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Diazoacetate polymerization has attracted considerable research attention because it is an effective approach for fabricating carbon–carbon (C–C) main chain polymers. However, diazoacetate polymerization based on inexpensive catalysts has been a long-standing challenge. Herein, we report a Ni(II) catalyst that can promote the living polymerization of various diazoacetates, yielding well-defined C–C main chain polymers, polycarbenes, with a predictable molecular weight (Mn) and low dispersity (Mw/Mn). Moreover, the Ni(II)-catalyzed sequential living polymerization of thiophene and diazoacetate monomers affords interesting π-conjugated poly(3-hexylthiophene)-block-polycarbene copolymers in high yields with a controlled Mn, variable compositions, and low Mw/Mn, although the structure and polymerization mechanism of the two monomers differ. Using this strategy, amphiphilic block copolymers comprising hydrophobic poly(3-hexylthiophene) and hydrophilic polycarbene blocks are facilely prepared, which were self-assembled into well-defined supramolecular architectures with tunable photoluminescence. |
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