title: Structures and redox characteristics of electron-deficient vanadyl phthalocyanines.
abstract: The first single-crystal X-ray structures of substituted vanadyl phthalocyanine materials reveal the high-valence vanadium ions (denoted as V(IV)), whose coordination by a highly electron-deficient ligand is facilitated by an axial oxo group. The metal center of the hydrophilic V═O core, encapsulated in F-rich hydrophobic pockets, reaches a coordination number of 6 by binding an additional H(2)O that, in turn, hydrogen-bonds with ketones, resulting in solvent-induced variable solid-state architectures. Fluoroalkyl (R(f)) ligand substituents hinder π-π stacking interactions and favor ordered long-range packing, as well as the facile formation of film materials that exhibit high thermal stability and oxidation resistance. Reversible redox chemistry and spectroscopic studies in both solution and the solid-state indicate single-site isolation in both phases and an R(f)-induced propensity for electron uptake and inhibition of electron loss. Repeated redox cycles reorganize the thin films to accommodate Li(+) ions and facilitate their migration. The facile reduction, combined with high stability and ease of sublimation imparted by the R(f) scaffold that suppresses oxidations, recommends the new materials for sensors, color displays, electronic materials, and redox catalysts, as well as other applications.
authors.affiliation: Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey 07102, USA.
authors.forename: Łukasz
authors.initials: Ł
authors.lastname: Łapok
authors.forename: Martin
authors.initials: M
authors.lastname: Lener
authors.forename: Olga
authors.initials: O
authors.lastname: Tsaryova
authors.forename: Stefanie
authors.initials: S
authors.lastname: Nagel
authors.forename: Christopher
authors.initials: C
authors.lastname: Keil
authors.forename: Robert
authors.initials: R
authors.lastname: Gerdes
authors.forename: Derck
authors.initials: D
authors.lastname: Schlettwein
authors.forename: Sergiu M
authors.initials: SM
authors.lastname: Gorun