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Issue 4, 2008
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Nickel dithiolenes containing pendant thiophene units: precursors to dithiolene–polythiophene hybrid materials

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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 π-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.

Graphical abstract: Nickel dithiolenes containing pendant thiophene units: precursors to dithiolene–polythiophene hybrid materials

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Publication details

The article was received on 18 Sep 2007, accepted on 19 Nov 2007 and first published on 07 Dec 2007


Article type: Paper
DOI: 10.1039/B714372A
Citation: J. Mater. Chem., 2008,18, 475-483
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    Nickel dithiolenes containing pendant thiophene units: precursors to dithiolene–polythiophene hybrid materials

    T. Anjos, S. J. Roberts-Bleming, A. Charlton, N. Robertson, A. R. Mount, S. J. Coles, M. B. Hursthouse, M. Kalaji and P. J. Murphy, J. Mater. Chem., 2008, 18, 475
    DOI: 10.1039/B714372A

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