Selective control of donor-acceptor Stenhouse adduct populations with non-selective stimuli

Multifaceted material responses upon exposure to stimuli are key for developing life-like materials. Developing such synthetic systems, though not trivial, typically relies on orthogonal stimuli to enable control of molecular systems that enable multi-responsive behavior. Access to complex tunable reaction mechanisms with diverse energy landscapes offers an alternative strategy for controlling out-of-equilibrium processes without requiring orthogonal stimuli for each responsive unit. Donor-acceptor Stenhouse adducts (DASAs) are a class of photoswitches that have complex, tunable, and environmentally sensitive reaction pathways. We present the control of donor-acceptor Stenhouse adduct equilibrium and photoswitching kinetics through changes in the polarity of their environment. Polarity and light can be used to selectively control the pathway outcomes of three DASA derivatives where the orthogonal response comes from changes in the energy landscape and is not driven by their orthogonal response to the given stimuli. This work paves the way to designing multi-responsive and self-regulating life-like materials.