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 (M_n ), narrow dispersity (Ð, 1.05-1.29), and high yield (>87 %). Moreover, its expansion to controlled polymerization (M_n =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 (E_g ^opt , 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.

Keywords: Catalyst-Transfer Polymerization; Conjugated Polymer; Donor-Acceptor Copolymers; Organic Semiconductors; Suzuki-Miyaura Coupling.

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