Conformational switching and exciton interactions in hemicyanine-based bichromophores

Abstract

Conformational changes in two hemicyanine-based bichromophores were demonstrated by varying the polarity as well as temperature of the medium. Dramatic changes in the ground and excited singlet state properties were observed upon folding of the bichromophores, due to the formation of intramolecular aggregates of H-type. These aspects were studied, in detail, using steady-state absorption and time-resolved fluorescence spectroscopy. Time-resolved fluorescence studies indicate that both the bichromophores exhibit a monoexponential decay, with a short lifetime, in mixed toluene-CH₂Cl₂ solvents having lower proportions of toluene. Interestingly, biexponential decay with short and long-lived species was observed at higher proportions of toluene, due to the presence of unfolded and folded forms. Folding results in the intramolecular stacking of the chromophores which restrict their torsional dynamics, leading to a longer lifetime. Upon laser excitation, the folded form of the bichromophore undergoes rapid conformational changes, due to photoinduced thermal dissociation.