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

Athiophene-functionalised macrocyclic ligand <i>trans</i>-6,13-dimethyl-6-((thiophen-3-ylmethyl)amino)-1,4,8,11-tetraazacyclotetradecane- 13-amine (L¹) has been prepared and complexed with Co^III. The ligand L¹ binds as a pentadentate in the crystallographically characterised complexes [CoL¹(OAc)](ClO₄)₂ and [CoL¹Cl]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 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⁺.