Hemicryptophane-assisted electron transfer: a structural and electronic studyElectronic supplementary information (ESI) available: 1H and 13C NMR spectra, voltammogram. See DOI: 10.1039/c2dt31530k

• Main Authors: Perraud, Olivier, Tommasino, Jean-Bernard, Robert, Vincent, Albela, Belén, Khrouz, Lhoussain, Bonneviot, Laurent, Dutasta, Jean-Pierre, Martinez, Alexandre
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt31530k

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. The synthesis and characterization of new Cu@hemicryptophane complexes incorporating the tren coordinating ligand are presented and their electrochemical properties in regard to the thermodynamics of the electron transfer are reported.