The title assembly diplays an emissive rhenium-to-pyridine charge-transfer state that is partially quenched by electron transfer to an attached acceptor (nitrobenzene). Quenching is preceded by intramolecular folding (J. Ant. Chem. Sec. 1993, 115, 2048). Variable-temperature quenching measurements can be used to determine the characteristic temperature, T-tr, above which unfolded photoexcited state conformations become favored over folded conformations. Similar information for the ground state can be obtained from variable-temperature NMR measurements. Studies in eight solvents show that excited state folding is (1)enthalpically favored but entropically disfavored (all solvents), (2) correlated (via T-tr) with the inverse dielectric strength of the solvent, and (3) enhanced in comparison to folding in the electronic ground state (studies in one solvent). The combined evidence points to a folding reaction that is driven by optimization of localized Coulombic interactions. Optimization of solvent cohesive interactions, however, may possibly also play a role in the folding reaction.