Structures and redox characteristics of electron-deficient vanadyl phthalocyanines

Document Type

Article

Publication Date

5-2-2011

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 H2O that, in turn, hydrogen-bonds with ketones, resulting in solvent-induced variable solid-state architectures. Fluoroalkyl (Rf) 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 Rf-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. © 2011 American Chemical Society.

Identifier

79955376951 (Scopus)

Publication Title

Inorganic Chemistry

External Full Text Location

https://doi.org/10.1021/ic2000365

ISSN

00201669

First Page

4086

Last Page

4091

Issue

9

Volume

50

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