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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 phosphorescencequenching behavior of compounds containing trifluorometh-[a] Section

Molybdenum and tungsten iodide clusters with the [M 6 I 8 ] cluster core show versatile photophysical properties that strongly depend on the nature of six apical ligands (L) in [M 6 I 8 L 6 ] 2-. In course of our syntheses we report a new efficient preparation of Cs 2 [Mo 6 I 14 ] as precursor. Target compounds (n Bu 4 N) 2 [M 6 I 8 (NCO) 6 ] with M = Mo, W with cyanate ligands were synthesized and structurally characterized

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Hybrid organic-inorganic cluster compounds A 2 [W 6 I 14 ] with A = Ph 4 P, PPN were prepared by cation exchange reactions from Cs 2 [W 6 I 14 ] with a corresponding organic halide; and a purification method for A 2 [W 6 I 14 ] compounds by column chromatography is introduced. Crystal structures of compounds were solved and refined based on single-crystal X-ray diffrac- [a]