Facile Synthesis of Polyfluorene-<i>b</i>-Poly(phenyl isocyanide) Copolymers Enables Engineered Morphological Diversity

Directed self-assembly of π-conjugated block copolymers is a promising nanofabrication strategy, but their synthesis remains challenging. In this work, diverse π-conjugated block copolymers consisting of polyfluorene (PF) and poly(phenyl isocyanide) (PPI) segments were facilely synthesized via postpolymerization modification. PF-b-PPI with pentafluorophenyl ester was prepared in one pot using Pd(II) as the catalyst. Then, postpolymerization modification of PF-b-PPI was achieved using a diverse range of alcohols and amines, enabling facile synthesis of functionalized π-conjugated block copolymers with tailored architectures. These structurally tailored copolymers can self-assemble into well-defined nanostructures, demonstrating their versatility for organic electronics. Our modular approach provides three key advantages: precise architectural control with simplified synthesis, broad functional group compatibility, and facile property tuning through straightforward modifications. This methodology establishes a robust platform for designing advanced π-conjugated block copolymers with tailored optoelectronic and nanofabrication capabilities.