Electrochemical behavior of the tris(pyridine) - Cu funnel complexes: An overall induced-fit process involving an entatic state through a supramolecular stress - Université de Bretagne Occidentale Access content directly
Journal Articles Journal of the American Chemical Society Year : 2005

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

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.

Dates and versions

hal-01175776 , version 1 (12-07-2015)

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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, 2005, 127 (15), pp.5280--5281. ⟨10.1021/ja043073h⟩. ⟨hal-01175776⟩
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