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Nickel dithiolenes containing pendant thiophene units: precursors to dithiolene-polythiophene hybrid materials

Nickel dithiolenes containing pendant thiophene units: precursors to dithiolene-polythiophene hybrid materials
Nickel dithiolenes containing pendant thiophene units: precursors to dithiolene-polythiophene hybrid materials
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.
conjugated metallopolymers, crystal-structures, conducting polymers, ray, molecular-structure, complexes, ligands, 2-dithiolene, metal, electron-transfer series, electropolymerization, multi-sulfur 1
475-483
Anjos, T.
f1e21519-708f-434c-9951-60560d161cf7
Roberts-Bleming, S.J.
d3cb3019-37a0-49f4-9595-4853395646b7
Charlton, A.
941b7f8a-0fca-42f5-8f59-5a70bcb130bf
Robertson, N.
6baa6741-1e83-422f-964b-2b7a0b03f07a
Mount, A.R.
88ffa99b-0154-4814-9da5-0f8287ca781f
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kalaji, M.
e5a383ec-cca2-4642-8c88-a88836eb6710
Murphy, P.J.
29a84176-c8b8-4159-b152-324f1630faea
Anjos, T.
f1e21519-708f-434c-9951-60560d161cf7
Roberts-Bleming, S.J.
d3cb3019-37a0-49f4-9595-4853395646b7
Charlton, A.
941b7f8a-0fca-42f5-8f59-5a70bcb130bf
Robertson, N.
6baa6741-1e83-422f-964b-2b7a0b03f07a
Mount, A.R.
88ffa99b-0154-4814-9da5-0f8287ca781f
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kalaji, M.
e5a383ec-cca2-4642-8c88-a88836eb6710
Murphy, P.J.
29a84176-c8b8-4159-b152-324f1630faea

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).

Record type: Article

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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More information

Published date: 2008
Keywords: conjugated metallopolymers, crystal-structures, conducting polymers, ray, molecular-structure, complexes, ligands, 2-dithiolene, metal, electron-transfer series, electropolymerization, multi-sulfur 1

Identifiers

Local EPrints ID: 54415
URI: https://eprints.soton.ac.uk/id/eprint/54415
PURE UUID: ca133c12-3750-4fa7-a245-0153d084cc93
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 05 Aug 2008
Last modified: 14 Mar 2019 01:48

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