One-Shot Library Synthesis of Sequence-Controlled Semiconducting Polymers via Halide-Pair-Driven Multicomponent Polymerization

Sequence-controlled semiconducting polymers are attractive materials for organic electronics, but their synthesis often requires multistep procedures. Herein, we report a halide-pair-driven multicomponent polymerization (MCP) strategy for the one-pot synthesis of sequence-controlled poly(triarylamine)s (PTAAs). By combining iodide/chloride reactivity differences with a catalyst-transfer-capable Buchwald–Hartwig amination system, programmed cascade aminations afforded alternating PTAAs with high sequence fidelity. The versatility of this approach was demonstrated through the library synthesis of various semiconducting PTAAs and dendronized derivatives. Mechanistic studies revealed that halide pairing is the primary factor governing sequence control. This modular MCP strategy provides a simple platform for the rapid discovery of functional semiconducting polymers.