Hemicryptophane-assisted electron transfer: a structural and electronic study

Olivier Perraud (1) , Jean-Bernard Tommasino (2) , Vincent Robert (3) , Belen Albela (1) , Lhoussain Khrouz (1) , Laurent Bonneviot (1) , Jean-Pierre Dutasta (1) , Alexandre Martinez (1)

1 LC - Laboratoire de Chimie - UMR5182
2 LMI - Laboratoire des Multimatériaux et Interfaces
3 Institut de Chimie de Strasbourg

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 N4Cu·H2O core, in accord with the energy-minimized structures obtained from DFT calculations. Cyclic voltammetry studies in CH2Cl2 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. Graphical abstract: Hemicryptophane-assisted electron transfer: a structural and electronic study

Domaines: Chimie théorique et/ou physique

Olivier Perraud, Jean-Bernard Tommasino, Vincent Robert, Belen Albela, Lhoussain Khrouz, et al.. Hemicryptophane-assisted electron transfer: a structural and electronic study. Dalton Transactions, 2013, 42 (5), pp.1530-1535. ⟨10.1039/c2dt31530k⟩. ⟨hal-01117205⟩