“…Among the reported π-conjugated polymers, polythiophenes (PTs), , poly(phenyleneethynylene)s (PPEs), , and polyfluorenes (PFs) − are widely investigated due to their high conductivity and adjustable optoelectronic characteristics. These polymers with controllable molar mass ( M n ) and narrow molecular weight distribution ( M w / M n ) are commonly prepared through the “living catalyst transfer polycondensation (CTP)”, which involve Kumada, Sonogashira, and Suzuki cross-coupling reactions using Ni(II) or Pd(II) catalysts. , Recently, we have developed a series of Pd(II) and Ni(II) catalysts, which can initiate the living polymerization of phenyl isocyanides (PIs), allenes, and dizaoacetates, and enable the controlled synthesis of helical poly(phenyl isocyanide) (PPI), − polyallene (PA), ,,− and polycarbene (PC), respectively. ,− Combining these polymerizations with CTP, block copolymers such as PT- b -PPI, − PT- b -PA, − PT- b -PC, PPE- b -PPI, , PF- b -PPI, , and PF- b -PC have been prepared via the one-pot living block copolymerization of two distinct monomers (Figure c). The living block copolymerization mechanisms provided the block copolymers in high yields, controllable M n , low M w / M n , and tunable compositions.…”