A series of six novel cluster complexes [M6I8(SArf)6]2− (M=Mo or W; SArf=p-SC6F4-C6F5, p-SC6F4Cl, or p-SC6F4CF3) was prepared by exchange reactions between [Mo6I14]2− or [W6I14]2− and silver salts of the corresponding thiols and characterized by X-ray single-crystal diffraction and elemental analysis, NMR, ESI-MS, and CV techniques. In the crystal structures all the thiolate ligands adopt an idiosyncratic orientation along one of the idealized three-fold axes passing through two opposite μ3-I ligands and the centers of two opposite faces of the M6 octahedra. This leads to shortened intramolecular C⋅⋅⋅I distances inside the cluster below 3.5 Å. The clusters exhibit red photoluminescence with relatively high quantum yield, up to 0.42 in the case of (Bu4N)2[W6I8(SC6F4CF3)6]. Moreover, all the compounds exhibit X-ray luminescence; the close values of the maxima in the photo- and X-ray induced emission spectra indicate that the luminescence is cluster-centered.
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- 1.04 ХИМИЧЕСКИЕ НАУКИ