Light triggers molecular shuttling in rotaxanes: control over proximity and charge recombinationElectronic supplementary information (ESI) available: Experimental details, additional data and graphs. CCDC 1864783. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc05328f

We present the synthesis of novel rotaxanes based on mechanically interlocked porphyrins and fullerene and their advanced investigations by means of photophysical measurements. To this end, a fullerene-capped dumbbell-type axle containing a central triazole was threaded through strapped (metallo)porphyrins-either a free-base or a zinc porphyrin. Femtosecond-resolved transient absorption measurements revealed charge-separation between the porphyrin and fullerene upon light excitation. Solvent polarity and solvent coordination effects induced molecular motion of the rotaxanes upon charge separation and enabled, for the first time, subtle control over the charge recombination by enabling and controlling the directionality of shuttling. The lifetime of a charge separated state is enhanced by the effects of solvent polarity and the coordination controlled shuttling of a dumbbell in a porphyrin/fullerene rotaxane.