The reactions between diphosphino-alkynyl gold complexes (PhC2Au)PPh2(C6H4)(n)PPh2(AuC2Ph) (n = 1, 2, 3) with Cu(+) lead to formation of the heterometallic aggregates, the composition of which may be described by a general formula [{Au(x)Cu(y)(C2Ph)2x}Au3{PPh2(C6H4)(n)PPh2}3](3+(y-x)) (n = 1, 2, 3; x = (n + 1)(n + 2)/2; y = n(n + 1)). These compounds display very similar structural patterns and consist of the [Au(x)Cu(y)(C2Ph)2x](y-x) alkynyl clusters "wrapped" in the [Au3(diphosphine)3](3+) triangles. The complex for n = 1 was characterized crystallographically and spectrally, the larger ones (n = 2, 3) were investigated in detail by NMR spectroscopy. Their luminescence behavior has been studied, and a remarkably efficient emission with a maximum quantum yield of 0.92 (n = 1) has been detected. Photophysical experiments demonstrate that an increase of the size of the aggregates leads to a decrease in photostability and photoefficiency. Computational studies have been performed to provide additional insight into the structural and electronic properties of these supramolecular complexes. The theoretical results obtained are in good agreement with the experimental data, supporting the proposed structural motif. These studies also suggest that the observed efficient long-wavelength luminescence originates from metal-centered transitions within the heterometallic Au-Cu core.

The reactions of diphosphino-alkynyl gold complexes (PhC 2 Au)PPh 2 (C 6 H 4 ) n PPh 2 (AuC 2 Ph) (n ) 1, 2, 3) with Ag + lead to the formation of supramolecular heterometallic aggregates, which consist of the [Au x Ag y (C 2 Ph) 2x ] y-x clusters (x ) (n+1)(n+2)/2; y ) n(n+1)) "wrapped" in gold-diphosphine "belts". The composition of the "belts" depends on the size of the heterometallic cluster; for n ) 1 it is an open-loop tetrametallic diphosphine-alkynyl [Au(C 2 Ph)Au 2 Ag(PPh 2 (C 6 H 4 ) 2 PPh 2 ) 3 ] 3+ complex, and for n ) 2, 3 it is a symmetrical closed triangle [Au 3 {PPh 2 (C 6 H 4 ) n PPh 2 } 3 ] 3+ . The complex for n ) 1 was characterized crystallographically and spectrally; the larger ones (n ) 2, 3) were investigated in detail by NMR spectroscopy. Their luminescence behavior has been studied, and an intense room-temperature solution emission with maximum quantum yield of 0.35 (n ) 2) was detected. Computational studies have been performed to provide additional insight into the structural and electronic properties of these supramolecular complexes. Theoretical results obtained are in good agreement with the experimental data, supporting the proposed structural motif. These studies also suggest that the observed efficient long-wavelength luminescence is associated with transitions within the central Au(I)-Ag(I) heterometallic fragment.

Treatment of Au(SC(4)H(8))Cl with a stoichiometric amount of hydroxyaliphatic alkyne in the presence of NEt(3) results in high-yield self-assembly of homoleptic clusters (AuC(2)R)(10) (R = 9-fluorenol (1), diphenylmethanol (2), 2,6-dimethyl-4-heptanol (3), 3-methyl-2-butanol (4), 4-methyl-2-pentanol (4), 1-cyclohexanol (6), 2-borneol (7)). The molecular compounds contain an unprecedented catenane metal core with two interlocked 5-membered rings. Reactions of the decanuclear clusters 1-7 with gold-diphosphine complex [Au(2)(1,4-PPh(2)-C(6)H(4)-PPh(2))(2)](2+) lead to octanuclear cationic derivatives [Au(8)(C(2)R)(6)(PPh(2)-C(6)H(4)-PPh(2))(2)](2+) (8-14), which consist of planar tetranuclear units {Au(4)(C(2)R)(4)} coupled with two fragments [AuPPh(2)-C(6)H(4)-PPh(2)(AuC(2)R)](+). The titled complexes were characterized by NMR and ESI-MS spectroscopy, and the structures of 1, 13, and 14 were determined by single-crystal X-ray diffraction analysis. The luminescence behavior of both Au(I)(10) and Au(I)(8) families has been studied, revealing efficient room-temperature phosphorescence in solution and in the solid state, with the maximum quantum yield approaching 100% (2 in solution). DFT computational studies showed that in both Au(I)(10) and Au(I)(8) clusters metal-centered Au → Au charge transfer transitions mixed with some π-alkynyl MLCT character play a dominant role in the observed phosphorescence.

A series of compounds possessing polyvalent iodine groups was prepared from onitroiodobenzene. Single crystal X-ray investigation revealed a strong interaction between iodine atom and one of the oxygen atoms of the nitro group. This interaction is strongest in trifluoroacetate of hydroxy(o-nitrophenyl)iodonium salt, which is formed from an iodosylarene and an acid being the first example of this new class of compounds. These compounds are also characterized by NMR-spectroscopy.

A simple procedure for conversion of S-glycosyl isothiourea derivatives into thioglycosides by promotion with triethylamine is described. The reaction conditions allow the synthesis of glycosyl thioesters and some thioglycosides, which cannot be prepared using the traditional approach. The procedure has been successfully applied for preparation of thiooligosaccharides, shown by syntheses of methyl 4-thio-a-cellobioside and methyl 4-thio-a-lactoside derivatives.