Ultrafast Excited-State Dynamics of Eosin B: A Potential Probe of the Hydrogen-Bonding Properties of the Environment

The photophysics of two dyes from the xanthene family, eosin B (EB), and eosin Y (EY) has been investigated in various solvents by femtosecond transient absorption spectroscopy, first, to clarify the huge disparity of the EB fluorescence lifetimes reported in literature, and, second, to understand the mechanism responsible for the ultrafast excited-state deactivation of EB in water. The excited-state lifetime of EB was found to be much shorter in water and in other protic solvents, due to the occurrence of hydrogen-bond assisted nonradiative deactivation. This mechanism is associated with the hydrogen bonds between the solvent molecules and the nitro groups of EB, which become stronger upon optical excitation due to the charge-transfer character of the excited-state. This process is not operative with EY, where the nitro groups are replaced by bromine atoms. Therefore, the excited-state lifetime of EB in solution is directly related to the strength of the solvent as a hydrogen-bond donor, offering the possibility to build a corresponding scale based on the fluorescence quantum yield or lifetime of EB. This scale of hydrogen-bonding strength could be especially useful for studies of liquid interfaces by time-resolved surface second harmonic generation.