水热条件下的原位配体反应得到了一种新型的锌取代多钒酸盐二聚体。

In situ ligand reactions under hydrothermal conditions afford a novel zinc-substituted polyoxovanadate dimer.

作者信息

Zheng Shou-Tian, Wang Ming-Hui, Yang Guo-Yu

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.

出版信息

Inorg Chem. 2007 Oct 29;46(22):9503-8. doi: 10.1021/ic700562m. Epub 2007 Oct 4.

DOI:10.1021/ic700562m

PMID:17915859

Abstract

A novel polyoxovanadate (POV), [Zn(2,2'-bpy)3]4[(ppz){{Zn(tepa)}2ZnAs8V13O41(H2O)}2][As8V14O42(0.5H2O)]2.4H2O (1, 2,2'-bpy = 2,2'-bipyridine, ppz = piperazine, tepa = tetraethylenepentamine), has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectra, thermogravimetric analysis, magnetic measurement, and single-crystal X-ray diffraction analysis. Crystal data for 1: orthorhombic, Aba2, a = 28.3414(14) A, b = 27.9995(16) A, c = 41.5819(16) A, V = 32997(3) A3, Z = 4, rho = 2.264 mg.cm-3. X-ray structure analysis shows that the structure of 1 consists of one unique zinc-substituted POV dimer and two POV monomers. Interestingly, the formation of the zinc-substituted POV dimer involves two new in situ ligand reactions under hydrothermal conditions, the intermolecular and intramolecular deamination coupling reactions of dien. Magnetization measurement revealed the presence of antiferromagnetic interaction between V(IV) ions in 1.

摘要

一种新型多钒酸盐（POV），[Zn(2,2'-联吡啶)3]4[(哌嗪){{Zn(四乙烯五胺)}2ZnAs8V13O41(H2O)}2][As8V14O42(0.5H2O)]2·4H2O（1，2,2'-联吡啶 = 2,2'-联吡啶，哌嗪 = 哌嗪，四乙烯五胺 = 四乙烯五胺），已通过水热法合成，并通过元素分析、红外光谱、热重分析、磁性测量和单晶X射线衍射分析对其结构进行了表征。1的晶体数据：正交晶系，Aba2，a = 28.3414(14) Å，b = 27.9995(16) Å，c = 41.5819(16) Å，V = 32997(3) Å3，Z = 4，ρ = 2.264 mg·cm-3。X射线结构分析表明，1的结构由一个独特的锌取代POV二聚体和两个POV单体组成。有趣的是，锌取代POV二聚体的形成涉及水热条件下的两个新的原位配体反应，即二烯的分子间和分子内脱氨偶联反应。磁化测量表明1中V(IV)离子之间存在反铁磁相互作用。