The wide application of photoswitches requires control over their isomerization dynamics.Utilizing noncovalent interactions is a promising strategy as it offers active regulation in-situ.However,this control strategy ...The wide application of photoswitches requires control over their isomerization dynamics.Utilizing noncovalent interactions is a promising strategy as it offers active regulation in-situ.However,this control strategy has not yet been explored in-depth to reach its full potential.In this work,we demonstrate that by directing noncovalent interactions to the central rotating bond of indigo-based photoswitches,their thermal relaxation dynamics were altered in two opposite directions(either slowed down or sped up)allowing for modulating the relaxation half-lives across four orders of magnitude.More importantly,our work established two distinct and orthogonal working mechanisms of noncovalent control over isomerization:(1)Thermodynamic stabilization of photoisomers;and(2)Facilitating an alternative reaction pathway through Brønsted/Lewis acid catalysis.This two-directional modulation(resembling agonists and inverse agonists in biological systems)via two orthogonal working mechanisms will enable more delicate manipulation of photoswitches for advanced applications.展开更多
文摘The wide application of photoswitches requires control over their isomerization dynamics.Utilizing noncovalent interactions is a promising strategy as it offers active regulation in-situ.However,this control strategy has not yet been explored in-depth to reach its full potential.In this work,we demonstrate that by directing noncovalent interactions to the central rotating bond of indigo-based photoswitches,their thermal relaxation dynamics were altered in two opposite directions(either slowed down or sped up)allowing for modulating the relaxation half-lives across four orders of magnitude.More importantly,our work established two distinct and orthogonal working mechanisms of noncovalent control over isomerization:(1)Thermodynamic stabilization of photoisomers;and(2)Facilitating an alternative reaction pathway through Brønsted/Lewis acid catalysis.This two-directional modulation(resembling agonists and inverse agonists in biological systems)via two orthogonal working mechanisms will enable more delicate manipulation of photoswitches for advanced applications.
