Kinetically Viable Pathways for Multitopic DCC

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In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor Jeffrey S. Moore of the Department of Chemistry at the University of Illinois, Urbana-Champaign is developing chemistry to synthesize new, shape-persistent, carbon-based cage molecules. He is investigating methods to link small precursor molecules into larger, hollow cage-like structures. Knowledge obtained from this project will directly impact the design and synthesis of important carbon-based materials. In addition, the three-dimensional structures contain voids on the order of a few nanometers in length and with persistent shapes, so these structures may sequester other small molecules. Professor Moore and his research group continue to participate in several mentoring and outreach activities to communicate the importance of scientific advances to K-12 audiences and the general public. They are involved in specific programs such as Encouraging Tomorrow's Chemists (ETC) and the Illinois Female Engineers in Academia Training (iFEAT). Professor Moore is exploring synthetic methods to construct cage molecules with defined cavities for host-guest interactions, adsorption, separation, and stabilization of reactive intermediates. The typical approach in this field is to use a heuristic, structure-focused strategy and design precursors with the appropriate geometry required for a targeted structure. However, this method frequently fails to produce the desired outcome, or yields no discernable products. In this project, Professor Moore is developing experimental methods to probe dynamic covalent chemistry (DCC) energy landscapes and to use that information in formulating strategies to direct DCC precursors along kinetically viable pathways while avoiding undesirable kinetic traps. The particular DCC method being used is alkyne metathesis, and the specific issues being addressed include how kinetic traps affect the outcome of multitopic DCC, what design strategies will direct DCC along kinetically viable pathways, and how strategies used to construct 2-dimensional structures can be adapted to the synthesis of 3-dimensional cages. Knowledge gained from this project is expected to relate directly towards the construction of other important classes of materials such as covalent organic frameworks (COFs).