Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H-Bonding Liquid Observed by Transient 2D-IR Spectroscopy.

Abstract

Intermolecular H-bonding dynamics around a photoexcited quadrupolar dye is directly observed using transient 2D-IR spectroscopy. Upon solvent-induced symmetry breaking, the H-bond accepting abilities of the two nitrile end-groups change drastically, and in extremely protic (superprotic) solvents, a tight H-bond complex forms at one end. The time evolution of the 2D C≡N lineshape in methanol points to rapid, 2-3 ps, spectral diffusion due to fluctuations of the H-bonding network. Similar behavior is observed in a superprotic solvent shortly after photoexcitation of the dye. However, at later times, the completely inhomogeneous band does not exhibit spectral diffusion for at least 5 ps, pointing to a glass-like environment around one side of the dye. About half of the excited dyes show this behavior attributed to the tight H-bond complex, whereas the others are loosely bound. A weak cross peak indicates partial exchange between these excited state subpopulations.