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2-Hydrazinobenzothiazole and 2-furaldehyde diethyl acetal were connected to complementarily functionalized tin sulfide clusters, with coupling of an acetal to a hydrazine-functionalized cluster being so far without precedence. Neither ethers nor an N,S combination of heteroatoms has so far been present in the ligand shell of tetrelchalcogenide clusters. The resulting cluster molecules are based on inorganic [Sn6S10] architectures and show different photoluminescence properties as a function of the attached ligands. [ABSTRACT FROM AUTHOR]

Reactions of the binary, pseudo-homoatomic Zintl anion (Pb2Bi2)2- with Ln(C5Me4H)3 (Ln=La, Ce, Nd, Gd, Sm, Tb) in the presence of [2.2.2]crypt in ethane-1,2-diamine/toluene yielded ten [K([2.2.2]crypt)]+ salts of lanthanide-doped semimetal clusters with 13 or 14 surface atoms. Single-crystal X-ray diffraction and energy-dispersive X-ray spectroscopy indicated the presence of the anions [Ln@Pb6Bi8]3-, [Ln@Pb3Bi10]3-, [Ln@Pb7Bi7]4-, or [Ln@Pb4Bi9]4- in single or double salts; the latter showed various ratios of the components in the solid state. The anions are the first ternary intermetalloid clusters comprising only elements of the sixth period of the periodic table, namely, Pb, Bi and lanthanides. This study, which was complemented by ESI mass spectrometry and 139La NMR spectroscopy in solution, rationalizes a continuous development of the ratio of 13:14-atom cages with the ionic radius of the embedded Ln3+ ion, which seems to select the most suitable cage type. Quantum chemical investigations helped to analyze this situation in more detail and to explain the observed subtle influence of the atomic radii. Magnetic measurements confirmed that the embedded Ln3+ ions keep their expected paramagnetic or diamagnetic nature. [ABSTRACT FROM AUTHOR]

A series of luminescent polynuclear copper(I) phenyl thiolate clusters with functional groups in the organic ligand shell has been synthesized and characterized by single-crystal X-ray diffraction. Cluster compounds 1- 5 with Me2N groups bound to the phenyl thiolate are described and feature different nuclearities and core geometries. The heptanuclear compound 6, which contains both phenyl thiolate and Me3SiO functionalized phenyl thiolate ligands, is an unusual example of a mixed thiolate cluster and exhibits a core almost identical to that of 5. The optical properties of these compounds, which range from binuclear complexes with large Cu ···Cu distances to cluster molecules with seven copper atoms and relatively short Cu ···Cu distances, have been investigated. Compounds 1- 5 show strong absorption below 500 nm. The intense luminescence covers a wide range of the visible spectrum ( 1: green; 2 and 3: blue; 4 and 5: yellow). It seems likely that the optical transitions occur between orbitals of the thiol ligands and metal-centered orbitals; for the species with short Cu ···Cu distances ( 3- 5), these interactions cause a further redshift of the spectra. In addition, the influence of functional groups on optical absorption and emission is shown by the two Cu7 clusters 5 and 6, which differ solely in the electron-donating nature of their functional groups. [ABSTRACT FROM AUTHOR]