噻吩-2,5-二羧酸锌配合物。该该配合物属于单斜晶系,空间群为<I>C</I>2<I>/c</I>,晶胞参数为a=18.5781(15)?,b=10.0613(5)?,c=17.9916(11)?,β=107.314(8)°,V=3210.6(4)?<Sup>3</Sup>,Z=8。本发明的所述制备方法具有工艺简单、重复性好、绿色环保等优点,成功的合成了3,4-乙撑二氧基噻吩-2,5-二羧酸锌配合物,为合成含氮杂环羧酸过渡金属配合物提供了一定的理论依据。(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.)

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.

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