Project Grant 2203396

This three-year, $274,094 National Science Foundation project grant supports collaborative research between Duke University and the University of South Carolina to develop metal-containing polymers that respond chemically to mechanical stress. Funded through NSF's Mathematical and Physical Sciences program (CFDA 47.049), the researchers aim to establish structure-activity relationships and reaction mechanisms for mechanochemical cleavage of metal-cyclopentadienyl bonds. They will synthesize main-chain metallocene-containing polymers and study their mechanochemical reactivity, exploring catalytic C-H functionalization and redox isomerization of half-sandwich metal complexes. The researchers will also incorporate conformational locks and counterions to sensitize metallocene mechanophores in macrocyclic metallocenophanes. Their work seeks to make metallocene activation reversible through reconstructive processes and employ density functional theory calculations to elucidate thermodynamic equilibria between dissociated states and sandwich constructs. Outcomes from this research have potential applications in catalysis and advanced materials.