On the kinetics of solvate formation through mechanochemistry. Issue 13 (23rd July 2018)

• Record Type: Journal Article
• Authors: Hasa, Dritan; Pastore, Mariana; Arhangelskis, Mihails; Gabriele, Benjamin; Cruz-Cabeza, Aurora J.; Rauber, Gabriela Schneider; Bond, Andrew D.; Jones, William
• Is Part Of: CrystEngComm. Volume 21:Issue 13(2019)
• Page Start: 2097
• Page End: 2104
• Publication Date: 2018-07-23
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/c8ce00871j
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : We demonstrate that solvates obtained through mechanochemistry are the thermodynamic products, and that the kinetics of solvate formation are related to the easiness of breaking the reactant crystals. Abstract : Theophylline : 2-pyrrolidone mono (1 : 1) and sesqui (2 : 3) solvates have been discovered through variable-amount liquid-assisted grinding (VALAG). The structures and stability of the solvates and the kinetics involved in their formation are investigated both experimentally and theoretically. Ex situ studies reveal a delayed appearance of the sesquisolvate and show that sesquisolvate formation occurs via the monosolvate rather than directly from pure theophylline. Theoretical calculations show that the obtained solvates are the thermodynamic products corresponding to the reactant ratio. The kinetics of the transformations was found to be related to the energy required to cleave the crystals through the softest planes. This was quantified by means of attachment energy calculations.