We report on the motional and proton transfer dynamics of the super photobase FR0-SB in the series of normal alcohols C1 (methanol) through C8 (n-octanol) and ethylene glycol. Steady-state and time-resolved fluorescence data reveal that the proton abstraction dynamics of excited FR0-SB depend on the identity of the solvent and that the transfer of the proton from solvent to FR0-SB*, forming FR0-HSB+*, fundamentally alters the nature of interactions between the excited molecule and its surroundings. In its unprotonated state, solvent interactions with FR0-SB* are consistent with slip limit behavior, and in its protonated form, intermolecular interactions are consistent with a much stronger interaction of FR0-HSB+* with the deprotonated solvent RO–. We understand the excited-state population dynamics in the context of a kinetic model involving a transition state wherein FR0-HSB+* is still bound to the negatively charged alkoxide, prior to solvation of the two charged species. Data acquired in ethylene glycol confirm the hypothesis that the rotational diffusion dynamics of FR0-SB* are largely mediated by solvent viscosity while proton transfer dynamics are mediated by the lifetime of the transition state. Taken collectively, our results demonstrate that FR0-SB* extracts solvent protons efficiently and in a predictable manner, consistent with a ca. 3-fold increase in dipole moment upon photoexcitation as determined by ab initio calculations based on the equation-of-motion coupled-cluster theory.

Two-photon excitation is an attractive means for controlling chemistry in both space and time. Isoenergetic one-and two-photon excitations (OPE and TPE) in non-centrosymmetric molecules are often assumed to reach the same excited state and, hence, to produce similar excitedstate reactivity. We compare the solvent-to-solute excited-state proton transfer of the super photobase FR0-SB following isoenergetic OPE and TPE. We find up to 62 % increased reactivity following TPE compared to OPE. From steady-state spectroscopy, we rule out the involvement of different excited states and find that OPE and TPE spectra are identical in non-polar solvents but not in polar ones. We propose that differences in the matrix elements that contribute to the twophoton absorption cross sections lead to the observed enhanced isoenergetic reactivity, consistent with the predictions of our high-level coupled-cluster-based computational protocol. We find that polar solvent configurations favor greater dipole moment change between ground and excited states, which enters the probability for two-photon excitations as the absolute value squared. This, in turn, causes a difference in the Franck-Condon region reached via TPE compared to OPE. We conclude that a new method has been found for controlling chemical reactivity via the matrix elements that affect two-photon cross sections, which may be of great utility for spatial and temporal precision chemistry.

We report on the changes in the dual fluorescence of two cyanine dyes IR144 and IR140 as a function of viscosity and probe their internal conversion dynamics from S2 to S1 via their dependence on a femtosecond laser pulse chirp. Steady-state and time-resolved measurements performed in methanol, ethanol, propanol, ethylene glycol, and glycerol solutions are presented. Quantum calculations reveal the presence of three excited states responsible for the experimental observations. Above the first excited state, we find an excited state, which we designate as S1′, that relaxes to the S1 minimum, and we find that the S2 state has two stable configurations. Chirp-dependence measurements, aided by numerical simulations, reveal how internal conversion from S2 to S1 depends on solvent viscosity and pulse duration. By combining solvent viscosity, transform-limited pulses, and chirped pulses, we obtain an overall change in the S2/S1 population ratio of a factor of 86 and 55 for IR144 and IR140, respectively. The increase in the S2/S1 ratio is explained by a two-photon transition to a higher excited state. The ability to maximize the population of higher excited states by delaying or bypassing nonradiative relaxation may lead to the increased efficiency of photochemical processes.

The significance of solvent structural factors in the excited-state proton transfer (ESPT) reactions of Schiff bases with alcohols is reported here. We use the super photobase FR0-SB and a series...