Anion Selective Recognition and Sensing by Novel Macrocyclic Transition Metal Receptor Systems. 1H NMR, Electrochemical, and Photophysical Investigations

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• 作者：Paul D. Beer ; Fridrich Szemes ; Vincenzo Balzani ; Claudio M. Salà ; Michael G. B. Drew ; Simon W. Dent ; and Mauro Maestri
• 刊名：Journal of the American Chemical Society
• 出版年：1997
• 出版时间：December 10, 1997
• 年：1997
• 卷：119
• 期：49
• 页码：11864 - 11875
• 全文大小：492K
• 年卷期：v.119,no.49(December 10, 1997)
• ISSN：1520-5126

文摘

A series of novel redox-active and photoactive ruthenium(II)and osmium(II) bipyridyl-, ferrocene-, andcobaltocenium-containing macrocyclic receptors with the dual capabilityof selectively sensing anionic guest speciesvia electrochemical and optical methodologies have beenprepared. Single-crystal X-ray structures of7·Cl^-,7·2Br^-,and 13·2OAc^- highlight the importanceof hydrogen bonding and respective macrocyclic cavity size to theanionrecognition process in the solid state. Proton NMR titrationstudies in deuterated DMSO solutions reveal thesereceptors form strong and remarkably selective complexes withCl^-, H₂PO₄^-,and OAc^- anions dependent upon theflexibility, topology, and size of the receptor cavity. Cyclic andsquare-wave voltammetric investigations havedemonstrated these receptors to electrochemically recognizeCl^-, H₂PO₄^-,and OAc^- anions. Photophysical studiesreveal emission spectral recognition of Cl^- inacetonitrile solutions is displayed by 7-12.With the hetero-dinuclearreceptors 8, 9, and 12, the rateconstants of the energy transfer process responsible for the quenchingof the luminescentruthenium excited state significantly decreased in the presence ofchloride anion.