Non-Covalent Bonding Caught in Action: From Amorphous-to-Cocrystalline Molecular Thin Films

We demonstrate the solvent-free amorphous-to-cocrystalline transformations of nanoscale molecular films. Exposing amorphous films to vapors of a haloarene results in the formation of a cocrystalline coating. This transformation proceeds by gradual strengthening of halogen-bonding interactions as a result of the crystallization process. The gas-solid diffusion mechanism involves formation of an amorphous metastable phase prior to crystallization of the films. In-situ optical microscopy shows mass transport during this process, which is confirmed by cross-section analysis of the final structures using focused ion beam (FIB) milling combined with scanning electron microscopy (SEM). Nanomechanical measurements support the role of rigidity of the amorphous films influences the crystallization process. This surface transformation results in molecular arrangements that are not readily obtained through other means. Whereas cocrystals grown in solution crystallize in a monoclinic centrosymmetric space group, whereas the on-surface halogen-bonded assembly crystallizes into a noncentrosymmetric material with a bulk second-order non-linear optical (NLO) response.