Multicomponent Crystals with Competing Intermolecular Interactions: In Situ X-ray Diffraction and Luminescent Features Reveal Multimolecular Assembly under Mechanochemical Conditions.

Supramolecular chemistry under mechanochemical conditions has drawn attention because it can induce low-solubility molecules to self-assemble, although most of the reported examples have been limited to two-component systems. We applied mechanochemical synthesis to achieve multimolecular self-assembly in more challenging three-component systems. The produced crystals showed multicolor solid-state luminescence depending on the components when exposed to UV light. Optical outputs and X-ray diffraction studies were used to examine the self-assembling behavior in greater depth. Using synchrotron radiation, in situ X-ray diffraction permitted direct observation of the milling process, which started the self-assembly process within 1 min. This research emphasizes the importance of multicomponent molecules with optical functions and self-assembling behavior and offers the possibility of developing more complicated multicomponent crystals and organic solid solutions for advanced materials.