Separated and Aligned Molecular Fibres in Solid State Self-Assemblies of Cyclodextrin [2]Rotaxanes

The conformations of two [2]rotaxanes, eachcompr ising a-cyclodextrin as the rotor, a stilbene as the axle and 2,4,6-trinitrophenyl substituents as the capping groups, have been examined in solution and in the solid state, using 1H NMR spectroscopy and X-ray crystallography, respectively. In solution, introducing substituents onto the stilbene prevents the cyclodextrin from being localized over one end of the axle. Instead the cyclodextrin moves back and forthalong the substituted stilbene. In the solid state, the axles of the rotaxanes form extended molecular fibres that are separated from eachoth er and aligned along a single axis. The molecular fibres are strikingly similar to those formed by the axle component of one of the rotaxanes in the absence of the cyclodextrin, but in the latter case they are neither separated nor all aligned.