Nickelocene-based polymeric materials have been synthesized via ring-opening polymerisation of strained ansa-bridged precursors, with dynamic behaviour in the polymer as a result of weak nickel-cyclopentadienyl bonds. The oxidation of 20 valence electron nickelocene moieties to their 19 valence electron nickelocenium cations results in the strengthening of this metal-ligand bond, and the redox chemistry of both the monomeric [n]nickelocenophanes and polymers was investigated in this study. Electrochemical results will be presented: a series of [n]nickelocenophanes were found to exhibit two single-electron Nernstian redox processes, and the molecular weight of the nickleocene-based polymer was estimated by comparing the diffusion coefficient associated with its first oxidation with that of a monomeric analogue. Chemical oxidation experiments were also performed, and the effect of this oxidation upon strucutral distortions in [n]nickelocenophanes related to ring-strain and polymerisation propensity will also be dicussed.

Redox chemistry of Nickelocene-based monomers and polymers

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ACS Fall 2022

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