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Steric effects in light-induced solvent proton abstraction

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d0cp03037f· OSTI ID:1823410
 [1];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2]
  1. Michigan State Univ., East Lansing, MI (United States); Michigan State University
  2. Michigan State Univ., East Lansing, MI (United States)
+ Show Author Affiliations
The significance of solvent structural factors in the excited-state proton transfer (ESPT) reactions of Schiff bases with alcohols is reported here. In this work, we use the super photobase FR0-SB and a series of primary, secondary, and tertiary alcohol solvents to illustrate the steric issues associated with solvent to photobase proton transfer. Steady-state and time-resolved fluorescence data show that ESPT occurs readily for primary alcohols, with a probability proportional to the relative –OH concentration. For secondary alcohols, ESPT is greatly diminished, consistent with the barrier heights obtained using quantum chemistry calculations. ESPT is not observed in the tertiary alcohol. We explain ESPT using a model involving an intermediate hydrogen-bonded complex where the proton is “shared” by the Schiff base and the alcohol. The formation of this complex depends on the ability of the alcohol solvent to achieve spatial proximity to and alignment with the FR0-SB* imine lone pair stabilized by the solvent environment.
Research Organization:
Michigan State Univ., East Lansing, MI (United States)
Sponsoring Organization:
Defense Advanced Research Projects Agency (DARPA); National Institutes of Health (NIH); National Science Foundation (NSF); USDOE
Grant/Contract Number:
FG02-01ER15228
OSTI ID:
1823410
Alternate ID(s):
OSTI ID: 1800017
OSTI ID: 1657311
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 35 Vol. 22; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Schiff bases
computational chemistry
excited-state proton transfer
primary, secondary, and tertiary alcohols
solvation models
solvent structural factors
steady-state absorbance and emission spectroscopy
steric effects
super photobases
time-dependent density functional theory
time-resolved fluorescence spectroscopy