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Rapid Electrochemical Reduction of Ni(II) Generates Reactive Monolayers for Conjugated Polymer Brushes in One Step

Roy, Anandi, Gao, Jing, Bilbrey, Jenna A., Huddleston, N. Eric, Locklin, Jason
Langmuir 2014 v.30 no.34 pp. 10465-10470
aromatic hydrocarbons, chlorine, diazonium compounds, electrochemistry, electrodes, gold, nickel, polymers, salts
This article reports the development of a robust, one-step electrochemical technique to generate surface-bound conjugated polymers. The electrochemical reduction of arene diazonium salts at the surface of a gold electrode is used to generate tethered bromobenzene monolayers quickly. The oxidative addition of reactive Ni(0) across the aryl halide bond is achieved in situ through a concerted electrochemical reduction of Ni(dppp)Cl₂. This technique limits the diffusion of Ni(0) species away from the surface and overcomes the need for solution deposition techniques which often require multiple steps that result in a loss of surface coverage. With this electrochemical technique, the formation of the reactive monolayer resulted in a surface coverage of 1.29 × 10¹⁴ molecules/cm², which is a 6-fold increase over previously reported results using solution deposition techniques.