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Organic−Inorganic Hybrid Materials:  Hydrothermal Syntheses and Structural Characterization of Bimetallic Organophosphonate Oxides of the Type Mo/Cu/O/RPO32-/Organoimine

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posted on 21.03.2002 by Robert C. Finn, Randy S. Rarig, Jon Zubieta
The hydrothermal reactions of a Cu(II) starting material, a molybdate source, 2,2‘-bipyridine or terpyridine, and the appropriate alkyldiphosphonate ligand yield two series of bimetallic organophosphonate hybrid materials of the general types [Cun(bpy)mMoxOy(H2O)p{O3P(CH2)nPO3}z] and [Cun(terpy)mMoxOy(H2O)p{O3P(CH2)nPO3}z]. The bipyridyl series includes the one-dimensional materials [Cu(bpy)(MoO2)(H2O)(O3PCH2PO3)] (1) and [{Cu(bpy)2}{Cu(bpy)(H2O)}(Mo5O15)(O3PCH2CH2CH2CH2PO3)]·H2O (5·H2O) and the two-dimensional hybrids [Cu(bpy)(Mo2O5)(H2O)(O3PCH2PO3)]·H2O (2·H2O), [{Cu(bpy)}2(Mo4O12)(H2O)2(O3PCH2CH2PO3)]·2H2O (3·2H2O), and [Cu(bpy)(Mo2O5)(O3PCH2CH2CH2PO3)](4). The terpyridyl series is represented by the one-dimensional [{Cu(terpy)(H2O)}2(Mo5O15)(O3PCH2CH2PO3)]·3H2O (7·3H2O) and the two-dimensional composite materials [Cu(terpy)(Mo2O5)(O3PCH2PO3)] (6) and [{Cu(terpy)}2(Mo5O15)(O3PCH2CH2CH2PO3)] (8). The structures exhibit a variety of molybdate building blocks including isolated {MoO6} octahedra in 1, binuclear subunits in 2, 4, and 6, tetranuclear embedded clusters in 3, and the prototypical {Mo5O15(O3PR)2}4- cluster type in 5, 7, and 8. These latter materials exemplify the building block approach to the preparation of extended structures.