Selective crystallization via vibrational strong coupling

The coupling of (photo)chemical processes to optical cavity vacuum fields is an emerging method for modulating molecular and material properties. Recent reports have shown that strong coupling of the vibrational modes of solvents to cavity vacuum fields can influence the chemical reaction kinetics of dissolved solutes. This suggests that vibrational strong coupling might also effect other important solution-based processes, such as crystallization from solution. Here we test this hitherto unexplored notion, investigating pseudopolymorphism in the crystallization from water of ZIF metal–organic frameworks inside optical microcavities. We find that ZIF-8 crystals are selectively obtained from solution inside optical microcavities, where the OH stretching vibration of water is strongly coupled to cavity vacuum fields, whereas mixtures of ZIF-8 and ZIF-L are obtained otherwise. Moreover, ZIF crystallization is accelerated by solvent vibrational strong coupling. This work suggests that cavity vacuum fields might become a tool for materials synthesis, biasing molecular self-assembly and driving macroscopic material outcomes.