Investigating solid-state properties of organic materials : cycloaddition reactions, thermal expansion, and thermosalience
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Although countless crystal structures have been determined since the discovery of X-ray diffraction by crystals over 100 years ago, there is still much to be learned. With the development of supramolecular chemistry, crystal engineering, and cocrystallization, crystalline solids with desirable properties can be developed, and their structure-function properties can be studied to further advance the field. The solid-state reactivity of crystalline materials is of great importance, as these reactions follow some rules of green chemistry, including being solvent free and typically having high atom efficiency. They also allow for regio- and stereo-control of the product(s) formed. Although the number of molecules that are reactive in the crystalline state are much less than for solution-state reactions, the number has been growing since the time of Gerhard Schmidt, who proposed rules for topochemical photodimerization in crystalline materials. The advancement of solid-state reactions has also been greatly influenced by cocrystallization, which can be used to 'template' the reactive materials to help align the reactive moieties for a solid-state reaction. Furthermore, these solid-state reactions can be used to modify the properties of crystalline materials. Thermal expansion, the response of a material to temperature change, has long been studied for various materials such as building materials (steel, concrete, various piping, etc.) has long been studied, but the thermal expansion of organic materials, especially that of cocrystals, is an emerging field. Materials scientists can benefit greatly from understanding thermal expansion and the key features that play a role in it in order to develop advanced materials, such as micro-electronic materials that would be exposed to fluctuating temperatures.
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Ph. D.