Versatile Halide‐Pair‐Driven Multicomponent Polymerization for Library Synthesis of Sequence‐Controlled Semiconducting Dendronized Polymers

Abstract

Abstract Sequence‐controlled semiconducting polymers represent a new frontier in organic electronics, where precise molecular sequence directly dictates device performance. However, achieving both high sequence fidelity and structural diversity remains a significant challenge using conventional synthetic protocols. To address this issue, we introduce a versatile halide‐pair‐driven multicomponent polymerization (MCP) strategy that enables the library synthesis of sequence‐controlled semiconducting poly(triarylamine)s (PTAAs). By optimizing halide pairing in conjunction with a rationally designed Buchwald ligand–Pd system featuring catalyst‐transfer capability, we achieved efficient sequential cascade aminations, thereby enabling the MCP. The versatility of this strategy was demonstrated through the synthesis of a library of sequence‐controlled PTAAs, including dendronized variants, underscoring its potential as a general platform for functional semiconducting material discovery.