Tuning the chaotropic effect as an assembly motif through one-electron transfer in a rhenium cluster.

We report how only one electron transfer from the hydrophilic reduced cluster [{Re6Se8}(CN)6]4- induces both a dramatic increase of the host-guest affinity with γ-cyclodextrin and a drastic alteration of the supramolecular dynamics. This striking behaviour, underlined by its thermochemical fingerprint, indicates that the self-assembly process is driven by a chaotropic effect.