Macrocyclic cobalt(III) complexes as precursors for metal-polythiophene hybrid materials

Bernhardt, P. and Kilah, N. (2007) Macrocyclic cobalt(III) complexes as precursors for metal-polythiophene hybrid materials. Polyhedron, 26 2: 392-399. doi:10.1016/j.poly.2006.07.001


Author Bernhardt, P.
Kilah, N.
Title Macrocyclic cobalt(III) complexes as precursors for metal-polythiophene hybrid materials
Journal name Polyhedron   Check publisher's open access policy
ISSN 0277-5387
Publication date 2007-01-01
Year available 2006
Sub-type Article (original research)
DOI 10.1016/j.poly.2006.07.001
Open Access Status DOI
Volume 26
Issue 2
Start page 392
End page 399
Total pages 8
Place of publication Oxford
Publisher Pergamon - Elsevier Science Ltd
Language eng
Subject C1
250201 Transition Metal Chemistry
780103 Chemical sciences
250107 Electrochemistry
Abstract A thiophene-functionalised macrocyclic ligand trans-6,13-dimethyl-6-((thiophen-3-ylmethyl) amino)-1,4,8,1 1-tetraazacyclotetradecane-13-amine (L-1) has been prepared and complexed with Co-III. The ligand L-1 binds as a pentadentate in the crystallographically characterised complexes [CoL1(OAc)](ClO4)(2) and [(CoLCI)-C-1]Cl-2. Electro-copolymerisation of [(CoLCl)-Cl-1]Cl-2 with 3,4-ethylenedioxythiophene (EDOT) in a 1:2 ratio on a preformed poly-3,4-ethylenedioxythiophene (PEDOT) film resulted in metal-polymer hybrid films of high quality, consistency and uniformity in appearance. The copolymerised films were characterised by XPS indicating a 1:11 ratio of incorporation of complex to EDOT. Electrochemistry of the Co-PEDOT film (cast on an indium-doped tin oxide working electrode) in water revealed a Co-III/II redox couple at a potential ca. -600 mV (vs Ag/AgCl) which is similar to that seen in solution for the monomeric aqua complex [CoL1(OH2)](3+) (c) 2006 Elsevier Ltd. All rights reserved.
Formatted abstract
A thiophene-functionalised macrocyclic ligand trans-6,13-dimethyl-6-((thiophen-3-ylmethyl) amino)-1,4,8,1 1-tetraazacyclotetradecane-13-amine (L-1) has been prepared and complexed with CoIII. The ligand L1 binds as a pentadentate in the crystallographically characterised complexes [CoL1(OAc)](ClO4)2 and [CoL1CI]Cl2. Electro-copolymerisation of [CoL1Cl]Cl2 with 3,4-ethylenedioxythiophene (EDOT) in a 1:2 ratio on a preformed poly-3,4-ethylenedioxythiophene (PEDOT) film resulted in metal-polymer hybrid films of high quality, consistency and uniformity in appearance. The copolymerised films were characterised by XPS indicating a 1:11 ratio of incorporation of complex to EDOT. Electrochemistry of the Co-PEDOT film (cast on an indium-doped tin oxide working electrode) in water revealed a CoIII/II redox couple at a potential ca. -600 mV (vs Ag/AgCl) which is similar to that seen in solution for the monomeric aqua complex [CoL1(OH2)]3+
Keyword Chemistry, Inorganic & Nuclear
Crystallography
macrocycle
conducting polymer
electrochemistry
cobalt
Electronic-energy-transfer
Conducting Polymers
Micellar-solution
Crystal-structure
Crown-ether
Films
3,4-ethylenedioxythiophene
Electropolymerization
6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine
Electroluminescence
Q-Index Code C1
Q-Index Status Confirmed Code

 
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Created: Tue, 19 Feb 2008, 02:08:37 EST