Morphology Engineering of Fullerene[C ] Microcrystals: From Perfect Cubes, Defective Hoppers to Novel Cruciform-Pillars.

Controlled crystallization of fullerene molecules into ordered molecular assemblies is important for their applications. However, the morphology engineering of fullerene[C ] assemblies is challenging, and complicated architectures have rarely been reported due to the low molecular symmetry of C molecules, which makes their crystallization difficult to control and the low production yield as well. Herein, with the assistance of solvent intercalation, a general reprecipitation approach is reported to prepare morphologically controllable C microcrystals with mesitylene as a good solvent and n-propanol as a poor solvent in one solvent system without replacing specific solvents. A series of C microcrystals with high uniformity from perfect cubes and defective hoppers to novel cruciform-pillars are obtained by intentionally tuning C concentration and the volume ratio of mesitylene to n-propanol. Among them, novel cruciform-pillar-shaped microcrystals are obtained for the first time by further decreasing the amount of mesitylene in the solvent-intercalated microcrystals. Notably, the C concentration is a key parameter for the selective growth of C hopper, rather than the volume ratio of mesitylene to n-propanol. Interestingly, the hopper-shaped microcrystals exhibit excellent photoluminescence properties relative to those of cubes and cruciform-pillars owing to the enhanced light absorption, proving their potential applications in optoelectronic devices. This study offers new insights into the morphology-controlled synthesis of other micro/nanostructured organic microcrystals and the fine tuning of photoluminescence properties of organic crystals.