Modulating Electron Transfer in an Organic Reaction
via Chemical Group Modification of the Photocatalyst
Posted on 2019-09-09 - 15:37
Tuning electron-transfer
(ET) rates from catalysts to substrates
is important for modulating photocatalytic organic reactions. In this
work, we have taken pyrene-based photocatalysts (Py’s) for
photocatalytic hydrodefluorination of polyfluoroarenes (FAs) as model
systems and conducted a first-principles study on modulating ET rates
from Py to FA via the chemical modification of Py with different electron-donating/withdrawing
groups (EDGs/EWGs). The computed spatial distributions of frontier
Kohn–Sham orbitals suggest that ET is energetically more favorable
for Py–EDGs than for Py–EWGs. The estimated ET rates
by a simplified Marcus model show that they are appreciably enhanced
by EDG substitution and weakened by EWG substitution. Noticeably,
the associated Gibbs free-energy change plays a dominant role. Our
findings of tuning ET rates for Py–FA complexes via chemical
group modifications cast new insight into the rational design of metal-free
photocatalysts for organic transformations.
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Liu, Ran; Yang, Li; Yang, Tongtong; Huang, Yan; Barbatti, Mario; Jiang, Jun; et al. (2019). Modulating Electron Transfer in an Organic Reaction
via Chemical Group Modification of the Photocatalyst. ACS Publications. Collection. https://doi.org/10.1021/acs.jpclett.9b01970