Lead Tetrakis(imidazolyl)borate Solids: Anion Exchange, Solvent Intercalation, and Self Assembly of an Organic Anion

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• 作者：Barton H. Hamilton ; Kathryn A. Kelly ; Todd A. Wagler ; Matthew P. Espe ; and Christopher J. Ziegler
• 刊名：Inorganic Chemistry
• 出版年：2004
• 出版时间：January 12, 2004
• 年：2004
• 卷：43
• 期：1
• 页码：50 - 56
• 全文大小：374K
• 年卷期：v.43,no.1(January 12, 2004)
• ISSN：1520-510X

文摘

The coordination polymer Pb[B(Im)₄](NO₃)(xH₂O), constructed by using sodium tetrakis(imidazolyl)borate and lead(II) nitrate solutions, is a layered material with the metal centers facing the interlayer spacing. As in naturallyoccurring layered minerals, this compound can readily undergo anion exchange and reversible intercalation ofsolvent water in the solid state with retention of crystallinity. We observed changes in solvent intercalation by ²⁰⁷Pbsolid state NMR (SSNMR) and thermogravimetric analysis (TGA). Stoichiometric exchange of ¹⁵N nitrate for nitrateand iodide for nitrate is monitored by ¹⁵N and ²⁰⁷Pb SSNMR, and single crystals of the iodide-exchanged materialPb[B(Im)₄]I were isolated. While the iodide compound can be obtained through facile exchange from the nitrateparent compound, the organic anion benzoate is placed in the interlayer spacing for nitrate under self-assemblyconditions and forms an alternating monolayer in Pb[B(Im)₄](C₆H₅COO)(0.5H₂O). The ion exchange versus self-assembly behavior correlates with the structural differences in the three compounds. In both Pb[B(Im)₄]I and Pb[B(Im)₄](C₆H₅COO)(0.5H₂O), the lead sites act as Lewis acids for the iodide and benzoate, respectively.