A square-shaped complex with an electron-acceptor ligand: unique cubic crystal symmetry and similarity to the inorganic mineral katoite
A square-shaped complex with an electron-acceptor ligand: unique cubic crystal symmetry and similarity to the inorganic mineral katoite
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具有电子受体配体的方形配合物：独特的立方晶体对称性和与无机矿物卡托石的相似性
DOI：
10.1039/d1ce00994j
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发表时间：
2021
期刊：
影响因子：
3.1
通讯作者：
Kitagawa Hiroshi
中科院分区：
文献类型：
--
作者：
Aoki Kentaro;Otsubo Kazuya;Kitagawa Hiroshi
正方形大环配合物由于其独特的结构和分子识别性能而引起人们的广泛关注。本文报道了一个以N，N′-二（4-吡啶基）-1，4，5，8-萘二酰亚胺（dpndi）为电子受体的正方形大环配合物[Pt（en）（dpndi）]4（SO 4）4·20 H2O（1，en：乙二胺）. 1的分子结构由单晶X射线晶体学确定，并且1是其结构由晶体学确定的最大Pt正方形（边长：2.6nm）。电化学研究表明，1每平方单位可以接受8个电子。在1中，在固态下观察到正方形单元之间的多重相互作用（氢键和孤对π π相互作用）。这与之前报道的正方形大环配合物形成鲜明对比，因为在这些结构中很少观察到正方形-正方形相互作用。1中的多个正方形-正方形相互作用导致正方形单元的对称堆积和独特的立方晶体对称性的结晶。此外，1的堆积结构显示出与天然矿物Katoite的高压相的强烈相似性。
Square macrocyclic complexes have attracted significant attention due to their unique structure and molecular recognition properties. Here, we report a square macrocyclic complex using an electron-acceptor ligand N,N′-di(4-pyridyl)-1,4,5,8-naphthalenediimide (dpndi), [Pt(en)(dpndi)]4(SO4)4·20H2O (1, en: ethylenediamine). The molecular structure of 1 was determined from single-crystal X-ray crystallography, and 1 is the largest Pt square (side: 2.6 nm) whose structure was crystallographically determined. Electrochemical study revealed that 1 can accept eight electrons per square unit. In 1, multiple interactions (hydrogen bonding and lone pair⋯π interactions) among the square units were observed in the solid state. This is in sharp contrast to the previous report of square macrocyclic complexes since the square–square interactions were rarely observed in these structures. The multiple square–square interactions in 1 led to the symmetrical packing of the square units and crystallization in a unique cubic crystal symmetry. Moreover, the packing structure of 1 showed a strong similarity to the high-pressure phase of the natural mineral katoite.