This thesis delineates modern strategies and methodologies for the preparation of chemically distinct, or functionalized, polyhedral oligomeric silsesquioxanes. These hybrid organic-inorganic molecules are found in countless applications, one of which is enhancing polymer properties. This work describes improvements over typical functionalization strategies, such as hydrosilylation. Additionally, this work employs the well-studied and sterically controlled activation of C(sp2) C-H bonds via iridium-catalyzed borylation in order to obtain polyfunctionalized double-decker silsesquioxanes. By selectively modifying the arene functionality of DDSQ, the linear functionalization of the tetrasilanol that has contributed to DDSQ’s popularity would be combined with the three-dimensional nanostructure functionality that has contributed to OPS’s popularity. Inspired by multiple erroneous reports regarding POSS functionalization, critical considerations for product characterization and the limitations of analyses are also described. The novel POSS synthesized herein, in addition to the methodologies developed, will serve as the steppingstones that materials scientists will follow to reach new polymers.
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