title: Electrochemical deposition of poly(trans-[RuCl2(4-vinylpyridine)4]) and its reductive desorption: cyclic voltammetry and electrochemical quartz crystal microbalance studies.
abstract: The electropolymerization of trans-[RuCl(2)(vpy)(4)](vpy = 4-vinylpyridine) on Au or Pt electrodes was studied by cyclic voltammetry and the electrochemical quartz crystal microbalance (EQCM) technique. Cyclic voltammetry of the monomer in DMSO on Au shows reductions at -2.0 and -2.2 V. Potential cycling over the first wave leads to polymer formation; however, scanning over the second wave leads to desorption of the polymer. These observations were confirmed by EQCM measurements which also revealed a high polymerization efficiency. Electrolysis, EQCM and XPS measurements showed that desorption was associated with substitution of chloride ligands by DMSO when the polymer was in a highly reduced state. The film also showed reversible mass changes due to the oxidation and accompanying ingress of charge-balancing anions and solvent into the film. Measurements on the dried films revealed that large quantities of solvent are trapped in the film during the electropolymerization process.
authors.affiliation: Universidade Federal de Santa Catarina, Campus Trindade-Depto. de Química-CFM, Florianópolis-SC, Brazil.
authors.forename: Merlin C E
authors.initials: MC
authors.lastname: Bandeira
authors.forename: Joe A
authors.initials: JA
authors.lastname: Crayston
authors.forename: César V
authors.initials: CV
authors.lastname: Franco
authors.forename: Andrew
authors.initials: A
authors.lastname: Glidle
mesh_terms: D000042:Absorption; D000097:Acetonitriles / Q000737:chemistry; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D004563:Electrochemistry; D004566:Electrodes; D004573:Electrolytes; D006046:Gold / Q000737:chemistry; D008024:Ligands; D036103:Nanotechnology; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010984:Platinum / Q000737:chemistry; D011108:Polymers / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry*; D011791:Quartz / Q000737:chemistry*; D017975:Ruthenium Compounds / Q000737:chemistry*; D013997:Time Factors
chemical_list: D000097:Acetonitriles; D004573:Electrolytes; D008024:Ligands; D009942:Organometallic Compounds; D011108:Polymers; D011725:Pyridines; D017975:Ruthenium Compounds; D011791:Quartz; D010984:Platinum; D006046:Gold; C029351:4-vinylpyridine; C038365:ruthenium chloride; D004121:Dimethyl Sulfoxide; C032159:acetonitrile