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In this context, microsolvation studies in the gas phase provide access to the conformational panorama of these systems in a size\u2010controlled hydrated environment. Here, we exploit this gas\u2010phase vantage point alongside quantum\u2010chemistry calculations to study the structural properties and microhydration dynamics of camphorquinone imine, a chiral molecule holding the functionality to engage in a motor\u2010like function upon light activation. Using molecular rotational resonance spectroscopy with supersonic jets, we detect and analyze the first\u2010 and second\u2010order water complexes of the chiral imine. Our findings reveal that initial hydration steps significantly impact the equilibrium between open (E) and closed (Z) forms, culminating in a reversal of relative stability for the switch states. Despite being captured at rotational temperatures near 1 K, we find that water molecules exhibit notable mobility due to the lack of prominent stabilizing secondary interactions. Additionally, the assignment of a key higher\u2010energy closed (Z) water complex provides insights into the energy required for switching between (E) and (Z) states during collisional cooling. We discuss these effects and rationalize them in terms of molecular forces and internal dynamics governing early solvation.<\/jats:p>","DOI":"10.1002\/anie.202506531","type":"journal-article","created":{"date-parts":[[2025,7,7]],"date-time":"2025-07-07T03:17:39Z","timestamp":1751858259000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Microhydration Dynamics in Molecular Photoswitches: Equilibrium State Reconfiguration in Imine\u2010Based Architectures"],"prefix":"10.1002","volume":"64","author":[{"given":"Nuno M.","family":"Campos","sequence":"first","affiliation":[{"name":"CFisUC, Department of Physics University of Coimbra, 3004\u2010516 Coimbra Portugal"}]},{"given":"Rita J. 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