Synthesis and Characterization of Novel Acyclic, Macrocyclic, and Calix[4]arene Ruthenium(II) Bipyridyl Receptor Molecules That Recognize and Sense Anions

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• 作者：Fridrich Szemes ; Dusan Hesek ; Zheng Chen ; Simon W. Dent ; Michael G. B. Drew ; Alistair J. Goulden ; Andrew R. Graydon ; Alan Grieve ; Roger J. Mortimer ; Trevor Wear ; John S. Weightman ; and Paul D. Beer
• 刊名：Inorganic Chemistry
• 出版年：1996
• 出版时间：September 25, 1996
• 年：1996
• 卷：35
• 期：20
• 页码：5868 - 5879
• 全文大小：364K
• 年卷期：v.35,no.20(September 25, 1996)
• ISSN：1520-510X

文摘

The Lewis acidic redox-active and photoactiveruthenium(II) bipyridyl moiety in combination with amide(CO-NH) groups has been incorporated into acyclic, macrocyclic, and lowerrim calix[4]arene structural frameworksto produce a new class of anion receptor with the dual capability ofsensing anionic guest species via electrochemicaland optical methodologies. Single-crystal X-ray structures of(1)Cl and(11)H₂PO₄ reveal theimportance ofhydrogen bonding to the overall anion complexation process. In theformer complex, six hydrogen bonds (twoamide and four C-H groups) stabilize the Cl^- anion andthree hydrogen bonds (two amide and onecalix[4]arenehydroxyl) effect H₂PO₄^-complexation with 11. Proton NMR titrationinvestigations in deuterated DMSO solutionsreveal these receptors form strong and, in the case of the macrocyclic5 and calix[4]arene-containing receptor11,highly selective complexes withH₂PO₄^-. Cyclic andsquare-wave voltammetric studies have demonstrated thesereceptors to electrochemically recognize Cl^-,Br^-, H₂PO₄^-,and HSO₄^- anions. Thecalix[4]arene anion receptor11 selectively electrochemically sensesH₂PO₄^- in the presence of10-fold excess amounts of HSO₄^- andCl^-.Fluorescence emission spectral recognition ofH₂PO₄^- in DMSO solutions isdisplayed by 3, 5, and11.