Enhanced Sampling Aided Design of Molecular Photoswitches

Advances
in the evolving field of atomistic simulations promise
important insights for the design and fundamental understanding of
novel molecular photoswitches. Here, we use state-of-the-art enhanced
simulation techniques to unravel the complex, multistep chemistry
of donor–acceptor Stenhouse adducts (DASAs). Our reaction discovery
workflow consists of enhanced sampling for efficient chemical space
exploration, refinement of newly observed pathways with more accurate ab initio electronic structure calculations, and structural
modifications to introduce design principles within future generations
of DASAs. We showcase our discovery workflow by not only recovering
the full photoswitching mechanism of DASA but also predicting a plethora
of new plausible thermal pathways and suggesting a way for their experimental
validation. Furthermore, we illustrate the tunability of these newly
discovered reactions, leading to a potential avenue for controlling
DASA dynamics through multiple external stimuli. Overall, these insights
could offer alternative routes to increase the efficiency and control
of DASA’s photoswitching mechanism, providing new elements
to design more complex light-responsive materials.