三个不同穿插的锌配合物的合成、结构和热动力学分析（英文）

发布时间：2018-05-11 01:18

  本文选题：配合物 + 穿插　； 参考：《物理化学学报》2016年06期

【摘要】：使用醋酸锌,柔性的1,4-二甲基咪唑丁烷(bib)和三个刚性直链型羧酸混合配体,在溶剂热条件下合成了三个具有不同穿插结构的配合物。并通过元素分析,红外,X射线单晶衍射进行了表征。配合物1是一个具有三种Z字链的四重穿插结构,配合物2是一个特殊的[2+2]型四重穿插结构,配合物3是一个具有双核结构单元的三重穿插结构。通过使用热重分析/微分热重和差示扫描量热(TG/DTG-DSC)技术研究了它们的热分解过程,由热重分析得出特殊的[2+2]型四重穿插结构稳定性最好,四重穿插结构比三重穿插结构稳定。使用Kissinger和Ozawa-Doyle法对配合物骨架坍塌过程进行了计算,得出配合物1-3的表观活化能分别为276.887、318.515、149.310 k J?mol~(-1),可以得出配合物1-3的反应速率关系为312。从热力学和动力学的角度来说明配合物的结构稳定性。其次,还对配合物1-3的荧光性质进行了表征。
[Abstract]:Three complexes with different intercalation structures were synthesized under solvothermal conditions using zinc acetate, a flexible 1-dimethylimidazolyl butadiene and three rigid straight chain carboxylic acid mixed ligands. The elemental analysis and IR X ray single crystal diffraction were used to characterize the structure. Complex 1 is a quaternary intercalation structure with three Z chains, complex 2 is a special [22] type quadruple intercalation structure, and complex 3 is a triple intercalation structure with double core structure. Thermogravimetric analysis / differential thermogravimetry and differential scanning calorimetry (TG- / DTG-DSC) were used to study their thermal decomposition process. The results of thermogravimetric analysis show that the special [22] type quadruple intercalation structure has the best stability, and the quadruple intercalation structure is more stable than the triple interlaced structure. Kissinger and Ozawa-Doyle methods were used to calculate the collapse process of complex skeleton. The apparent activation energy of complex 1-3 was 276.887318.515kJ / mol / L ~ (-1) ~ (-1), respectively. The reaction rate relationship of complex 1-3 was 31212K. The structure stability of the complex is explained from the viewpoint of thermodynamics and kinetics. Secondly, the fluorescence properties of complex 1-3 were also characterized.
【作者单位】： 西北大学化学与材料科学学院教育部合成与天然功能分子化学重点实验室;商洛学院化工与现代材料科学学院陕西省尾矿资源利用重点实验室;
【基金】：supported by the National Natural Science Foundation of China(21543001,21273137) Open Foundation of Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education,China(338080041) Open Foundation of the Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources,China(2014SKY-WK002)~~
【分类号】：O641.4
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本文编号：1871775