biostudies-literatureUnknown14(11)Zhang ZRecently, exploring new type polymerization protocols has been a major driving force in advancing organic polymers into highly functional materials. Herein we report a new polycondensation protocol to implant the phosphorus (P) atom in the main backbone of crosslinked polythiophenes. The polycondensation harnesses a Stille phosphorus-carbon (P-C) coupling reaction between phosphorus halides and aryl stannanes that has not been reported previously. Mechanistic studies uncovered that the P-electrophile makes the reactivity of a catalytic Pd-center highly sensitive towards the chemical structures of aryl stannanes, which is distinct from the typical Stille carbon-carbon coupling reaction. The efficient P-C polycondensation afforded a series of P-crosslinked polythiophenes (PC-PTs). LeveragingChemical science2990-2998https://www.ebi.ac.uk/biostudies/studies/S-EPMC10016342biostudies-literatureStille type P-C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution.PMC10016342Zhang ZXue CRen YHan XChen HZhang BPeng MMa GfalseStille type P-C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution.Recently, exploring new type polymerization protocols has been a major driving force in advancing organic polymers into highly functional materials. Herein we report a new polycondensation protocol to implant the phosphorus (P) atom in the main backbone of crosslinked polythiophenes. The polycondensation harnesses a Stille phosphorus-carbon (P-C) coupling reaction between phosphorus halides and aryl stannanes that has not been reported previously. Mechanistic studies uncovered that the P-electrophile makes the reactivity of a catalytic Pd-center highly sensitive towards the chemical structures of aryl stannanes, which is distinct from the typical Stille carbon-carbon coupling reaction. The efficient P-C polycondensation afforded a series of P-crosslinked polythiophenes (PC-PTs). Leveraging2023-01-01T00:00:00Z2023 Mar2025-05-29T14:37:12.99Z2025-05-29T14:37:12.99ZS-EPMC100163423693760010.1039/d2sc06702a