Collect. Czech. Chem. Commun. 2003, 68, 1488-1514

Redox-Induced Ring Shuttling and Evidence for Folded Structures in Long and Flexible Two-Station Rotaxanes

Tohru Yamamotoa, Hsian-Rong Tsenga, J. Fraser Stoddarta,*, Vincenzo Balzanib, Alberto Credib, Filippo Marchionib and Margherita Venturib,*

a Department of Chemistry and Biochemistry, University of California, Los Angeles 405 Hilgard Avenue, Los Angeles, CA 90095-1569, U.S.A.
b Dipartimento di Chimica "G. Ciamician", Università di Bologna, Via Selmi 2, 40126 Bologna, Italy


Two dumbbell-shaped components with tetraarylmethane-type stoppers - one hydrophobic and one hydrophilic - and a rod-like section containing a tetrathiafulvalene (TTF) unit and a 1,5-dioxynaphthalene (DNP) moiety as electron-donating units, and their [2]rotaxanes, incorporating the cyclobis(paraquat-p-phenylene) (CBPQT4+) cyclophane as their electron-accepting ring component, have been synthesized, the latter using template-directed protocols. The two amphiphilic [2]rotaxanes, which differ from each other only in the lengths of the polyether chains associated with their hydrophilic stoppers, were designed in order (i) to have them exhibit enhanced amphiphilicities and, by altering the lengths of polyether chains, (ii) to improve the qualities of their Langmuir-Blodgett films, and by removing the phenolic residues, (iii) to increase the oxidative stabilities of these switchable molecules, and so extend the lifetimes of electronic devices fabricated from amphiphilic hysteretic molecular switches of this type. UV-VIS absorption and 1H NMR spectra, as well as electrochemical measurements, show that both [2]rotaxanes exist to all intents and purposes in solution as the translational isomer in which the CBPQT4+ cyclophane surrounds the TTF unit. Evidence has also been obtained for the presence in solution of folded conformations of these [2]rotaxanes. While ox/red stimulation of the TTF unit causes shuttling of the CBPQT4+ cyclophane between the TTF and DNP stations, reduction of CBPQT4+ causes unfolding of the [2]rotaxane molecules.

Keywords: Molecular shuttles; Rotaxanes; Tetrathiafulvalene; Cyclophanes; Charge-transfer interactions; Bipyridinium ions; Photochemistry; Electrochemistry.

References: 59 live references.