Exploring the Effects of Vibrational Strong Coupling on Supramolecular Chemistry—Perylene Crystallization in a Fabry-Perrot Cavity

The coupling of molecular vibrations or electronic transitions to optical cavity vacuum fields was shown to alter molecular and material properties i.e., by modifying the reactivity of organic reactions [1] and enhancing the electrical current in organic semiconductors [2] by an order of magnitude, reflecting an increase of the carrier mobility. The alteration of chemical reactivity has been attributed to a reshaping of the Morse potential of the coupled bond modified by VSC, predicting a shortening or strengthening of the coupled bond and hence a change of its energy. Therefore, if the energy and the strength of a bond involved in intermolecular interactions would be altered by coupling with the vacuum field, VSC may influence crystal nucleation as well as crystal growth. As first examples, the modification of the supramolecular aggregation of a conjugated polymer [3] and the influence on the pseudo-polymorphism of zeolite imidazolate frameworks [4] are confirming the influence of VSC in supramolecular chemistry.<br/>In a typical setup, molecular vibrations are coupled to an optical mode by placing materials between two metal mirrors in a standard Fabry-Perrot (FP) cavity. This work is focused on the crystallization of perylene in a FP cavity, to explore the effect of VSC on crystal growth and polymorphism. Together with the optimization of crystallization parameters, the main challenges to perform crystallization in a FP cavity are presented and results of cooperative VSC in a recrystallization experiment of perylene are shown.<br/>[1] A. Thomas et al., Science, 363, 615-619.<br/>[2] E. Orgiu et al., Nat. Mater., 2015, 14, 1123-1130.<br/>[3] K. Joseph et al., Angew. Chem. Int. Ed.2021,60, 19665–19670<br/>[4] K. Hirai et al., Chem. Sci<b>.</b>, 2021,12, 11986-11994