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; M. Campion; G. Izzet; O. Reinaud; Bénédicte Douziech; Y. Le Mest

doi:10.1021/ja043073h

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.

Type de document :

Article dans une revue

Journal of the American Chemical Society, American Chemical Society, 2005, 127 (15), pp.5280--5281. 〈10.1021/ja043073h〉

Domaine :

Chimie / Chimie de coordination

Chimie / Chimie analytique

Liste complète des métadonnées

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

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

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

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