Multiple Bismuth(III)-Thioether Secondary Interactions Integrate Metalloporphyrin Ligands into Functional Networks

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• 作者：Kunhao Li ; Guo Huang ; Zhengtao Xu ; Mingliang Zhang ; Matthias Zeller ; Allen D. Hunter ; Stephen Sin-Yin Chui ; Chi-Ming Che ; Wai-Yeung Wong
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：June 11, 2007
• 年：2007
• 卷：46
• 期：12
• 页码：4844 - 4849
• 全文大小：166K
• 年卷期：v.46,no.12(June 11, 2007)
• ISSN：1520-510X

文摘

We introduce the 1,2,3-tris(organylthiophenyl) group as a symmetrical, multidentate chelation link for buildingcoordination networks. For this, zinc(II) 5,10,15,20-tetrakis[3',4',5'-tris(methylthio)phenyl]porphyrin was synthesizedand integrated into a two-dimensional network via coordination with BiBr₃. The coordination link exhibits an unusuallycomplex bonding pattern, involving six S atoms from two neighboring ligands that form multiple Bi-S interactions(distances ranging from 3.08 to 3.63 Å) with a dimerlike unit of Bi₂Br₆. The electronic interaction between theporphyrin center and the Bi₂Br₆ block was illustrated by the diffuse-reflectance spectrum of the network compound,in which a modest red-shifted feature at 1.8 eV was seen (while the Q-band absorption of the metalloporphyrincore continues to be dominant at 1.9 eV).