title: Phthalocyaninato complexes with peripheral alkylthio chains: disk-like adsorbate species for the vertical anchoring of ligands on gold surfaces.
abstract: Thin metalorganic films were prepared on gold by self-assembly of thioether-functionalised phthalocyaninato complexes from solution. The phthalocyaninato ligands used contain eight peripheral, β-positioned, alkylthio substituents SR (1a: R = n-C(8)H(17), 1b: R = n-C(12)H(25)), which serve as headgroups for surface binding and promote lateral assembly, while the disk-like phthalocyaninato core offers the scope for the attachment of axial ligands to the adsorbed molecules. This process was mimicked by coordination of pyridine (Py) to [Zn(1a)] and [Zn(1b)], respectively. The crystal structures of the products [Zn(1a)(Py)] and [Zn(1b)(Py)] were determined. The crystal structures of 4,5-bis(octylthio)phthalodinitrile and 4,5-bis(dodecylthio)phthalodinitrile were also determined. The films fabricated from [Mn(1a)Cl] and [Mn(1b)Cl] on gold were characterised by XPS, ToF-SIMS and NEXAFS spectroscopy, which revealed the presence of well-defined and homogeneous self-assembled monolayers (SAMs), whose constituents are bound to the substrate by thioether-gold linkages. The orientation of the macrocycles is predominantly parallel to the surface. Strong electronic interaction of the manganese(III) centre with the substrate leads to Cl loss upon adsorption and its reduction to Mn(II).
authors.affiliation: Institute of Chemistry, University of Kassel, 34109 Kassel, Germany.
authors.forename: Ulrich
authors.initials: U
authors.lastname: Siemeling
authors.forename: Christian
authors.initials: C
authors.lastname: Schirrmacher
authors.forename: Ulrich
authors.initials: U
authors.lastname: Glebe
authors.forename: Clemens
authors.initials: C
authors.lastname: Bruhn
authors.forename: Joe E
authors.initials: JE
authors.lastname: Baio
authors.forename: Líney
authors.initials: L
authors.lastname: Arnadóttir
authors.forename: David G
authors.initials: DG
authors.lastname: Castner
authors.forename: Tobias
authors.initials: T
authors.lastname: Weidner