A series of diketopyrrolopyrrole (DPP)-based copolymers, with DPP and bithiophene (BT) as the electron-acceptor and donor backbone units, respectively, are synthesized with branched alkyl side chains that are either directly coupled to the N-positions of DPP or separated by an alkyl ester group. The ester moieties in the side chains induce specific cohesive molecular interactions between these side chains, as compared to the alkyl-only side chains with weak van der Waals interactions. Structure analysis of the DPPBT-based copolymers demonstrated that the introduction of a proper alkyl ester spacer to the branched alkyl chains can shorten the π-π stacking distance between the DPPBT backbones down to 3.
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