Acid-Enhanced Photoiniferter Polymerization under Visible Light.

Photoiniferter (PI) is a promising polymerization methodology, often used to overcome restrictions posed by thermal reversible addition-fragmentation chain-transfer (RAFT) polymerization. However, in the overwhelming majority of reports, high energy UV irradiation is required to effectively trigger photolysis of RAFT agents and facilitate the polymerization, significantly limiting its potential, scope, and applicability. Although visible light PI has emerged as a highly attractive alternative, most current approaches are limited to the synthesis of lower molecular weight polymers (i.

Specific Adsorption of Alkaline Cations Enhances CO-CO Coupling in CO Electroreduction.

Electrolyte alkaline cations can significantly modulate the reaction selectivity of electrochemical CO reduction (eCOR), enhancing the yield of the valuable multicarbon (C) chemical feedstocks. However, the mechanism underlying this cation effect on the C-C coupling remains unclear. Herein, by performing constant-potential AIMD simulations, we studied the dynamic behavior of interfacial K ions over Cu surfaces during C-C coupling and the origin of the cation effect.

Investigating Competing Inner- and Outer-Sphere Electron-Transfer Pathways in Copper Photoredox-Catalyzed Atom-Transfer Radical Additions: Closing the Cycle.

This integrated computational and experimental study comprehensively examines the viability of competing inner-sphere electron transfer (ISET) and outer-sphere electron transfer (OSET) processes in [Cu(dap)]-mediated atom-transfer radical additions (ATRA) of olefins and CFSOCl that can deliver both R-SOCl and R-Cl products. Five sterically- and electronically-varied representative alkenes were selected from which to explore and reconcile a range of experimentally observed outcomes. Findings are consistent with photoexcited [Cu(dap)] initiating photoelectron transfer via ISET and the subsequent regeneration of the oxidized catalyst via ISET in the ground state to close the catalytic cycle and liberate products.

Maximizing Photon-to-Electron Conversion for Atom Efficient Photoredox Catalysis.

Photoredox catalysis is a powerful tool to access challenging and diverse syntheses. Absorption of visible light forms the excited state catalyst (*PC) but photons may be wasted if one of several unproductive pathways occur. Facile dissociation of the charge-separated encounter complex [PC:D], also known as (solvent) cage escape, is required for productive chemistry and directly governs availability of the critical PC intermediate.