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Issue 6, 2014
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pH-controlled assembly of hybrid architectures based on Anderson-type polyoxometalates and silver coordination units

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Abstract

Three new architectures based on Anderson-type polyoxometalates, (3-H2pya)[(3-Hpya)2Ag][AgAlMo6H6O24]·3H2O 1, HNa2[(3-pya)(3-Hpya)Ag]2[AlMo6H6O24]·8H2O 2 and [(3-Hpya)2Ag][(H2O)2Ag]2[AlMo6H6O24]·2H2O 3 (3-Hpya = 3-(3-pyridyl)acrylic acid), have been synthesized at the different pH values and characterized by elemental analysis, IR spectroscopy, TG analysis, powder X-ray diffraction and single crystal X-ray diffraction. Compound 1 was obtained at lower pH value (2.50), and represents a 3D host–guest compound containing the Ag-3-Hpya coordination complex guest and the 3D [AgAlMo6H6O24]2− host. The host framework exhibits a 4-connected diamond topology, and is constructed from [AlMo6H6O24]3− clusters connected by Ag+ cations. When the pH value was increased slightly, compound 2 was obtained with a 1D chain structure built up of Anderson polyoxoanions, Ag-3-Hpya coordination complexes and binuclear sodium clusters. By further increasing the pH value (3.50), compound 3 was isolated as a 2D network in which [AlMo6H6O24]3− clusters are linked together by Ag+ cations and Ag-3-Hpya coordination complexes. Their structural differences reveal that the pH value of the reaction system is the key factor influencing the structure and topology of three compounds. The UV-visible-NIR diffuse reflectivity spectra of 1–3 show that they can be regarded as a wide gap semiconductor. Furthermore, the pyrolysis of 1–3 produces three nanocomposites 1′–3′ composed of silver microparticles dispersed in the metal oxides. The photocatalytic properties of 1′–3′ have been investigated.

Graphical abstract: pH-controlled assembly of hybrid architectures based on Anderson-type polyoxometalates and silver coordination units

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Publication details

The article was received on 23 Oct 2013, accepted on 17 Nov 2013 and first published on 19 Nov 2013


Article type: Paper
DOI: 10.1039/C3DT52987H
Citation: Dalton Trans., 2014,43, 2488-2498
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    pH-controlled assembly of hybrid architectures based on Anderson-type polyoxometalates and silver coordination units

    Y. Hu, H. An, X. Liu, J. Yin, H. Wang, H. Zhang and L. Wang, Dalton Trans., 2014, 43, 2488
    DOI: 10.1039/C3DT52987H

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