The post‐polymerization modification of selenophene‐containing (co)polymers is presented based on the electrochemical polymer reaction (ECPR). Selenophene‐ or thiophene‐containing (co)polymers, which are known to be promising materials in optoelectronic devices, were synthesized through Kumada catalyst transfer polymerization to give their homopolymers and block‐ or statistical copolymers with various side chains. Each of the series of polymers was subjected to post‐modification through the ECPR, and the reaction efficiencies were systematically compared. Selenophene‐containing polymers were successfully modified with better ECPR reaction efficiencies than their thiophene analogues. Moreover, the dramatic inhibiting effect of a branched side chain on the ECPR was observed and rationalized, which was very unexpected. Based on the basic tendency observed here, we have finally demonstrated the selective modification of a single segment of a rod−rod block copolymer for the first time.
The Inside Cover picture describes the unprecedented segment‐selective electrochemical transformation of a rod–rod diblock copolymer, in which the reaction proceed at a single segment of the copolymer, owing to the difference in oxidation potentials and side‐chain structures of the segments. More details can be found in the Communication by N. Shida et al. on page 1824 in Issue 8, 2017 (DOI: 10.1002/celc.201700205).
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