Bistability in Fc-PTM crystals: The role of intermodular electrostatic interactions

Fc-PTM is a valence tautomeric radical, where the ferrocene (Fc) group, a good electron donor, is linked by an ethylenic spacer to a perchlorotriphenylmethyl radical (PTM•), a good electron acceptor. In solution this compound exists mainly in the neutral Fc-PTM • form which can be photoexcited through an intramolecular electron transfer to the zwitterionic Fc+•-PTM- form. By contrast, in crystals of Fc-PTM at room temperature both the neutral and the zwitterionic forms coexist, pointing to a true bistability phenomenon. We rationalize these findings accounting for the role of intermolecular electrostatic interactions in Fc-PTM crystals. In fact the energy of the zwitterionic Fc+•-PTM- form is lowered in the crystal by attractive electrostatic intermolecular interactions and the cooperative nature of these interactions explains the observed coexistence of neutral Fc-PTM• and zwitterionic Fc+•-PTM- species. The temperature evolution of Mössbauer spectra of Fc-PTM is quantitatively reproduced adopting a bottom-up modeling strategy that combines a molecular model, derived from optical spectra of Fc-PTM in solution, with a model for intermolecular electrostatic interactions, supported by quantum-chemical calculations. Fc-PTM then offers the first experimental demonstration of bistability induced by electrostatic interactions in crystals of valence tautomeric donor-acceptor molecules. © 2008 American Chemical Society.