An Unprecedented M–O Cluster Constructed from Nanosized {[C5NH5]9[H31MoV12O24CoII12(PO4)23(H2O)4]}2– Anions Exhibiting Interesting Nonlinear-Optical Properties

A novel high-nuclear nanosized cluster modified by conjugated organic ligands (pyridine and imidazole), [C5NH5]8­[C3H5N2]2­{[C5NH5]9​­[H31Mo12O24Co12​­(PO4)23­(H2O)4]}·12H2O (1), has been successfully isolated under hydrothermal conditions and structurally characterized. Compound 1 consists of 12 CoII and 12 MoV ions linked by 23 {PO4} groups, exhibiting unprecedented nanosized ship-shaped clusters. The magnetic measurements reveal that compound 1 exhibits dominant antiferromagnetic interactions. Additionally, pyridine and imidazole ligands enhance the delocalized electron effects of clusters, and the third-order nonlinear-optical response of compound 1 is excellent.

本研究通过水热条件成功分离得到一例由共轭有机配体（conjugated organic ligands，吡啶（pyridine）与咪唑（imidazole））修饰的新型高核纳米团簇，其化学式为[C5NH5]8­[C3H5N2]2­{[C5NH5]9​­[H31Mo12O24Co12​­(PO4)23­(H2O)4]}·12H2O（编号为化合物1），并对其完成了结构表征。化合物1由12个二价钴离子（CoII）与12个五价钼离子（MoV）通过23个磷酸根基团（{PO4}）桥联构成，呈现出前所未有的船形纳米团簇结构。磁性测试结果表明，化合物1主要表现出反铁磁相互作用。此外，吡啶与咪唑配体可增强团簇的离域电子效应，且化合物1展现出优异的三阶非线性光学响应（third-order nonlinear-optical response）。