Syntheses, Polymorphic Transformations, and Functions of Ionic Crystals Based on Mononuclear Bismuth(III) Complexes and Polyoxometalates
Syntheses, Polymorphic Transformations, and Functions of Ionic Crystals Based on Mononuclear Bismuth(III) Complexes and Polyoxometalates
复制标题
基于单核铋(III)配合物和多金属氧酸盐的离子晶体的合成、多晶型转化和功能
DOI：
10.1002/cnma.202100479
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发表时间：
2022
期刊：
影响因子：
3.8
通讯作者：
S. Uchid
中科院分区：
文献类型：
--
作者：
T. Iwano;D. Akutsu;Z. Weng;N. Ogiwara;S. Uchid
以晶体工程为基础的分子、离子和配体的受控组装导致了各种功能晶体固体的产生。特别是，多金属氧酸盐(POMS)是一种阴离子金属氧化物簇合物，在晶体工程中一直是一个热门的主题。为了重新认识简单的单核金属配合物作为多金属有机化合物的反阳离子，合成了7种以单核铋(III)配合物为反阳离子的Keggin或Dawson型多金属有机化合物离子晶体。铋(III)中心以二甲基亚砜或N-二甲基甲酰胺为配体，呈三角形十二面体、方形反棱柱或拟立方八配位几何构型。离子晶体随合成条件或重结晶条件的不同而呈现多晶型转变。作为一种探索官能度的方法，在潮湿条件下测量了离子晶体的质子电导。高孔率、叔胺基团或配位水的离子晶体具有较高的质子电导率，较大的活化能表明质子主要通过载体机制与水分子转移。
The controlled assembly of molecules, ions, and ligands as building blocks based on crystal engineering leads to various functional crystalline solids. In particular, polyoxometalates (POMs), which are anionic metal oxide clusters, have been a popular motif in crystal engineering. To revisit simple mononuclear metal complexes as counter cations of POMs, seven ionic crystals based on Keggin‐ or Dawson‐type POMs with mononuclear bismuth(III) complexes as counter cations were synthesized. The bismuth(III) center exhibited triangular dodecahedron, square antiprism, or pseudo‐cubic eight‐coordination geometries, with dimethyl sulfoxide orN,N‐dimethylformamide as ligands. The ionic crystals showed polymorphic transformation depending on the synthetic or recrystallization conditions. As a method for exploring functionality, proton conductivities of the ionic crystals were measured under humidified conditions. The ionic crystals with high porosity, tertiary amine moieties, or coordination water exhibited high proton conductivities, and large activation energies indicate that protons are transferred mainly with water molecules via the vehicle mechanism.