Collect. Czech. Chem. Commun. 1996, 61, 1-43

Template-Directed Syntheses of Rotaxanes

Martin Bělohradskýa, Françisco M. Raymob and J. Fraser Stoddartb

a Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague 6, Czech Republic
b School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, United Kingdom


Rotaxanes are molecules comprised of a dumbbell-shaped component encircled by one or more macrocyclic components. The early syntheses of rotaxanes were mainly based upon statistical threading or upon directed methodologies involving chemical conversion. However, with the advent of supramolecular chemistry, a series of host-guest and template-directed approaches to rotaxanes have been developed and employed successfully. We have devised a template-directed approach to rotaxanes incorporating π-electron deficient bipyridinium-based components and π-electron rich hydroquinone-based polyether components. The noncovalent bonding interactions responsible for the self-assembly of these molecular compounds are (i) π-π stacking interactions between the complementary aromatic units, (ii) hydrogen bonding interactions between the acidic hydrogen atoms in the α-positions with respect to the nitrogen atoms on the bipyridinium units and some of the polyether oxygen atoms, as well as, (iii) edge-to-face T-type interactions between some of the hydrogen atoms on the hydroquinone rings and the π-clouds of the aromatic spacers separating the bipyridinium units. By employing these methodologies, we have synthesised a range of [2]rotaxanes, [3]rotaxanes, and [4]rotaxanes. Furthermore, the dynamic processes involving the shuttling of the cyclic components along the dumbbell-shaped components associated with some of these rotaxanes have been investigated in some detail. The reversible control of the process via external stimuli - such as chemical and electrochemical - has been achieved in the case of a [2]rotaxane incorporating benzidine and biphenol recognition sites. These results suggest the possibility of generating, on the nanoscopic level, molecular devices in the shape of rotaxanes able to store and process informations, thus, affording molecular machines.

Keywords: Molecular shuttle; Rotaxane; Self-assembly; Template-directed synthesis.