title: Proton Transfer Dynamics of 4'-N,N-Dimethylamino-3-hydroxyflavone Observed in Hydrogen-Bonding Solvents and Aqueous Micelles.
abstract: Photophysical studies on the 4'-N,N-dimethylamino-3-hydroxyflavone fluorophore were performed in hydrogen-bonding solvents. Both in hydrogen-bonding acids and bases, clear evidence of excited state intramolecular proton transfer (ESIPT) emerged from steady-state and time-resolved spectroscopies. The same was also observed for the fluorophores residing in the hydrophilic shell region of aqueous micelles, where they come into close contact with water molecules at the micelle-water interface. Slow ∼100 ps ESIPT time-constants were determined in these systems that correlated well with solvation dynamics. The slow ESIPT time-constants are attributed to activated barrier crossing from the solvent-relaxed enol form to tautomer form in the excited state energy surface of the flavone. In contrast to the barrier-less ESIPT occurring in early (<1 ps) time-scales, this activated proton-transfer event necessarily requires extensive reorganization of flavone···solvent intermolecular hydrogen bonds, a process heavily modulated by the relatively slower dynamics of solvent relaxation around the excited fluorophore.
authors.forename: Deborin
authors.initials: D
authors.lastname: Ghosh
authors.affiliation: ‡Bio-Organic Chemistry Lab, Department of Chemistry, Visva-Bharati University, Santiniketan 731 235, India.
authors.forename: Shaikh
authors.initials: S
authors.lastname: Batuta
authors.affiliation: ‡Bio-Organic Chemistry Lab, Department of Chemistry, Visva-Bharati University, Santiniketan 731 235, India.
authors.forename: Sreeparna
authors.initials: S
authors.lastname: Das
authors.affiliation: ‡Bio-Organic Chemistry Lab, Department of Chemistry, Visva-Bharati University, Santiniketan 731 235, India.
authors.forename: Naznin Ara
authors.initials: NA
authors.lastname: Begum
authors.forename: Debabrata
authors.initials: D
authors.lastname: Mandal