Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 24, Pages 7069-7073Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202005121
Keywords
crystal growth; high-pressure chemistry; kinetic crystallization; nucleation; polymorphism
Categories
Funding
- Polish National Science Centre [PRELUDIUM 2017/27/N/ST5/00693]
- PLGrid Infrastructure
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The new polymorphs beta and gamma of bis-3-nitrophenyl disulphide crystallized above 0.3 GPa are less dense than the ambient-pressure polymorph alpha, due to high-entropy nucleation and kinetic crystallization. Pressure-compensated high entropy and temperature product promotes varied conformers and increased chemical potential, resulting in kinetic polymorphs in accordance with Ostwald's rule of stages, contrasting with mechanochemical techniques favoring high-density polymorphs.
New polymorphs beta and gamma of bis-3-nitrophenyl disulphide, crystallized above 0.3 GPa, are less dense than the ambient-pressure polymorph alpha. This counterintuitive density relation results from the high-entropy nucleation and subsequent kinetic crystallization. The work performed by pressure compensates the high entropy and temperature product, substantiated in varied conformers and increased chemical potential. Pressure-increased viscosity promotes the kinetic polymorphs, in accordance with empirical Ostwald's rule of stages. It contrasts to mechanochemical techniques, favouring high-density polymorphs.
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