Boosting the
Release of Leaving Group from Blebbistatin
Derivative Photocages via Enhancing Intramolecular Charge Transfer
and Stabilizing Cationic Intermediate
posted on 2023-12-15, 16:15authored byZicong Situ, Manlin Lu, Wenbin Chen, Zuoti Xie, Shun Li Chen, Li Dang, Ming-De Li
Blebbistatin
(Bleb) derivatives are a visible light
photocage platform. During the photocleavage process, intramolecular
charge transfer (ICT) and cationic intermediates play a decisive
role. However, slow photolysis rate and low photolysis quantum yield
are the main problems for Bleb’s derivatives.
Herein, by introducing a substituted OCH3 group at the para-position of the D ring, Bleb and Bleb derivatives with various leaving groups were synthesized
and studied, and the photolysis performance was unveiled by steady-state
spectra, photolysis rate experiments, photolysis quantum yield, and
density functional theory calculations. Substituted OCH3 derivatives of Bleb may enhance the photolysis rate
and increase the photolysis quantum yield because the electron-donating
group can promote the ICT process and stabilize the cationic intermediate
during the photolytic reaction. More generally, the insights gained
from this structure–reactivity relationship may provide theoretical
guidance and aid in the development of new highly efficient photoreactions.