The semiconducting properties of conjugated molecular systems are determined by the intermolecular/interchain pi-pi interactions and ordered packing. But, more and more studies manifest that apart from the conjugated backbones the side alkyl chains can dictate the self-organization of the polymer owing to the need for the side chains to form low-energy, space-filling structures. In many cases, the attractive van der Waals interactions between the alkyl side chains can exert an important influence on the interchain packing and backbone conformation, and as a result the thin film microstructure and charge transporting are affected. In this presentation, I will introduce our recent explorations in this aspect, including conjugated D-A polymers with both branching and linear alkyl chains and these with functional groups such amino and urea. The results demonstrate that semiconducting performance of these conjugated polymers can be largely improved by varying the side chains, and side-chain engineering becomes a new strategy for development of high performance of organic/polymeric semiconductors.
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