The slipping approach to self-assembling [n]rotaxanes

Masumi Asakawa, Peter R. Ashton, Roberto Ballardini, Vincenzo Balzani, Martin Bělohradský, Maria Teresa Gandolfi, Oldrich Kocian, Luca Prodi, Francisco Raymo, J. Fraser Stoddart, Margherita Venturi

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Abstract

A synthetic approach - namely slippage - to self-assembling [n]rotaxanes incorporating π-electron deficient bipyridinium-based dumbbell-shaped components and π-electron-rich hydroquinone- and/or dioxynaphthalene-based macrocyclic polyether components has been developed. The kinetics of rotaxane formation by the slipping procedure were investigated by absorption UV-visible and 1H-NMR spectroscopies in a range of temperatures and solvents, varying systematically the size of both the stoppers and the macrocyclic components. As expected, the rate constants for these processes are affected by the size complementarity between macrocycles and stoppers. Furthermore, the enthalpic and entropic contributions to the free energies of activation associated with the slippage and the effect of solvent polarity upon the outcome of these processes have been evaluated. In addition, the spectroscopic and electrochemical properties of some of the rotaxanes are presented and discussed with reference to the properties of their chromophoric and electroactive units.

Original languageEnglish
Pages (from-to)302-310
Number of pages9
JournalJournal of the American Chemical Society
Volume119
Issue number2
DOIs
StatePublished - Jan 15 1997
Externally publishedYes

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ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Asakawa, M., Ashton, P. R., Ballardini, R., Balzani, V., Bělohradský, M., Gandolfi, M. T., Kocian, O., Prodi, L., Raymo, F., Stoddart, J. F., & Venturi, M. (1997). The slipping approach to self-assembling [n]rotaxanes. Journal of the American Chemical Society, 119(2), 302-310. https://doi.org/10.1021/ja961817o