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Reactions of copper(I) acetate with 2-mercaptothiazoline (HS-thiaz) in the presence of tertiary phosphines lead to the formation of tetranuclear sulphur-bridged copper complexes. Depending on the reaction conditions, isolated clusters ([[Cu.sub.4][(S-thiaz).sub.4][(P[R.sub.3]).sub.2]] (P[R.sub.3] = P[Ph.sub.3] (1), [Pet.sub.2]Ph (2), P[Et.sub.3] (3)), oligomeric compounds ([[[Cu.sub.4][(S-thiaz).sub.4]].sub.2] (4) and [[[Cu.sub.4][(S-thiaz).sub.4]].sub.4] (5)), or a one-dimensional polymer [([[Cu.sub.4][(S-thiaz).sub.4].sub.∞] (6)) are formed. The structures of the compounds 2-5 have been determined by single crystal X-ray analysis. Key words: copper, 2-mercaptothiazoline, single crystal X-ray analysis. Les reactions de l'acetate de cuivre(I) avec la 2-mercaptothiazoline (HS-thiaz), en presence de phosphines tertiaires, conduisent a la formation de complexes de cuivre tetranucleaires comportant des ponts de soufre. Suivant les conditions reactionnelles, il y a formation d'agregats isoles, ([[Cu.sub.4][(S-thiaz).sub.4][(P[R.sub.3]).sub.2]] (P[R.sub.3] = P[Ph.sub.3] (1); P[Et.sub.2]Ph (2); P[Et.sub.3] (3)), des composes oligomeres, [([[Cu.sub.4][(S-thiaz).sub.4]].sub.2] (4) ou [Cu4(S-thiaz)4]4 (5)), ou d'un polymere unidimensionnel, [[[Cu.sub.4][(S-thiaz).sub.4]].sub.∞] (6). Les structures des composes 2, 3, 4 et 5 ont ete determinees par diffraction des rayons X sur un cristal unique. Mots cles : cuivre, 2-mercaptothiazoline, diffraction des rayons X par un cristal unique. [Traduit par la Redaction], Introduction The chemistry of copper(I) in combination with chalcogen derivatives provides a large variety of compounds. Many clusters with increasing numbers of metal atoms have been synthesized, the biggest cluster [...]

The copper tellurolate cluster [[([Cu.sub.6](TePh).sub.6][(Pet[Ph.sub.2]).sub.5]] (1) has been loaded into the pores of a trimethylsilylated MEM-41 (TMS-MCM-41) framework. Solutions of 1 in tetrahydrofuran lead to good impregnation weight % (~10 wt%, 1). The resulting material was analysed by powder X-ray diffraction (PXRD), nitrogen sorption isotherms, thermogravimetric analysis (TGA), energy dispersive X-ray (EDX) analysis, [sup.31]P CP MAS NMR spectroscopy, and transmission electron microscopy (TEM). It was observed that the loading process proceeds with the intact cluster 1 being present within the hexagonal architecture. The intact nature of 1 makes it an ideal candidate for condensation by photochemical or thermal means. Both of these condensation treatments increase the Cu:Te ratio of 1 to approach that observed in binary semiconductor [Cu.sub.2]Te. The condensation process was analysed by GC-MS spectrometry and characterization of the condensed, isolated composites was performed by TGA, EDX analysis, 31p CP MAS NMR spectroscopy, nitrogen adsorption, and TEM measurements. Thermal condensation results in the formation of [Cu.sub.2]Te particles, whereas photochemical condensation yields larger copper-tellurolate nanoclusters. Key words: copper, tellurium, cluster, MEM-41, trimethylsilylated, photolysis, thermolysis, [Cu.sub.2]Te, composite, mesoporous material. L'agregat de tellurolate de cuivre [[([Cu.sub.6](TePh).sub.6][(Pet[Ph.sub.2]).sub.5]] (1) a ete introduit clans les pores d'un squelette de MEM-41 trimethylsilyle (TMS-MCM-41). Des solutions du compose 1 clans le tetrahydrofurane conduisent a de bonnes impregnations allant jusqu'a 10% de 1, en poids. On a analyse le produit qui en est resulte par diffraction des rayons X par des poudres, par des isothermes de sorption d'azote, par analyse thermogravimetrique (ATG), par analyse de la dispersion d'Energie de rayons X (DEX), par spectroscopie RMN du [sup.31]P, a l'angle magique de rotation avec polarisation croisee (RMN du [sup.31]P << CP MAS >>) et par la microscopie de transmission electronique (MTE). On a observe que le processus d'impregnation se produit tout en maintenant l'agregat 1 intact dans l'architecture hexagonale. La nature intacte du compose 1 en fait un candidat ideal pour des condensations par des mEthodes photochimiques ou thermiques. Ces deux traitements de condensation augmentent le rapport Cu : Te du compose 1 pour lui permettre d'approcher celui observe dans le semiconducteur binaire CuzTe. On a analyse le processus de condensation par le biais de la spectroscopie de masse liee a la chromatographie gazeuse et on a procede a une caracterisation des composites qui ont ete isoles de la condensation par le biais de l'ATG, d'analyses de DEX, de RMN du [sup.31]P CP MAS, d'adsorption d'azote et de mesures de MTE. La condensation thermique conduit h la formation de particules de [Cu.sub.2]Te alors que la condensation photochimique conduit a des nano-agregats pius gros de tellurolate de cuivre. Mots cles: cuivre, tellure, agreagat, MEM-41, trimethylsilyle, photolyse, thermolyse, [Cu.sub.2]Te, composite, materiel mesoporeux. [Traduit par la Redaction], Introduction A wide array of transition-metal-chalcogen nanoclusters has been prepared and characterized with diverse composition, size, and structure (1). Numerous routes to metalchalcogenide particles have been described from the con [...]

The photoluminescence (PL) properties of several newly synthesized ligand-stabilized polynuclear gold(I) selenide complexes are investigated. [Au18Se8(dppe)6]Br2 {dppe = bis(diphenylphosphanyl) ethane} is distinguished by the bright-red long-lived PL (phosphorescence) in the solid state, photosensitization of singlet oxygen, (super 1)O2, in solution, and high photostability.

The binary materials ZnS, ZnSe, and ZnTe are prepared within the mesoporous framework of MCM-41 at room temperature through the use of silylated chalogen reagents. The ZnE-MCM-41 materials are characterized and the observed blue shift in the absorption maximum has agreed well with the expected quantum confinement of these materials given the nanometer dimensions of the mesoporous architecture of the silicate host.