Cold-Captured Dynamic Hydration Networks in Oxime-Based Photoswitches: A Theoretical Challenge Uncovered by Rotational Spectroscopy.

With the goal of manipulating (bio)chemical processes, photoswitches emerge as important assets in molecular nanotechnology. To guide synthetic strategies toward increasingly more efficient systems, conformational dynamics studies performed with atomic rigor are in demand, particularly if this information can be extracted with control over the size of a perturbing solvation layer. Here, we use jet-cooled rotational spectroscopy and quantum chemistry calculations to unravel the structure and micro-hydration dynamics of a prototype photoswitch.

Microhydration Dynamics in Molecular Photoswitches: Equilibrium State Reconfiguration in Imine-Based Architectures.

The functional performance of a molecular photoswitch relies strongly on its ability to undergo structural changes in solution. In this context, microsolvation studies in the gas phase provide access to the conformational panorama of these systems in a size-controlled hydrated environment. Here, we exploit this gas-phase vantage point alongside quantum-chemistry calculations to study the structural properties and microhydration dynamics of camphorquinone imine, a chiral molecule holding the functionality to engage in a motor-like function upon light activation.