The application of ultrasound to crystallization (i.e., sonocrystallization) can dramatically affect the properties of the crystalline products. Sonocrystallization induces rapid nucleation that generally yields smaller crystals of a more narrow size distribution compared to quiescent crystallizations. The mechanism by which ultrasound induces nucleation remains unclear although reports show the potential contributions of shockwaves and increases in heterogeneous nucleation. In addition, the fragmentation of molecular crystals during ultrasonic irradiation is an emerging aspect of sonocrystallization and nucleation. Decoupling experiments were performed to confirm that interactions between shockwaves and crystals are the main contributors to crystal breakage. In this review, we build upon previous studies and emphasize the effects of ultrasound on the crystallization of organic molecules. Recent work on the applications of sonocrystallized materials in pharmaceutics and materials science are also discussed.
Cocrystals are modular multicomponent solids with exceptional utility in synthetic chemistry and materials science. A variety of methods exist for the preparation of cocrystals, yet, some promising cocrystal phases have proven to be intractable synthetic targets. We describe a strategy for the synthesis of the pharmaceutically relevant (caffeine)$(benzoic acid) cocrystal (1), which persistently failed to form using a broad range of established techniques. State-of-the-art crystal structure prediction methods were employed to assess the possible existence of a thermodynamically stable form of 1, hence to identify appropriate heteronuclear seeds for cocrystallization. Once introduced, the designed heteronuclear seeds facilitated the formation of 1 and, significantly they (or seeds of the product cocrystal) continued to act as long-lasting laboratory "contaminants", which encouraged cocrystal formation even when present at such low levels as to evade detection. The seeding technique described thus enables the synthesis of cocrystals regarded as unobtainable under desired conditions, and potentially signifies a new direction in the field of materials research.
Ag(I) is used to form a π-stacked metal-organic solid that exhibits remarkably high electrical conductivity. The solid undergoes a single-crystal-to-single-crystal [2+2] photodimerization to generate a 1D coordination polymer with over 40% higher conductivity. The Ag(I) complex represents the first example of an increase in conductivity resulting from a [2+2] photodimerization. Density of states calculations show a higher contribution from Ag(I) ions to the valence band in the photodimerized solid, supporting the increase in conductivity.
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