Studies using ultraviolet photoelectron spectroscopy (UPS) and density functional theory (DFT) demonstrate that M 4 X 6 (M = W, Mo and X = O, S) clusters show large gaps (about 2 eV) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), indicative of their high stability and chemical inertness. In particular, W 4 O 6 has a lower symmetry and a larger HOMO-LUMO gap than other hitherto discovered magic clusters. Although the similarity between the electronic structures of W 4 O 6 and Mo 4 S 6 may be regarded as an indication that both clusters have similar geometric structures, our detailed DFT-calculations reveal otherwise. This result implies that synergetic approach using theoretical and experimental methods are essential to shed light on cluster geometries.

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Electronic and geometric structures of M x S y (M = W, Mo; x = 1, 2, 4; y = 1-12) clusters have been studied using density functional theory calculations, and compared to experimental photoelectron spectra. For the metal atoms, an uptake of up to six sulfur atoms has been observed, which can be explained by the bonding of S − 3 chains. A structural difference to the corresponding oxides is the preference of bridging sites for S, which might be the origin of the differences between the structures of bulk MO 3 and MS 2. For x = 1, 2 the HOMO-LUMO gaps vary irregularly. For x = 4, a large HOMO-LUMO gap has been found for y = 6, 7, and 8 and the W 4 S 6 and Mo 4 S 6 clusters have been found to be magic with an extraordinarily high stability.

(1)H, (13)C, and (81)Br NMR spectra of the neat room-temperature ionic liquid (RTIL), namely, 1-decyl-3-methyl-imidazolium bromide ([C(10)mim][Br]) as well as its solutions in acetonitrile, dichloromethane, methanol, and water have been investigated. The most important observation of the present work is the significant broadening of (81)Br NMR signal in the solutions of [C(10)mim][Br] in organic solvents, which molecules tend to associate into hydrogen bond networks and the appearance of the complex contour of (81)Br NMR signal in the neat RTIL as well as in the liquid crystalline (LC) ionogel formed in RTIL/water solution. The complex structure of (81)Br signal changes upon heating and dilution in water. It disappears at ca. 353 K and in the aqueous solution below ca. 0.1 mol fraction of RTIL. Several new (1)H NMR signals appear at the [C(10)mim][Br]/water compositions just before the solidification of the sample (approximately 0.3 mol fraction of [C(10)mim][Br]). These additional peaks can be attributed to the H(2)O protons placed in inhomogeneous regions of the sample or due to the appearance of nonequivalent water sites in LC ionogel, the exchange between which is highly restricted or even frozen. The complex shape of (81)Br NMR signal can originate from the presence of supra-molecular structures (mesoscopic domains) that live over the period of the NMR time-scale due to a very high viscosity of [C(10)mim][Br]. These domains exhibit some features of partially disordered solids (liquid- or plastic crystals). To evaluate the static and dynamic contributions into the relaxation rate of (81)Br nuclei, the quantum chemistry calculations of the electronic structure, magnetic shielding, and electric field gradient (EFG) tensors of [C(10)mim][Br] and related model systems (Br(-).6H(2)O cluster, with addition of the dipoles (hydrogen fluoride) and charged particles - cations: H(+) or C(1)mim(+)) were performed.