Structures and Redox Characteristics of Electron-Deficient Vanadyl Phthalocyanines

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• 作者：艁ukasz 艁apok ; Martin Lener ; Olga Tsaryova ; Stefanie Nagel ; Christopher Keil ; Robert Gerdes ; Derck Schlettwein ; Sergiu M. Gorun
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：May 2, 2011
• 年：2011
• 卷：50
• 期：9
• 页码：4086-4091
• 全文大小：880K
• 年卷期：v.50,no.9(May 2, 2011)
• ISSN：1520-510X

文摘

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鈺怬 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 (R_f) ligand substituents hinder 蟺鈭捪€ 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.