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）

Synthesis,Structure and Thermodynamics/Kinetics Analysis of Three Different Interpenetrating Zinc(Ⅱ) Coordination Architectures

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3>1>2。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。

Based on flexible 1,4-bis（2-methyl-imidazol-1-yl）butane（bib） and three rigid line-shaped carboxylate mix-ligands,three Zn（II） coordination polymers,{[Zn_2（bib）_2（1,4-ndc）_2]？H_2O}n（1）,{[Zn_（0.5）（bib）_（0.5）（bdc-Br_2）_（0.5）]？0.5H_2O}n（2）,{[Zn_2（bib）（4,4′-bpdc）_2] ？ H_2O}_n（3）（1,4-H_2ndc = 1,4-naphthalenedicarboxylic acid,H_2bdc-Br_2= 2,5-dibromoterephthalic acid,4,4′-H_2bpdc = 4,4′-biphenyldicarboxylic acid） have been synthesized under solvothermal conditions and characterized by elemental analysis,infrared（IR） spectrometry,and single crystal X-ray diffraction.1 presents a 4-fold interpenetrating framework including three kinds of zigzag chains.2 exhibits an unusual [2 ＋ 2] interpenetrating framework.3 features a 3-fold interpenetrating network.Their thermal decomposition behaviors were investigated by simultaneous thermogravimetry/differential thermal gravity and differential scanning calorimetry（TG/DTG-DSC） techniques.The TG curves indicate that the unusual [2 ＋ 2]interpenetrating framework exhibits the highest thermal stability of the three frameworks,and the 4-fold interpenetrating framework exhibits higher thermal stability than the 3-fold interpenetrating framework.The thermodynamics and kinetics of skeleton collapse for the complexes were calculated by the integral Kissinger′s method and Ozawa-Doyle′s method.The activation energies（E） of 276.887,318.515,and 149.310 k J？mol^（-1） illustrate the relationship of the reaction rates of complexes 1-3：3 1 2.The structural characteristics could be elucidated from the thermodynamics and kinetics.Moreover,the fluorescent properties of complexes 1-3were also studied.