10.1021/ja0113652.s001
Frederick D. Lewis
Frederick D.
Lewis
Xiaobing Zuo
Xiaobing
Zuo
Rajdeep S. Kalgutkar
Rajdeep S.
Kalgutkar
Jill M. Wagner-Brennan
Jill M.
Wagner-Brennan
Miguel A. Miranda
Miguel A.
Miranda
Enrique Font-Sanchis
Enrique
Font-Sanchis
Julia Perez-Prieto
Julia
Perez-Prieto
Temperature-Dependent Photochemistry of 1,3-Diphenylpropenes. The
Di-π-Methane Reaction Revisited
American Chemical Society
2001
unactivated processes
activation parameters
singlet state
rate constants
quantum yields
rearrangement
Kinetic modeling
isomerization
product ratios
nonradiative decay
unactivated fluorescence
temperature range
process yields
intersystem
2001-11-09 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Temperature-Dependent_Photochemistry_of_1_3-Diphenylpropenes_The_Di-_-Methane_Reaction_Revisited/3635253
The temperature-dependent photochemical behavior of 1,3-diphenylpropene and several of its
3-substituted derivatives has been investigated over a wide temperature range. The singlet state is found to
decay via two unactivated processes, fluorescence and intersystem crossing, and two activated processes, trans,cis isomerization and phenyl-vinyl bridging. The latter activated process yields a diradical intermediate which
partitions between ground-state reactant and formation of the di-π-methane rearrangement product. Kinetic
modeling of temperature-dependent singlet decay times and quantum yields of fluorescence, isomerization,
di-π-methane rearrangement, and nonradiative decay provides rate constants and activation parameters for
each of the primary and secondary processes. Substituents at the 3-position are found to have little effect on
the electronic spectra or unactivated fluorescence and intersystem crossing pathways. However, they do effect
the activated primary and secondary processes. Thus, the product ratios are highly temperature dependent.