Precision Synthesis of Various Low‐Bandgap Donor–Acceptor Alternating Conjugated Polymers via Living Suzuki–Miyaura Catalyst‐Transfer Polymerization

Herein, we demonstrate that living Suzuki-Miyaura catalyst-transfer polymerization (SCTP) using a RuPhos Pd G3 precatalyst is a versatile method for the precision synthesis of various donor-acceptor alternating conjugated polymers (DA ACPs). First, the living SCTP of biaryl monomers with combinations of both medium to strong A and D were optimized to produce DA ACPs with controlled number average molecular weight (Mn ), narrow dispersity (Ð, 1.05-1.29), and high yield (>87 %). Moreover, its expansion to controlled polymerization (Mn =9.2-40.0 kg mol-1 ) of an A1 -D-A2 -D quateraryl monomer containing diketopyrrolopyrrole (DPP; strong A) was successful. The living SCTP also enabled the efficient one-pot synthesis of various diblock and triblock copolymers. Lastly, the DA ACPs showed tunable optical band gap (Egopt , from 1.29 to 1.77 eV) and highest occupied molecular orbital (HOMO) level (from -5.57 to -4.75 eV), while their block copolymers exhibited broad absorption ranges and promising visible light-harvesting properties.