title: 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.
authors.affiliation: Laboratoire de Chimie, Electrochimie Moléculaires et Chimie Analytique, UMR CNRS 6521, Université de Bretagne Occidentale, 6 av. Le Gorgeu, 29238 Brest Cedex 3, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Le Poul
authors.forename: Morgan
authors.initials: M
authors.lastname: Campion
authors.forename: Guillaume
authors.initials: G
authors.lastname: Izzet
authors.forename: Bénédicte
authors.initials: B
authors.lastname: Douziech
authors.forename: Olivia
authors.initials: O
authors.lastname: Reinaud
authors.forename: Yves
authors.initials: Y
authors.lastname: Le Mest
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry; D047250:Calixarenes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004563:Electrochemistry; D004578:Electron Spin Resonance Spectroscopy; D057927:Hydrophobic and Hydrophilic Interactions; D007700:Kinetics; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D010636:Phenols; D011725:Pyridines; C476540:calix(6)arene; D047250:Calixarenes; D003300:Copper