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Sullivan, RA; Davey, RJ; Sadiq, G; Dent, G; Back, KR; Ter Horst, JH; Toroz, D; Hammond, RB (2014)
Publisher: American Chemical Society
Languages: English
Types: Article
Subjects:
There has been much recent interest in the role of solution chemistry and in particular the importance of molecular self-assembly in the nucleation of crystalline phases. Techniques such as FTIR and NMR have highlighted the existence of solution-phase dimers which in many cases mirror the structural synthons found in the resulting macroscopic crystals. However, there are no reported examples in which this new insight into the solution phase has been linked directly to the kinetics of crystal nucleation. Here for the first time, using a combination of solution FTIR, computational chemistry, and measured crystal nucleation rate data, such a link is demonstrated for p-aminobenzoic (PABA) and benzoic acids nucleating from polar and nonpolar solvents. Solute dimerization and desolvation are found to be rate-determining processes in the overall nucleation pathway.
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