Anodic Chlorination of Selenophene‐Containing Polymers: Reaction Efficiency and Selective Reaction of Single Segment in Rod−Rod Diblockcopolymer. Issue 8 (4th April 2017) - Shida, Naoki
Abstract: 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. Abstract : Time to split : Electrochemical post‐functionalization, namely, the electrochemical polymer reaction (ECPR), of various selenophene‐containing (co)‐polymers is comprehensively investigated. In the anodic chlorination of these polymer films, the degree of chlorination dramatically changes, depending on the main chain and side chain structures. Finally, a block copolymer is designed, which is capable of segment‐selective ECPR.