Polyoxometalate-mediated syntheses of three structurally new silver clusters.

Three structurally new polyoxometalate-templated silver clusters, homometallic [(SiWO)@Ag(PrS)(DPPP)Cl](SiWO) (Ag), heterometallic [(SiWO)@AgCu(PrS)(DPPP)Cl](SbF) (AgCu) and {Ag(PrS)(DPPP)(CHCOO)[Co(OH)(HO)SiWO]}·(CHCN) (AgCo) (PrS = isopropanethiolate, DPPP = 1,3-bis(diphenylphosphino)propane, SbF = hexafluoroantimonate) have been successfully synthesized using a facile solvothermal approach. The introduction of copper and cobalt ions can induce obvious changes in the molecular configuration of the obtained clusters, leading to distinct temperature-dependent photoluminescence and photothermal conversion properties.

Structurally-New Hexadecanuclear Ni-Containing Silicotungstate with Catalytic Hydrogen Generation Activity.

A structurally-new, carbon-free hexadecanuclear Ni-containing silicotungstate, [Ni(HO)(OH)(PO)(SiWO)], has been facilely synthesized using a one-pot, solution-based synthetic method systematically characterized by single-crystal X-ray diffraction and several other techniques. The resulting complex works as a noble-metal-free catalyst for visible-light-driven catalytic generation of hydrogen, by coupling with a [Ir(coumarin)(dtbbpy)][PF] photosensitizer and a triethanolamine (TEOA) sacrificial electron donor. Under minimally optimized conditions, a turnover number (TON) of 842 was achieved for TBA--catalyzed hydrogen evolution system.

All-Inorganic Bis-SbO-Functionalized A-Type Anderson-Evans Polyoxometalate for Visible-Light-Driven Hydrogen Production.

An all-inorganic, novel bis-SbO-functionalized A-type Anderson-Evans polyoxometalate, [Ni(HO)]KH[NiMoO(SbO)]·5HO (), has been synthesized under hydrothermal conditions. The chemical composition, molecular structure, and elemental oxidation states of the resulting compound have been systematically characterized by various techniques, including single-crystal X-ray diffraction, thermogravimetric analysis, Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy. The title complex has been investigated for the first time as a catalyst for visible-light-driven hydrogen production by coupling with a [Ir(coumarin)(dtbbpy)][PF] photosensitizer and a triethanolamine (TEOA) sacrificial electron donor.

One-Step versus Two-Step Valence Tautomeric Transitions in Tetraoxolene-Bridged Dinuclear Cobalt Compounds.

The syntheses of valence tautomeric compounds with multistep transitions using new redox-active ligands are the long-term goal of the field of bistable materials. The redox-active tetraoxolene ligand, 2,7-di--butylpyrene-4,5,9,10-tetraone (pyrene), is now developed to synthesize a pair of dinuclear compounds {[CoL](pyrene)}[Co(CO)]·CHCl·2CHCH (, = 2, L = 1,10-phenanthroline, phen; , = 1.5, L = 2,2'-bipyridine, bpy).