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The synthesis of crownlike [[Et.sub.4]N][sub.4][([mu.sub.5]-W[Se.sub.4])(CuI)[sub.5](mu-I)[sub.2]] and octahedral polymeric [([mu.sub.6]-W[Se.sub.4][Cu.sub.6][I.sub.4](py)[sub.4]][sub.n] is reported by coordination of additional Cu(I) ions to the planar cluster [[Et.sub.4]N][sub.4][([mu.sub.4]-W[Se.sub.4])[Cu.sub.4][I.sub.6]]. The molecular structures and spectroscopic properties, as also the optical nonlinearities of these heteroselenometallic clusters, are presented.

The heterometallic Sb(III)/Li cage complex [[{Sb[(P-t-Bu).sub.3]}.sub.2][Li.sub.6] * 6THF] (1) is obtained by the low-temperature (<0[degrees]C) reaction of Sb[(N[Me.sub.2]).sub.3] with t-BuPHLi (1:3 equiv) in THF. Thermolysis of this reaction solution leads to the formation of the bicyclic distibane [[[(t-BuP).sub.3][Sb].sub.2]] (2). [sup.31]P NMR spectroscopic studies reveal that this process involves initial formation of [[(t-Bu[P).sub.3][Sb].sup.-]] and [[t-Bu(H)PP-t-Bu].sup.-] anions. Complexes 1 and 2 have been characterized in the solid state by X-ray diffraction studies. Key words: antimony, lithium, cage.

The synthesis and characterization of five new selenometallic clusters, (argentoselenometalatic compounds) containing univalent silver (I) ion and phosphine ligands are presented. The fact that the properties of the presented metal clusters can be finetuned by altering the constituent elements and skeleton structures make them promising candidates of optical limiting materials among all the selenometallic clusters studied to date.

Isocyanides are important ligands in coordination chemistry as they bind on gold and other metals. An investigation of the coordination behavior of 1,1'-diisocyanoferrocene toward gold (I) leads to an unprecedented diauraferrocenophane.

The sol‐gel metathesis reaction was used to synthesize a new family of aerogels called a rare‐earth chalcophosphate aerogel KY(P2S6)2·K+ and the rare‐earth metal cations Y3+ connect [P2S6]2– anions to form an amorphous white gel. Supercritical drying of the resulting gel produced porous materials with a BET surface area of 443 m2·g–1. The adsorption properties of the rare‐earth chalcophosphate aerogel were studied using volatile organic hydrocarbons (VOCs) and gases as adsorptives. The results showed preferential adsorption of toluene vapor over cyclohexane and cyclopentane vapor. The adsorption capacity toward toluene was 703 mg·g–1. Favored adsorption of CO2 over CH4, N2, or H2 was also observed for the aerogel: KY(P2S6)2 (CO2/H2: 308, CO2/CH4: 67, Co2/N2: 177). Pd doped aerogel showed significant enhancement toward toluene (1291 mg·g–1) for 1 wt % Pd @ KY(P2S6)2, (2064 mg·g–1) for 3 wt % Pd @ KY(P2S6)2 and (1108 mg·g–1) for 5 wt % Pd @ KY(P2S6)2. It also showed a noticeable improvement in the gas selectivity (CO2/H2: 337, CO2/CH4: 85, Co2/N2: 205) for 1 wt % Pd @ KY(P2S6)2, (CO2/H2: 345, CO2/CH4: 109, Co2/N2: 212) for 3 wt % Pd @ KY(P2S6)2 and (CO2/H2: 319, CO2/CH4: 73, Co2/N2: 187) for 5 wt % Pd @ KY(P2S6)2. [ABSTRACT FROM AUTHOR]

Three new quaternary compounds Na2BiSbQ4 (Q = S, Se, Te) have been synthesized by the direct combination reaction between Bi, Sb, Q and the corresponding Na2Q. All phases, sulfide, selenide and telluride, are isostructural and crystallize in the NaCl-type cubic space group Fm3̅m (no. 225) with lattice constants of a = 5.760(7), 5.964(9) and 6.331(5) Å, respectively. The unique feature of these structures is the existence of only one crystallographic metal site in the unit cell. These mixed position sites provide the desirable lattice complexity with a random distribution of the Na, Bi and Sb atoms. Consequently, extremely low thermal conductivities at room temperature have been observed for the studied phases. All three compounds are semiconductors and their Uv/Vis spectra exhibit redshifts toward narrower bandgap energies from sulfide to selenide to telluride. [ABSTRACT FROM AUTHOR]