3 years ago

Luminescence Quenching of Ligand-Substituted Molybdenum and Tungsten Halide Clusters by Oxygen and Their Oxidation Electrochemistry

Luminescence Quenching of Ligand-Substituted Molybdenum and Tungsten Halide Clusters by Oxygen and Their Oxidation Electrochemistry
Georg Zitzer, Thomas Jüstel, David Enseling, Andreas Schank, Alexander Seyboldt, Hans-Jürgen Meyer, Bernd Speiser, Arin-Daniel Fuhrmann
Cluster compounds (TBA)2[Mo6I8(CF3SO3)6], (TBA)2[W6I8(CF3SO3)6], and (TBA)2[W6Br8(CF3SO3)6] are prepared and structurally characterized from single-crystal X-ray diffraction data. All compounds show red emission on photoexcitation at 400 nm. However, the phosphorescence of crystalline samples is quenched in the presence of oxygen, depending on the partial pressure of oxygen. The distinct phosphorescence-quenching behavior of compounds containing trifluoromethanesulfonato (CF3SO3–) ligands is compared with corresponding compounds with trifluoroacetato (CF3COO–) and p-toluolsulfonato (CH3C6H4SO3–) ligands. By studying these compounds, we investigate the relationship of more- or less-electron-withdrawing ligands (L) of (TBA)2[M6X8L6] halide (X) clusters, their redox potentials (E0), and their phosphorescence-quenching behavior under variable oxygen partial pressures. [M6X8L6]2– clusters (M = Mo, W; X = Br, I; L = ligand) are prepared with various ligands (L) and studied to explore the relationship between more- or less-electron-withdrawing ligands, redox potentials, and phosphorescence quenching under different partial pressures of oxygen.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201700763

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