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Luminescence Quenching of Ligand‐Substituted Molybdenum and Tungsten Halide Clusters by Oxygen and Their Oxidation Electrochemistry
Author(s) -
Fuhrmann ArinDaniel,
Seyboldt Alexander,
Schank Andreas,
Zitzer Georg,
Speiser Bernd,
Enseling David,
Jüstel Thomas,
Meyer HansJürgen
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700763
Subject(s) - chemistry , phosphorescence , quenching (fluorescence) , molybdenum , halide , luminescence , ligand (biochemistry) , oxygen , electrochemistry , photochemistry , redox , photoexcitation , inorganic chemistry , tungsten , crystallography , fluorescence , excited state , organic chemistry , biochemistry , physics , receptor , optoelectronics , electrode , quantum mechanics , nuclear physics
Cluster compounds (TBA) 2 [Mo 6 I 8 (CF 3 SO 3 ) 6 ], (TBA) 2 [W 6 I 8 (CF 3 SO 3 ) 6 ], and (TBA) 2 [W 6 Br 8 (CF 3 SO 3 ) 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 (CF 3 SO 3 – ) ligands is compared with corresponding compounds with trifluoroacetato (CF 3 COO – ) and p ‐toluolsulfonato (CH 3 C 6 H 4 SO 3 – ) ligands. By studying these compounds, we investigate the relationship of more‐ or less‐electron‐withdrawing ligands (L) of (TBA) 2 [M 6 X 8 L 6 ] halide (X) clusters, their redox potentials ( E 0 ), and their phosphorescence‐quenching behavior under variable oxygen partial pressures.