Redox Chemistry of Nickelocene-Based Monomers and Polymers

The oxidation of [n]nickelocenophanes [Ni(?5-C5H4)2(CH2)3] (3), [Ni(?5-C5H4)2(SiMe2)2] (10), [Ni(?5-C5H4)2(SiMe2)2O] (11), [Ni(?5-C5H4)2(CH2)4] (12), and poly(nickelocenylpropylene) [Ni(?5-C5H4)2(CH2)3]n (4) to both the monocationic dicationic species was investigated in dichloromethane by cyclic voltammetry (CV) square-wave voltammetry. presence acetonitrile on potentials 3 also CV. 10–12 exhibited two single-electron Nernstian redox processes, monocations [3]+, [10]+, [11]+, [12]+ were isolable as [B(C6F5)4]? salts after chemical oxidation, structurally characterized. Ni–Cpcent distances all four monomers decreased upon with a structural distortion manifested ring-tilt angle, ?, among other angles. CV studies reversible first process polyelectrolyte {[Ni(?5-C5H4)2(CH2)3]+}n ([4]n+) used estimate molecular weight polymeric material (Mw = 5300 g mol–1) comparing its diffusion coefficient that monomeric analogue, second electrochemical polymer 4 found be only partially chemically reversible.