Matchmaking in Catalyst-Transfer Polycondensation: Optimizing Catalysts based on Mechanistic Insight

CONSPECTUS: Catalyst-transfer polycondensation (CTP) has emerged as a useful living, chain-growth polymerization method for synthesizing conjugated (hetero)arene-based polymers with targetable molecular weights, narrow dispersities, and controllable copolymer sequences all properties that significantly influence their performance in devices. Over the past decade, several phosphine- and carbene-ligated Ni- and Pd-based precatalysts have been shown to be effective in CTP. One current limitation is that these traditional CTP catalysts lead to nonliving, non-chain-growth behavior when complex monomer scaffolds are utilized. Because these monomers are often found in the highest-performing materials, there is a significant need to identify alternative CTP catalysts. Recent mechanistic insight into CTP has laid the foundation for designing new catalysts to expand the CTP monomer scope. Building off this insight, we have designed and implemented model systems to identify effective catalysts by understanding their underlying mechanistic behaviors and systematically modifying catalyst structures to improve their chain-growth behavior. In this Account, we describe how each catalyst parameter the ancillary ligand(s), reactive ligand(s), and transition metal-influences CTP. As an example, ancillary ligands often dictate the turnover-limiting step of the catalytic cycle, and perhaps more importantly, they can be used to promote the formation of the key intermediate (a metal arene associative complex) and its subsequent reactivity. The fidelity of this intermediate is central to the mechanism for the living, chain-growth polymerization. Reactive ligands, on the other hand, can be used to improve catalyst solubility and accelerate initiation. Additional advantages of the reactive ligand include providing access points for postpolymerization modification and synthesizing polymers directly off surfaces. While the most frequently used CTP catalysts contain nickel, palladium-based catalysts exhibit a higher functional group tolerance and broader substrate scope (e.g., monomers with boron, magnesium, tin, and gold transmetalating agents). Overall, we anticipate that applying the tools and lessons detailed in this Account to other monomers should facilitate a better matchmaking process that will lead to new catalyst-transfer polycondensations.