一维链状配位聚合物[Zn(acac)_2(4,4′-bipy)]_n的合成、表征及量子化学研究

Synthesis,Characterization and Quantum Chemistry Study of a One-dimensional Chain Coordination Polymer [Zn(acac)_2(4,4′-bipy)]_n

以Zn(ClO4)2·6H2O,4,4′-联吡啶及乙酰丙酮(物质的量比1∶1∶2)在甲醇中通过溶剂热法合成得到了标题聚合物[Zn(acac)2(4,4′-bipy)]n.经元素分析、红外光谱、核磁共振氢谱、热重及X射线单晶衍射等表征,其晶体属单斜晶系,P2(1)/c空间群,晶胞参数:a=1.1366(10)nm,b=1.4914(14)nm,c=1.5534(10)nm,β=132.00(4)°,V=1.957(3)nm3,Z=4.标题聚合物分子由Zn(acac)2与4,4′-bipy是以分子比1∶1形成一维无限的链状结构.热重分析结果表明,聚合物在197℃以下稳定性良好.运用Gaussian03W对聚合物结构单元进行了量化计算分析,原子电荷分布及前沿占据轨道组成很好地佐证了晶体结构的配位环境.

A novel one-dimensional zinc（Ⅱ） coordination polymer [Zn（acac）2（4,4＇-bipy）]n was solvothermally synthesized and characterized by IR, elemental analysis, thermal analysis, ^1H NMR, and X-ray diffraction methods. The complex crystallized in monoclinic system, space group P2（1）/c with a=1.1366（10）nm,b=1.4914（14）nm,c=1.5534（10）nm,β=132.00（4）°,V=1.957（3）nm^3,Z=4. It was confirmed that the Zn（acac）2 and 4,4＇-bipy formed a one-dimension linear structure with molecular ratio of 1：1. The result of TG analysis showed that the title complex was stable under 197 ℃. The distribution of charges and the composition of frontier molecular orbits provided a good testimony for the coordination condition in the crystal structure.