title: Surface Functionalization of Oxide-Covered Zinc and Iron with Phosphonated Phenylethynyl Phenothiazine.
abstract: Phenothiazines are redox-active, fluorescent molecules with potential applications in molecular electronics. Phosphonated phenylethynyl phenothiazine can be easily obtained in a four-step synthesis, yielding a molecule with a headgroup permitting surface linkage. Upon modifying hydroxylated polycrystalline zinc and iron, both covered with their respective native oxides, ultrathin organic layers were formed and investigated by use of infrared (IR) reflection spectroscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), contact angle measurement, and ellipsometry. While stable monolayers with upright oriented organic molecules were formed on oxide-covered iron, multilayer formation is observed on oxide-covered zinc. ToF-SIMS measurements reveal a bridging bidentate bonding state of the organic compound on oxide-covered iron, whereas monodentate complexes were observed on oxide-covered zinc. Both organically modified and unmodified surfaces exhibit reactive wetting, but organic modification makes the surfaces initially more hydrophobic. Cyclic voltammetry (CV) indicates redox activity of the multilayers formed on oxide-covered zinc. On the other hand, the monolayers on oxide-covered iron desorb after electrochemical modifications in the state of the oxide, but are stable at open circuit conditions. Exploiting an electronic coupling of phenothiazines to oxides may thus assist in corrosion protection.
authors.affiliation: †Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Strasse 1, 40237 Düsseldorf, Germany.
authors.forename: Julian
authors.initials: J
authors.lastname: Rechmann
authors.affiliation: †Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Strasse 1, 40237 Düsseldorf, Germany.
authors.forename: Adnan
authors.initials: A
authors.lastname: Sarfraz
authors.affiliation: ‡Chair of Organic Chemistry, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, 40225 Düsseldorf, Germany.
authors.forename: Alissa C
authors.initials: AC
authors.lastname: Götzinger
authors.affiliation: ‡Chair of Organic Chemistry, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, 40225 Düsseldorf, Germany.
authors.forename: Elena
authors.initials: E
authors.lastname: Dirksen
authors.affiliation: ‡Chair of Organic Chemistry, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, 40225 Düsseldorf, Germany.
authors.forename: Thomas J J
authors.initials: TJ
authors.lastname: Müller
authors.affiliation: †Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Strasse 1, 40237 Düsseldorf, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Erbe