Proton Abstraction Mediates Interactions between the Super Photobase FR0-SB and Surrounding Alcohol Solvent

Lahiri, Jurick; Moemeni, Mehdi; Kline, Jessica; Borhan, Babak; Magoulas, Ilias; Yuwono, Stephen H.; Piecuch, Piotr; Jackson, James E.; Dantus, Marcos; Blanchard, G. J.

doi:10.1021/acs.jpcb.9b06580

Proton Abstraction Mediates Interactions between the Super Photobase FR0-SB and Surrounding Alcohol Solvent

Journal Article · Wed Sep 18 00:00:00 EDT 2019 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.9b06580· OSTI ID:1593466

Lahiri, Jurick ^[1]; Moemeni, Mehdi ^[2]; Kline, Jessica ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; Jackson, James E. ^[2]; Dantus, Marcos ^[2]; ^[2]

Michigan State Univ., East Lansing, MI (United States); Michigan State University
Michigan State Univ., East Lansing, MI (United States)

Here, 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^-. Furthermore, 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. three-fold increase in dipole moment upon photoexcitation as determined by ab initio calculations based on the equation-of-motion coupled-cluster theory.

View Accepted Manuscript (DOE)

Research Organization:: Michigan State Univ., East Lansing, MI (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Science

Grant/Contract Number:: FG02-01ER15228

OSTI ID:: 1593466

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 40 Vol. 123; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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