title: Hemicryptophane-assisted electron transfer: a structural and electronic study.
abstract: Three copper(II)@hemicryptophane complexes with various cavity sizes and shapes, Cu(II)@1, Cu(II)@2 and Cu(II)@3, were synthesized and characterized by near-IR/vis and EPR spectroscopies. The spectroscopic data are consistent with the presence of a trigonal-bipyramidal geometry of the N(4)Cu·H(2)O core, in accord with the energy-minimized structures obtained from DFT calculations. Cyclic voltammetry studies in CH(2)Cl(2) showed irreversible redox processes, whereas electrolysis coulometry indicated that Cu(II)/Cu(I) complexes could be interconverted. Electrochemistry data of the complexes stress the crucial role of the cage structure of the hemicryptophane in the thermodynamics of the electron transfer.
authors.affiliation: Laboratoire de Chimie, CNRS, Université Claude Bernard Lyon 1, École Normale Supérieure de Lyon, 46 Allée d'Italie, F-69364 Lyon, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Perraud
authors.forename: Jean-Bernard
authors.initials: JB
authors.lastname: Tommasino
authors.forename: Vincent
authors.initials: V
authors.lastname: Robert
authors.forename: Belén
authors.initials: B
authors.lastname: Albela
authors.forename: Lhoussain
authors.initials: L
authors.lastname: Khrouz
authors.forename: Laurent
authors.initials: L
authors.lastname: Bonneviot
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Dutasta
authors.forename: Alexandre
authors.initials: A
authors.lastname: Martinez
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D003300:Copper / Q000737:chemistry; D055664:Electrochemical Techniques; D004578:Electron Spin Resonance Spectroscopy; D004579:Electron Transport; D004583:Electrons; D008958:Models, Molecular; D010084:Oxidation-Reduction; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D056831:Coordination Complexes; D011083:Polycyclic Compounds; D003300:Copper