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In the absence of CB[8], the two-electron reduction of the "thread" (14+) generates the bis(radical cation) species which exists as a complicated mixture of a monomeric species with a linear structure, a monomeric species with a folded structure derived from intramolecular pairing of the terminal viologen radical cation units, and dimeric (and/or oligomeric) species produced by intermolecular pairing as judged by a spectroelectrochemical study.
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Controlled threading-dethreading in self-complexing systems, which may be viewed as a folding/unfolding motion, has been reported, see a) P. R. Ashton, R. Ballardini, V. Balzani, S. E. Boyd, A. Credi, M. T. Gandolfi, M. Gómez-López, S. Iqbal, D. Philp, J. A. Preece, L. Prodi, H. G. Ricketts, J. F. Stoddart, M. S. Tolly, M. Venturi, A. J. P. White, D. J. Whiliams, Chem. Eur. J. 1997, 3, 152; b) L. Fabbrizzi, M. Licchelli, P. Pallavicini, L. Parodi, Angew. Chem. 1998, 110, 838; Angew. Chem. Int. Ed. 1998, 37, 800; c) V. Balzani, P. Ceroni, A. Credi, M. Gómez-López C. Hamers, J. F. Stoddart, R. Wolf, New J. Chem. 2001, 25, 25.
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Controlled threading-dethreading in self-complexing systems, which may be viewed as a folding/unfolding motion, has been reported, see a) P. R. Ashton, R. Ballardini, V. Balzani, S. E. Boyd, A. Credi, M. T. Gandolfi, M. Gómez-López, S. Iqbal, D. Philp, J. A. Preece, L. Prodi, H. G. Ricketts, J. F. Stoddart, M. S. Tolly, M. Venturi, A. J. P. White, D. J. Whiliams, Chem. Eur. J. 1997, 3, 152; b) L. Fabbrizzi, M. Licchelli, P. Pallavicini, L. Parodi, Angew. Chem. 1998, 110, 838; Angew. Chem. Int. Ed. 1998, 37, 800; c) V. Balzani, P. Ceroni, A. Credi, M. Gómez-López C. Hamers, J. F. Stoddart, R. Wolf, New J. Chem. 2001, 25, 25.
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Semiempirical AM1 calculations were carried out by using GAMESS-USA: M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su, T. L. Windus, M. Dupuis, J. A. Montgomery, J. Comput. Chem. 1993, 14, 1347.
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4+ revealed by diffusion NMR studies upon two-electron reduction and the linear dependence of the absorbance on concentration over two orders of magnitude favors the intramolecular pairing of the terminal viologen radical cation units within CB[8] leading to the loop structure.
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