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Facile access to coil-rod-coil-type block copolymers by CuAAC-based macromolecular clicking


Defect-free and perfectly linear polyarylenebutadiynylenes can be readily synthesized through acetylenic oxidative polymerizations of diethynyl arene monomers. Although these polymers are ideal semiconducting polymers with a rigid main chain backbone, they often have solubility issues even with the introduction of alkyl side chain groups. We recently reported the synthesis of a poly(thieno[3,2-b]thiophen-2,5-diylbutadiynylene) derivative and its semicrystalline feature due to the limited solubility of this compound. To increase the processability of this polymer in solution, we utilized a Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click postfunctionalization to introduce polystyrenes into the polymer terminals. The molecular weights estimated from gel permeation chromatography (GPC) were reasonably increased, and the temperature-dependent absorption spectra suggested that the CuAAC-based functionalization was successful and furnished a coil-rod-coil type triblock copolymer. The resulting block copolymer exhibited higher solubilities in common organic solvents, but the electronic properties of the poly(thieno[3,2-b]thiophen-2,5-diylbutadiynelene) unit were retained in the solid thin film state.

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This work is supported by JSPS KAKENHI Grant 19H02786.

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Correspondence to Tsuyoshi Michinobu.

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Ogita, K., Yomogita, N., Otep, S. et al. Facile access to coil-rod-coil-type block copolymers by CuAAC-based macromolecular clicking. Polym J 55, 427–432 (2023).

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