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Three cobalt(II)-containing tungstophosphate compounds, Na8Li8Co5[Co5.5(H2O)19P8W48.5O184] ⋅60 H2O ( 1), K2Na4Li11Co5[Co7(H2O)28P8W48O184]Cl ⋅ 59 H2O ( 2), and K2Na4LiCo11[Co8(H2O)32P8W48O184](CH3COO)4Cl ⋅47 H2O ( 3), have been synthesized and characterized by IR spectroscopy, thermogravimetric analysis, elemental analyses, and magnetic measurements. The pH value impacts the formation of distinct cobalt-linked frameworks. The cyclic cavity of the polyanion accommodates 5.5, 7, and 8 cobalt ions in 1, 2, and 3, respectively. In compounds 1 and 2, each {Co5.5P8W48} and {Co7P8W48} fragment links to four others through multiple {Co-O-W} coordination bonds to generate a two-dimensional network. Compound 3 can be considered as a 3D network based on the {Co-O-W} coordination bonds and the {Co3(CH3COO)2(H2O)10} linkers between the {P8W48} fragments. Interestingly, acetate ligands have been employed to form the {Co3(CH3COO)2(H2O)10} unit, thereby inducing the construction of a 12-connected framework. To the best of our knowledge, compound 3 contains the largest-ever number of cobalt ions in a {P8W48}-based polyoxometalate when counterions are taken into account and the {P8W48} unit shows the highest number of connections thanks to the carboxyl bridges. The UV/Vis diffuse reflectance spectra of these powder samples indicate that the corresponding well-defined optical absorption associated with Eg can be assessed at 2.58, 2.48, and 2.73 eV and reveal the presence of an optical band gap. The photocatalytic H2 evolution activities of these {P8W48}-based compounds are evaluated. [ABSTRACT FROM AUTHOR]

Two Fe-substituted Dawson-type nanoscale selenotungstate clusters, {Fe6Se6W34} and {Fe10Se8W62} involving {α-Se2W14} and {γ-Se2W14} building blocks, have been isolated, which exhibit photocatalytic H2 evolution activity. Their electrochemical behaviours and magnetic properties were also investigated.

Three cobalt(II)-containing tungstophosphate compounds, Na8Li8Co5[Co5.5(H2O)19P8W48.5O184]⋅60 H2O (1), K2Na4Li11Co5[Co7(H2O)28P8W48O184]Cl⋅ 59 H2O (2), and K2Na4LiCo11[Co8(H2O)32P8W48O184](CH3COO)4Cl⋅47 H2O (3), have been synthesized and characterized by IR spectroscopy, thermogravimetric analysis, elemental analyses, and magnetic measurements. The pH value impacts the formation of distinct cobalt-linked frameworks. The cyclic cavity of the polyanion accommodates 5.5, 7, and 8 cobalt ions in 1, 2, and 3, respectively. In compounds 1 and 2, each {Co5.5P8W48} and {Co7P8W48} fragment links to four others through multiple {Co-O-W} coordination bonds to generate a two-dimensional network. Compound 3 can be considered as a 3D network based on the {Co-O-W} coordination bonds and the {Co3(CH3COO)2(H2O)10} linkers between the {P8W48} fragments. Interestingly, acetate ligands have been employed to form the {Co3(CH3COO)2(H2O)10} unit, thereby inducing the construction of a 12-connected framework. To the best of our knowledge, compound 3 contains the largest-ever number of cobalt ions in a {P8W48}-based polyoxometalate when counterions are taken into account and the {P8W48} unit shows the highest number of connections thanks to the carboxyl bridges. The UV/Vis diffuse reflectance spectra of these powder samples indicate that the corresponding well-defined optical absorption associated with Eg can be assessed at 2.58, 2.48, and 2.73 eV and reveal the presence of an optical band gap. The photocatalytic H2 evolution activities of these {P8W48}-based compounds are evaluated., (Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first macrocycle-based high-nuclearity nanocluster [Ag(20)(S(t)Bu)(10)(CF(3)COO)(2)](8+) in complex 1, with a sandwich-like structure constructed by bilevel inversion Ag(5)S(5) pentagrams and an interlayer Ag(10) ring, has been obtained. Structure analysis indicates that Cl(-) acts as an anion template to direct the formation of 1. In addition, the photoluminescent property of complex 1 is also investigated.

An unprecedented organic-inorganic hybrid {[Cu(6)L(6)(H(2)O)(3)][Nb(10)V(4)O(40)(OH)(2)]}(2)·13H(2)O (1) (L = 1,10-phenanthroline) containing the unreported {Nb(10)V(4)O(40)(OH)(2)}(12-) building blocks has been successfully synthesized and its photoluminescent properties, IR spectra, thermogravimetric analyses and single-crystal X-ray diffraction were investigated., (This journal is © The Royal Society of Chemistry 2012)