Template-directed synthesis in the solid state: Inorganic templates, metal-organic hosts, and computational studies.

摘要

Template-directed solid-state synthesis enables chemists to preorganize molecules in a stacked arrangement to react to form single or multiple covalent bonds. This approach of juxtaposing molecules to react could have widespread applications in chemical synthesis and materials science. With these concepts in mind, both wet-lab experiments and computational studies have been employed to illustrate the power of this method, as well as its applications.; In the first part of the dissertation, it is demonstrated that the ability of silver (I) salts can serve as templates by directing the synthesis of cyclobutanes in the solid state. Argentophilic forces provide an alternative to hydrogen bonds to direct the [2+2] photodimerization regio- and stereospecifically and in high yield. It is further shown that the method enables achievement of reaction homology in the solid state. Moreover, a tetranuclear molecular square that hosts molecules as guests is constructed by the product of the template-directed solid-state synthesis.; The second part of the thesis utilizes molecular modeling to demonstrate a linear relationship between Hammett substituent constants and the strength of hydrogen bonding within hydrogen-bonded discrete assemblies. Finally, a crystal mutation, which is a novel method to predict structures of molecular assemblies from structures of homologous crystals, is studied.