Electrochemical polymerisation studies of aza-15-crown-5 vinyl-2,2'-bipyridine ruthenium(II) complexes

Journal article

The electrochemical polymerisation of the mono(ligand) and tris(ligand) ruthenium(II) complexes, [RuL1,2(bipy)2]2+ and [RuL1,23]2+ (bipy = 2,2′-bipyridine, L1 = 4-methyl-4′-(N-styryl-aza-15-crown-5)-2,2′-bipyridine, L2 = 4,4′-bis(N-styryl-aza-15-crown-5)-2,2′-bipyridine), has been investigated in acetonitrile. Preparation of electroactive polymer films was established on reductive electropolymerisation of the tris(ligand) ruthenium(II) complexes. Electropolymerisation of [RuL1(bipy)2]2+ did not take place, suggesting that the polymer formation mechanism involves radical-radical hydrodimerisation for pairs of vinyl groups rather than 'polyvinyl-type' chain propagation. Lack of electropolymerisation for [RuL2(bipy)2]2+, with two vinyl linkages on the same ligand, is explained by steric constraints preventing repeated linkages between aza-15-crown-5 vinyl-pyridine units. While polymer formation via the alternative route of oxidative coupling of the N-styryl-aza-15-crown-5 moieties might be anticipated, electro-oxidation for the [RuL2(bipy)2]2+ and [RuL1,23]2+ complexes led only to the formation of electroinactive orange films with concurrent electrode passivation.

Authors: Beer, P; Kocian, O; Mortimer, R; Ridgway, C; Stradiotto, N

• Publication status: Published
• Journal: JOURNAL OF ELECTROANALYTICAL CHEMISTRY
• Volume: 408
• Issue: 1-2
• Pages: 61-66
• Publication date: 1996-05-30
• DOI: 10.1016/0022-0728(95)04465-5
• ISSN: 0022-0728
• Language: English
• Keywords: electropolymerisation; ruthenium(II) complexes