title: Oxidative acetylenic coupling reactions as a surface chemistry tool.
abstract: A novel method to prepare redox monolayers on silicon electrodes has been developed that employs Cu(I)-catalyzed oxidative acetylenic coupling reactions for molecular electronic type applications. As the first case study, ethynylferrocene was covalently immobilized onto an acetylene-terminated monolayer on a Si(100) surface to give a 1,3-diyne (C≡C-C≡C-) linked redox assembly. The derivatization process requires no protection/de-protection steps, nor activation procedures. The effect of the conjugated diyne linkage on the rate of electron transfer between tethered ferrocenyl units and the silicon electrode is benchmarked against well-established "click" products (i.e. 1,2,3-triazole linkage). The surfaces, after each step, are characterized thoroughly using X-ray reflectivity (XRR), X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The coupling chemistry provides a useful strategy for functionalizing silicon surfaces and contributes to an expanding repertoire of wet chemistry routes for the functionalization of solid substrates.
authors.affiliation: School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia.
authors.forename: Simone
authors.initials: S
authors.lastname: Ciampi
authors.forename: Michael
authors.initials: M
authors.lastname: James
authors.forename: Nadim
authors.initials: N
authors.lastname: Darwish
authors.forename: Erwann
authors.initials: E
authors.lastname: Luais
authors.forename: Bin
authors.initials: B
authors.lastname: Guan
authors.forename: Jason B
authors.initials: JB
authors.lastname: Harper
authors.forename: J Justin
authors.initials: JJ
authors.lastname: Gooding