Redox-driven intramolecular anion translocation between a metal centre and a hydrogen-bond-donating compartment |
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Authors: | Amendola Valeria Colasson Benoît Fabbrizzi Luigi Rodriguez Douton Maria-Jesús |
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Institution: | Dipartimento di Chimica Generale, Università di Pavia via Taramelli 12, 27100 Pavia, Italy. |
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Abstract: | 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. |
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Keywords: | anion recognition copper hydrogen bonds molecular machines redox chemistry |
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