Electrochemical behavior of the tris(pyridine) - Cu funnel complexes: An overall induced-fit process involving an entatic state through a supramolecular stress

Nicolas Le Poul 1 M. Campion 1 G. Izzet 2 O. Reinaud 2 Bénédicte Douziech 1 Y. Le Mest 1
1 CEMCA - Chimie, Electrochimie Moléculaires et Chimie Analytique
2 LCBPT - UMR 8601 - Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques
Abstract : The electrochemical behavior of the tris(pyridine) calix[6]arene Cu adducts is unique as compared to that of most classical Cu complexes in a strain-free environment. The presence of MeCN buried inside the cavity is a prerequisite for a quasi-reversible behavior in a dynamic mode. The CV behavior assisted by simulation outlines that the coordination adaptability of the Cu(II)/Cu(I) redox states is completely reversed, with a Td geometry enforced at either redox states. Hence, the supramolecular control of the Cu coordination by a protein-like pocket determines the dynamics of the electron transfer process, its thermodynamics, and the kinetics of the reorganizational barrier and generates a preorganized state for oxidation. This redox behavior corresponds to an overall induced-fit process generating a truly entatic highly oxidizing Cu(II) state through a protein-like strain by involvement of the secondary coordination sphere.
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Article dans une revue
Journal of the American Chemical Society, American Chemical Society, 2005, 127 (15), pp.5280--5281. 〈10.1021/ja043073h〉
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http://hal.univ-brest.fr/hal-01175776
Contributeur : Nicolas Le Poul <>
Soumis le : dimanche 12 juillet 2015 - 21:16:50
Dernière modification le : jeudi 11 janvier 2018 - 06:19:22

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UNIV-BREST | UNIV-PARIS5 | INC-CNRS | USPC | CEMCA-BREST

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Nicolas Le Poul, M. Campion, G. Izzet, O. Reinaud, Bénédicte Douziech, et al.. Electrochemical behavior of the tris(pyridine) - Cu funnel complexes: An overall induced-fit process involving an entatic state through a supramolecular stress. Journal of the American Chemical Society, American Chemical Society, 2005, 127 (15), pp.5280--5281. 〈10.1021/ja043073h〉. 〈hal-01175776〉

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