Graduation Year


Document Type




Degree Granting Department


Major Professor

Michael J. Zaworotko, Ph.D.


Supramolecular chemistry, Supramolecular synthon, Hydrogen bond, Co-crystal, Polymorphism


Neutral or charge-assisted hydrogen bonds occurring between organic molecules represent strong and directional forces that mediate the molecular self-assembly into well defined supramolecular architectures. A proper understanding of hydrogen bonding interactions, their types, geometries, and occurrence in supramolecular motifs, is a prerequisite to crystal engineering, i.e. to the rational design of functional solid materials.Multiple-component organic crystals represent ideal systems to study the intermolecular interactions between the constituent molecules that can be pre-selected for their hydrogen bonding sites and geometrical capabilities. In particular, the systematic structural analysis of supramolecular systems that are comprised of simple molecules facilitates the development of strategies for the rational design of new multiple-component compounds involving more complex components such as drug molecules.The work presented herein shows a combination of systematic database and experimental studies in the context of reliability and hierarchy of several hydrogen bonded supramolecular synthons that exist in a series of model co-crystals and organic salts. The acquired paradigms are ultimately utilized in crystal engineering of pharmaceuticals. In addition, the viability of a mechanichemical approach toward supramolecular synthesis in the context of its efficacy and the effect on polymorphism in multiple-component compounds is also addressed.