A Novel Tantalum Cluster Chalcohalide Ta4S1.5Se7.5I8
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Single crystals of Ta4S1.5Se7.5I8 are obtained by heating Ta, S, Se and I2 at 300 °C in 4.0:1.0:8.0:4.4 molar ratio. The structure was determined by X-ray analysis and consists of molecular clusters [Ta4(μ4-S)(μ2-QaxSeeq)4I8] (Q ≈ Se0.87S0.13). The tantalum atoms form a square with long Ta…Ta distances (3.26–3.32 Å), with four dichalcogenide ligands bridging the Ta–Ta edges and a sulfur atom capping the square. Each Ta atom has two terminal iodine atoms. Raman spectroscopy study shows the presence of the characteristic absorption band at 396 cm−1 which is due to the Ta4–μ4-S vibrations. Cyclic voltammetry shows that Ta4S1.5Se7.5I8 in solid state undergoes quasi-reversible one-electron oxidation which is metal-centered.
KeywordsTantalum Chalcogen Chalcohalide Cluster Crystal structure
The authors thank Drs. Alexandr V. Virovets and Eugenia V. Peresypkina for carrying out X-ray diffraction experiment and Technical University of Denmark for an H.C. Ørsted Post-doctoral Fellowship (to ALG).
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