The structures of several one- and two-station [2]rotaxanes have been probed in both solid and solution phases. It is shown that the cyclophane, comprising two 4,4’-bipyridinium dications Linked via 1,4-xylyl groups, resides preferentially over a dialkoxybenzene subunit incorporated into the "string". The terminal stoppers, anthracene or ferrocene subunits, associate with the exterior of the cyclophane, via pi-stacking, so as to form closed conformations. Excitation into the anthracene stoppers is followed by rapid, but reversible, electron transfer to the cyclophane. Direct excitation into the charge-transfer absorption band results in formation of an intimate radical ion pair in which an electron has been transferred from the central dialkoxybenzene donor to the cyclophane acceptor. Rapid charge recombination occurs but can be partially intercepted by hole transfer to an appended ferrocene stopper. In this latter case, the ground state is restored by relatively slow electron transfer from the reduced cyclophane to the terminal ferrocenium cation. It is proposed that the closed conformation unwinds subsequent to this second electron-transfer step in order to minimize electrostatic repulsion. To some extent, therefore, the rates of electron transfer are controlled by conformational exchange.