Computational models for the shuttling motion of the macrocycle in rotaxane-based molecular switches.

The shuttling motion of a macrocycle in rotaxane-based molecular switching devices has been studied by computational density functional methods. In the test case, energy profiles corresponding to the dethreading process of different types of guest molecules in a cyclobis(paraquat-p-phenylene) host verified the experimental preference of the tetrathiafulvalene recognition site over the dioxynaphthalene site in a Stoddart-Heath type molecular device. Furthermore, modification of the redox state of either the macrocycle or the guest molecule resulted in considerable changes in the computational energy profiles, which can be utilized in explaining the behavior of the host-guest system. In order to study the effect of chemical oxidation/reduction in the guest molecule, we have investigated a prototypical shaft including two octahedral ruthenium complexes linked by a conjugated C(14) carbon chain, where the shuttling motion can be triggered by changing the electronic environment of the active complexes with ligand exchange reactions. The computational results also indicated effective communication between the macrocycle and the conjugated carbon chain, therefore showing the importance of non-covalent host-guest interactions in the control of the motion.