Abstract

High-pressure polymorphism is a developing interdisciplinary field. Pressure up to 20 GPa is a powerful thermodynamic parameter for the study and fabrication of hydrogen-bonded polymorphic systems. This review describes how pressure can be used to explore polymorphism and surveys the reports on examples of compounds that our group has studied at high pressures. Such studies have provided insight into the nature of structure–property relationships, which will enable crystal engineering to design crystals with desired architectures through hydrogen-bonded networks. Experimental methods are also briefly surveyed, along with two methods that have proven to be very helpful in the analysis of high-pressure polymorphs, namely, the ab initio pseudopotential plane–wave density functional method and using Hirshfeld surfaces to construct a graphical overview of intermolecular interactions.

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