The nitroxide-mediated polymerization of various styrenic triarylamines (TARA) and naphthalene diimide (NDI) employing commercially available initiators is detailed. The monomers are readily prepared by Pd-catalysed Hartwig-Buchwald coupling (TARA) or a step-wise condensation route (NDI). The kinetics of the polymerization was followed by NMR, MS and SEC analysis and confirmed the �living character� up to 50% conversion, supported by the steady molar mass increase over time and a low dispersity. Subsequent re-initiation furnished the preparation of block-copolymers with an internal redox cascade, tuned by the substituent of the triarylamine monomer (X = F, Me, OMe). The precise decoration of the chain-end by a photo-redox active ruthenium complex was achieved by simple nucleophilic substitution at the terminal benzyl chloride moiety of the initiator fragment. This methodology was readily applied to prepare the naphthalene diimides congeners. The detailed NMR and electrochemical analysis showed only marginal influence on the chemical shifts and redox-properties of the TARA units, while in case of NDI a mutual interaction of the planar pi-systems was observed. In summary, hierarchical macromolecules with tailored redox-properties can be prepared in only a few synthetic steps, which are attractive candidates as electron relays in light-driven charge separation devices.

Nitroxide-mediated polymerization of styrenic triarylamines and naphthalene diimide: Synthesis and end-functionalization of hierarchical redox-active macromolecules

248th National Meeting (2014)

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