Anjos, T., Roberts-Bleming, S.J., Charlton, A., Robertson, N., Mount, A.R., Coles, S.J., Hursthouse, M.B., Kalaji, M. and Murphy, P.J. (2008) Nickel dithiolenes containing pendant thiophene units: precursors to dithiolene-polythiophene hybrid materials. Journal of Materials Chemistry, 18 (4), 475-483. (doi:10.1039/b714372a).
Abstract
The synthesis, electrochemical and spectroscopic properties of the new thiophene-substituted metal dithiolene complexes [Ni(b-3ted)2] ( 3) and [NBu4][Ni(b-3ted)2] ([NBu4][ 3]) are described [b-3ted = bis(3-thienyl)-1,2-ethylenedithiolene] and compared with new studies of the known compounds [Ni(b-2ted)2] ( 2) and [NBu4][Ni(b-2ted)2] ([NBu4][ 2]). X-Ray structures were determined for the neutral complexes 2 and 3 and both showed planar nickel dithiolene units with thiophene groups twisted out of the molecular plane, precluding close molecular -stacking. Electrochemical investigations revealed two redox processes corresponding to interconversion between neutral, monoanionic and dianionic species for 3, analogous to 2. Oxidation of 0.1 mM [ 3]– in CH3CN was shown to give a green molecular film of 3 which, in contrast to as-prepared crystals of 3, showed significant conductivity. Electrochemical polymerisation of 3 carried out at different concentrations resulted in films; electrochemical, SNIFTIRS and UV-Vis results were consistent with incorporation of the intact metal dithiolene complex in these films. In contrast, electrochemical polymerisation of 2 gave a film charateristic of a polymerised thiophene but with no evidence of incorporation of the intact metal dithiolene complex. Copolymerisation of 3 with thiophene gave a gold-coloured electropolymerised film of significant conductivity that, upon dissolution in CH2Cl2, showed the characteristic low energy absorption of the Ni-dithiolene complex, confirming its incorporation. This copolymerisation approach offers a versatile route to the synthesis of metal dithiolene–polythiophene hybrid films.
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