Spectroscopic, Structural, and Theoretical Studies of Halide Complexes with a Urea-Based Tripodal Receptor

详细信息    查看全文

• 作者：Avijit Pramanik ; Douglas R. Powell ; Bryan M. Wong ; Md. Alamgir Hossain
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：April 2, 2012
• 年：2012
• 卷：51
• 期：7
• 页码：4274-4284
• 全文大小：658K
• 年卷期：v.51,no.7(April 2, 2012)
• ISSN：1520-510X

文摘

A urea-based tripodal receptor L substituted with p-cyanophenyl groups has been studied for halide anions using ¹H NMR spectroscopy, density functional theory (DFT) calculations, and X-ray crystallography. The ¹H NMR titration studies suggest that the receptor forms a 1:1 complex with an anion, showing a binding trend in the order of fluoride > chloride > bromide > iodide. The interaction of a fluoride anion with the receptor was further confirmed by 2D NOESY and ¹⁹F NMR spectroscopy in DMSO-d₆. DFT calculations indicate that the internal halide anion is held by six NH路路路X interactions with L, showing the highest binding energy for the fluoride complex. Structural characterization of the chloride, bromide, and silicon hexafluoride complexes of [LH⁺] reveals that the anion is externally located via hydrogen bonding interactions. For the bromide or chloride complex, two anions are bridged with two receptors to form a centrosymmetric dimer, while for the silicon hexafluoride complex, the anion is located within a cage formed by six ligands and two water molecules.