Effect of Microheterogeneity of Different Aqueous Binary Mixtures on the Proton Transfer Dynamics of [2,2'-Bipyridyl]-3,3'-diol: A Femtosecond Fluorescence Upconversion Study.

Abstract

In this article, we have investigated the excited-state intramolecular double proton transfer dynamics of [2,2′-bipyridyl]-3,3′-diol, BP(OH)2, in three alcohol–water binary mixtures, namely, ethanol (EtOH)–water, n-propanol (PrOH)–water, tert-butyl alcohol (TBA)–water, and dimethyl sulfoxide (DMSO)–water utilizing the femtosecond fluorescence upconversion technique. We have found that in alcohol–water binary mixtures the proton transfer (PT) pathway of BP(OH)2 is sequential and the anomalous slowdown in PT dynamics is observed in mole fraction (χ) ranges χEtOH = 0.04–0.07, χEtOH = 0.23–0.28, χPrOH = 0.17–0.30, χTBA = 0.12–0.21, and χTBA = 0.40–0.46. Our study sheds light on the involvement of water network in the PT dynamics. Reduction in water accessibility due to the involvement of water molecules in cluster formation results in hindered PT dynamics, and this retardation is more for the TBA–water binary mixture compared to that for the other two mixtures. Additionally, we have found two anomalous regions for the DMSO–water binary mixture in ranges χDMSO = 0.12–0.16 and χDMSO = 0.26–0.34. However, most interestingly, beyond χDMSO = 0.40, we do not find any growth component in the femtosecond fluorescence upconversion trace, which may be due to the change in the PT mechanism from a sequential water-mediated pathway to a concerted intramolecular pathway.