基于琥珀酸配体的锌/镉配合物的合成、结构及性质

Synthesis,Structure,and Properties of Zinc/Cadmium Complexes Based on Succinic Acid Ligand

在水热条件下获得了2个过渡金属配合物[Zn(suc)(HL)]_(n)(1)和[Cd(suc)_(0.5)(L)]_(n)(2)(H_(2)suc=琥珀酸,HL=3-(2-吡啶基)吡唑),并通过元素分析、IR光谱、单晶X射线衍射、热重分析、荧光光谱和粉末X射线衍射对结构进行了表征。在配合物1中,羧基配体suc^(2-)通过双齿和单齿模式桥联金属中心形成了二维网络结构。在2中,suc^(2-)和L^(-)配体连接Cd(Ⅱ)离子也形成了二维框架。此外,通过基于Gaussian16程序的PBE0/LANL2DZ方法,对从1和2的晶体结构中选出的“分子碎片”进行了量子化学计算。计算结果表明,配位原子与Zn(Ⅱ)离子、Cd(Ⅱ)离子之间存在着明显的共价相互作用。

Two transition-metal complexes,[Zn(suc)(HL)]_(n)(1)and[Cd(suc)_(0.5)(L)]_(n)(2)(H_(2)suc=succinic acid,HL=3-(2-pyridyl)pyrazole),have been achieved under hydrothermal conditions and structurally characterized by elemental analysis,IR spectrum,single-crystal X-ray diffraction,thermogravimetric analysis,fluorescent spectroscopy,and powder X-ray diffraction.In complex 1,the carboxyl ligand suc^(2-) bridges the metal centers via bidentate and monodentate modes.The metal centers are coordinated by suc^(2-) to form a 2D network structure.In 2,suc^(2-) and L^(-) ligands linked the Cd(Ⅱ)ions to form a 2D framework too.Besides,the quantum-chemical calculations were finished on‘molecular fragments’selected from the crystal structure of 1 and 2 by the PBE0/LANL2DZ method in the Gaussian16 program.The calculation results indicate the distinct covalent interaction between the coordinated atoms and Zn(Ⅱ)ion/Cd(Ⅱ)ion.