Spectral Tuning and Photoisomerization Efficiency in Push–Pull Azobenzenes: Designing Principles

Abstract

This work demonstrates how <i>push</i>-<i>pull</i> substitution can induce spectral tuning toward the visible range and improve the photoisomerization efficiency of azobenzene-based photoswitches, making them good candidates for technological and biological applications. The red-shifted bright ππ* state (S₂) behaves like the lower and more productive dark nπ* (S₁) state because less potential energy along the planar bending mode is available to reach higher energy unproductive nπ*/S₀ crossing regions, which are responsible for the lower quantum yield of the parent compound. The stabilization of the bright ππ* state and the consequent increase in isomerization efficiency may be regulated <i>via</i> the strength of <i>push</i>-<i>pull</i> substituents. Finally, the torsional mechanism is recognized here as the unique productive route because structures with bending values attributable to the inversion mechanism were never detected, out of the 280 ππ* time-dependent density functional theory (RASPT2-validated) dynamics simulations.