Issue 5, 2013
From the journal:

Dalton Transactions

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

Olivier Perraud,a   Jean-Bernard Tommasino,b   Vincent Robert,c   Belén Albela,a   Lhoussain Khrouz,a   Laurent Bonneviot,a   Jean-Pierre Dutasta*a  and  Alexandre Martinez*a  

* Corresponding authors

a Laboratoire de Chimie, CNRS, Université Claude Bernard Lyon 1, École Normale Supérieure de Lyon, 46 Allée d'Italie, F-69364 Lyon, France
E-mail: alexandre.martinez@ens-lyon.fr, jean-pierre.dutasta@ens-lyon.fr
Fax: +33 4 7272 8860
Tel: +33 4 7272 8382

b Laboratoire des Multimatériaux et Interfaces, CNRS, Université Claude Bernard Lyon 1, 2 Avenue Grignard, F-69622 Villeurbanne, France
E-mail: jbtomasi@univ-lyon1.fr
Tel: +33 4 7244 8220

c Laboratoire de Chimie Quantique, Institut de Chimie, UMR CNRS 7177, Université de Strasbourg, 4 rue Blaise Pascal, F-67070 Strasbourg, France
E-mail: vrobert@unistra.fr
Tel: +33 3 6885 1302

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 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

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Article information

DOI
https://doi.org/10.1039/C2DT31530K
Article type
Paper
Submitted
11 Jul 2012
Accepted
22 Oct 2012
First published
08 Nov 2012

Dalton Trans., 2013,42, 1530-1535

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Hemicryptophane-assisted electron transfer: a structural and electronic study

O. Perraud, J. Tommasino, V. Robert, B. Albela, L. Khrouz, L. Bonneviot, J. Dutasta and A. Martinez, Dalton Trans., 2013, 42, 1530 DOI: 10.1039/C2DT31530K

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