title: Thiolate chemistry: a powerful and versatile synthetic tool for immobilization/functionalization of oligothiophenes on a gold surface.
abstract: The synthesis and characterization of a series of quaterthiophenes (4Ts) with thiolate groups protected with 2-cyanoethyl (CNE), 2-trimethylsilylethyl (TMSE), and acetyl (Ac) groups are described. Sequential cleavage of these different protecting groups allows for the preparation of 4Ts derivatized with ferrocene and/or alkanethiol chains. The electrochemical behavior of these compounds has been analyzed in solution by cyclic voltammetry (CV). A ferrocene-derivatized dithiol 4T 14 and a dithiol 4T 15 with two TMSE-protected thiolate groups have been immobilized on a gold surface as monolayers that have been characterized by CV, ellipsometry, contact-angle measurement, and X-ray photoelectron spectroscopy (XPS). The results show that molecules 14 and 15 are doubly grafted with a horizontal orientation of the conjugated system relative to the surface. Furthermore, application of the deprotection/alkylation sequence of the remaining protected thiolate groups on a monolayer of 15 allows for efficient post-functionalization.
authors.affiliation: University of Angers, CNRS, Laboratoire MOLTECH-Anjou, Linear Conjugated Systems Group, 2 Bd Lavoisier, 49045 Angers, France.
authors.forename: Truong Khoa
authors.initials: TK
authors.lastname: Tran
authors.forename: Quentin
authors.initials: Q
authors.lastname: Bricaud
authors.forename: Maïténa
authors.initials: M
authors.lastname: Oçafrain
authors.forename: Philippe
authors.initials: P
authors.lastname: Blanchard
authors.forename: Jean
authors.initials: J
authors.lastname: Roncali
authors.forename: Stéphane
authors.initials: S
authors.lastname: Lenfant
authors.forename: Sylvie
authors.initials: S
authors.lastname: Godey
authors.forename: Dominique
authors.initials: D
authors.lastname: Vuillaume
authors.forename: David
authors.initials: D
authors.lastname: Rondeau