Hemicryptophane-assisted electron transfer: a structural and electronic study.

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.