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Redox‐Driven Intramolecular Anion Translocation between a Metal Centre and a Hydrogen‐Bond‐Donating Compartment
Author(s) -
Amendola Valeria,
Colasson Benoît,
Fabbrizzi Luigi,
Rodriguez Douton MariaJesús
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200601865
Subject(s) - chemistry , acetonitrile , redox , cyclic voltammetry , intramolecular force , hydrogen bond , ion , chelation , inorganic chemistry , metal , metal ions in aqueous solution , bimetallic strip , copper , electrolysis , photochemistry , medicinal chemistry , electrochemistry , stereochemistry , molecule , organic chemistry , electrode , electrolyte
Dicationic ligands incorporating two 2,2′‐bipyridine units and two imidazolium moieties, [ 1 ] 2+ and [ 2 ] 2+ , form stable chelate complexes with Cu II and Cu I in acetonitrile solution. Each Cu II complex binds two X − ions according to two stepwise equilibria, the first involving the Cu II centre and the second involving the bis‐imidazolium compartment. Cu I complexes are able to host only one NO 3 − ion in the bis‐imidazolium cavity, while other anions induce demetallation. Thus, in the presence of one equivalent of NO 3 − , the Cu II /Cu I redox change makes the anion translocate quickly and reversibly from one binding site to the other within the [Cu II,I ( 1 )] 4+/3+ system, as demonstrated by cyclic voltammetry and controlled‐potential electrolysis experiments.