Colossal Strain Release by Conformational Energy Up-Conversion in a Compressed Molecular Crystal

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• 作者：Szymon Sobczak ; Andrzej Katrusiak
• 刊名：Journal of Physical Chemistry C
• 出版年：2017
• 出版时间：February 9, 2017
• 年：2017
• 卷：121
• 期：5
• 页码：2539-2545
• 全文大小：533K
• ISSN：1932-7455

文摘

External stimuli trigger conformational up-conversion in the molecules of di-p-tolyl disulfide (CH₃–C₆H₄–S−)₂, compensating the stress and absorbing its energy. These mechanochemical transformations explain at the molecular level the lubricating performance of di-p-tolyl disulfide and suggest new applications for storing energy. High pressure induces the conversion either in the solid state, as a phase transition, or at the nucleation stage on the solution-solid interphase as a detour of crystallization preference. The discontinuous transition at 1.6 GPa reduces the symmetry of ambient-pressure monoclinic phase α (space group P2₁) to triclinic phase β (space group P1). The recrystallizations above 0.45 GPa yield a new polymorph γ (space group P2₁/c), most spectacular in the conformational up-conversion absorbing 6 kJmol^–1.