Ligand-Induced Formation of Copper(I) Iodide Clusters: Exocyclic Coordination Polymers with Bis-dithiamacrocycle Isomers

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• 作者：Seulgi Kim ; Arlette Deukam Siewe ; Eunji Lee ; Huiyeong Ju ; In-Hyeok Park ; Ki-Min Park ; Mari Ikeda ; Yoichi Habata ; Shim Sung Lee
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：March 7, 2016
• 年：2016
• 卷：55
• 期：5
• 页码：2018-2022
• 全文大小：368K
• ISSN：1520-510X

文摘

A comparative study on the formation of guest clusters induced by different shapes (or sizes) of exocyclic binding sites embedded in the bis-macrocyclic host isomers is reported. CuI reacts with two regioisomers of a bis-dithiamacrocycle, o-bis-L (W-shaped binding site) and m-bis-L (U-shaped binding site), to yield one-dimensional coordination polymers {[(μ₄-Cu₄I₄)(o-bis-L)]·2CH₃CN}_n (1a) and [(μ₄-Cu₂I₂)(m-bis-L)]_n (2). In 1a, the o-bis-L ligand isomer is linked by a spacious cubane [Cu₄I₄] cluster, while the m-bis-L ligand in 2 is linked by a smaller rhomboid [Cu₂I₂] cluster because of the different exocyclic binding sites. The results observed illustrate the possibility for the metal clusters including [Cu_nI_n] (n = 2 or 4) to adopt a controlled formation through the binding site alternation or design. Because of the adaptive cluster formations, the products show different photophysical properties. Additionally, sliding of the one-dimensional chains in 1a was observed upon loss of the lattice solvent molecules in ambient condition.