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Spectroelectrochemical characterisation of poly[Ni(saltMe)]-modified electrodes

Lookup NU author(s): Professor Paul ChristensenORCiD


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Electrogenerated polymers based on the nickel(II) complex 2,3-dimethyl-N,N′-bis(salicylidene)butane-2,3-diaminatonickel(II), poly[Ni(saltMe)], were characterised by in situ FTIR and UV/Vis spectroscopy and ex-situ EPR spectroscopy in order to gain insights into film structure, electronic states and charge conduction. The role of the nickel ions during film oxidation was probed by using EPR to study naturally abundant Ni and 61Ni-enriched polymers. The data from all the spectroscopic techniques are consistent, and clearly indicate that polymerisation and redox switching are associated with oxidative ligand based processes; coulometry suggests that one positive charge was delocalised through each monomer unit. EPR provided evidence for the non-direct involvement of the metal in polymer oxidation: the polymer is best described as a polyphenylene-type compound (conducting polymer), rather than an aggregation of nickel complexes (redox polymer), and the main charge carriers are identified as polarons. An explanation for the high electrochemical stability and conductivity of poly[Ni(saltMe)] with respect to that of poly[Ni(salen)] is proposed, based on stereochemical repulsion between monomeric units; this can impose a less compact supramolecular structure on polymers with bulkier substituents.

Publication metadata

Author(s): Christensen PA; Vilas-Boas M; Freire C; De Castro B; Hillman AR

Publication type: Article

Publication status: Published

Journal: Chemistry - A European Journal

Year: 2001

Volume: 7

Issue: 1

Pages: 139-150

ISSN (print): 0947-6539

ISSN (electronic): 1521-3765

Publisher: Wiley - VCH Verlag GmbH & Co