Reference : Computational, Structural, and Mechanistic Analysis of the Electrochemically Driven P...
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
Computational, Structural, and Mechanistic Analysis of the Electrochemically Driven Pirouetting Motion of a Copper Rotaxane
Periyasamy, Ganga [Université de Liège - ULiège > Département de physique > Physique théorique des matériaux >]
Sour, A. [> > > >]
Collin, Jacques mailto [Université de Liège - ULiège > Services généraux (Faculté des sciences) > Relations académiques et scientifiques (Sciences) >]
Sauvage, Jacques mailto [Centre Hospitalier Universitaire de Liège - CHU > > Dermatopathologie >]
Remacle, Françoise mailto [Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique >]
Journal of Physical Chemistry B
American Chemical Society
Yes (verified by ORBi)
[en] A mechanism for the electrochemically driven reorganization of a model copper [2]pseudorotaxane is proposed on the basis of density functional theory computations and validated by comparing to experimental results. We investigate in detail the ligand reorganization around the Cu ion from a 4 to 5 coordination number that follows the conversion of the oxidation state from +1 to +2. It is found that for both the oxidation and the reduction processes the rearrangement proceeds in a concerted fashion via a single transition state. Energy paths involving stable decoordinated-coordinated intermediates are computed to be higher in energy. The cyclic voltammogram simulated using the computed transition theory state rate constants in solvent medium is in good agreement with the experimental voltammogram. Further, we report on the computed concentration change of stable (Cu-4(+), Cu-5(2+)) and metastable species (Cu-4(2+), Cu-5(+)) during single cyclic voltammetry (CV) cycle as a function of the applied voltage or time (the subscripts 4 and 5 refer to the coordination number of the copper center).

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