Abstract / Description of output
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 p- 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.
Original language | English |
---|---|
Pages (from-to) | 475-483 |
Number of pages | 9 |
Journal | Journal of Materials Chemistry |
Volume | 18 |
Issue number | 4 |
DOIs | |
Publication status | Published - 2008 |
Keywords / Materials (for Non-textual outputs)
- MULTI-SULFUR 1,2-DITHIOLENE
- ELECTRON-TRANSFER SERIES
- RAY CRYSTAL-STRUCTURES
- CONDUCTING POLYMERS
- CONJUGATED METALLOPOLYMERS
- MOLECULAR-STRUCTURE
- COMPLEXES
- METAL
- ELECTROPOLYMERIZATION
- LIGANDS