Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 21st October 2020 from 07:00 AM to 07:00 PM (BST).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 34, 2009
Previous Article Next Article

Synthesis, structure and spectroscopic properties of a new class of polymerisable nickel dithiolenes

Author affiliations

Abstract

The synthesis, structure and spectroscopic properties of a new class of asymmetric nickel dithiolene complex containing pendent thiophene units [Ni(R2pipdt)(b-3ted)] are described {R = Bz (3), iPr (4); pipdt = piperazine-3,2-dithione; b-3ted = bis(3-thienyl)-1,2-ethylenedithiolene}. X-ray crystallography of both neutral species shows planar nickel dithiolene units and the thiophene groups twisted out of the molecular plane, with the R group having a large effect on the packing structure. DFT geometry calculations show good agreement with experimental data for 3 and 4 and confirm that the low energy absorption, assigned to a HOMO → LUMO transition, is inter-ligand charge-transfer in character. Solid state calculations show greater band dispersion in 4, which corresponds to a closer packing in the crystal lattice. Cyclic voltammetry of both complexes displays three reversible processes, corresponding to an interconversion between cationic, neutral, anionic and dianionic species, with tuning of the redox potentials by variation of the R group. Electrochemical polymerisation of 3 shows incorporation of intact dithiolene units into a polymer film with redox functionality similar to that of the monomer, whereas co-polymerisation of 3 with thiophene yields a highly conductive film with redox functionality similar to polythiophene and enhanced absorption across the near IR.

Graphical abstract: Synthesis, structure and spectroscopic properties of a new class of polymerisable nickel dithiolenes

Back to tab navigation

Supplementary files

Article information


Submitted
07 Apr 2009
Accepted
11 Jun 2009
First published
08 Jul 2009

J. Mater. Chem., 2009,19, 6194-6200
Article type
Paper

Synthesis, structure and spectroscopic properties of a new class of polymerisable nickel dithiolenes

S. Dalgleish, C. A. Morrison, D. S. Middlemiss, A. R. Mount, A. Collins, L. Pilia, A. Serpe, M. L. Mercuri, S. J. Roberts-Bleming, A. Charlton, P. Deplano, P. J. Murphy and N. Robertson, J. Mater. Chem., 2009, 19, 6194
DOI: 10.1039/B907028A

Search articles by author

Spotlight

Advertisements