Chemically Controlled Ring Motions

Some examples of chemically controlled ring motions in catenanes through electron transfer or charge transfer processes have been reported. 

The electrochemical behavior of 11+ is particularly clean and interesting since only the 4- and the 5- coordinate geometries can be obtained by translating the metal complexed-ring from the phen site to the terpy site [44]. The electro chemically induced molecular motions (square scheme) similar to those represented in Fig. 7 but now involving stoppered compounds can be monitored by cyclic voltammetry (CV) and controlled potential electrolysis experiments [44]. 

The electrochemical and chemical behavior of rotaxane 7 + was analyzed by CV and controlled potential electrolysis experiments.34,35 From the CV measurements at different scan rates (from 0.005 to 2 V/s) both on the copper(I) and on the copper(II) species, it could be inferred that the chemical steps (motions of the ring from the phenanthroline to the terpyridine and vice versa) are slow on the timescale of the experiments. As the two redox couples involved in these systems are separated by 0.7 V, the concentrations of the species in each environment (tetra- or pentacoor-dination) are directly deduced from the peak intensities of the redox signals. In Fig. 14.13 are displayed some voltammograms (curves a-e) obtained on different oxidation states of the rotaxane 7 and at different times. 

As already pointed out in the case of rotaxanes, mechanical movements can also be induced in catenanes by chemical, electrochemical, and photochemical stimulation. Catenanes 164+ and 174+ (Fig. 19) are examples of systems in which the conformational motion can be controlled electrochemically [82, 83], They are made of a symmetric electron acceptor, tetracationic cyclophane, and a desymmetrized ring comprising two different electron donor units, namely a tetrathiafulvalene (TTF) and a dimethoxybenzene (DOB) (I64 1) or a dimethoxynaphthalene (DON) (174+) unit. Because the TTF moiety is a better electron donor than the dioxyarene units, as witnessed by the potentials values for their oxidation, the thermodynamically stable conformation of these catenanes is that in which the symmetric cyclophane encircles the TTF unit of the desymmetrized macrocycle (Fig. 19a, state 0). 

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