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Template- and pH-Directed Assembly of Diruthenium Diphosphonates with Different Topologies and Oxidation States

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posted on 15.05.2006, 00:00 by Bin Liu, Ping Yin, Yi, Song Gao, Li-Min Zheng
In the presence of organic templates, six diruthenium diphosphonates, namely, [H3N(CH2)3NH3]2[Ru2(hedp)2] (1), [H3N(CH2)4NH3]2[Ru2(hedp)2]·4H2O (2), [H3N(CH2)5NH3]2[Ru2(hedp)2]·4H2O (3), [H3N(CH2)3NH3][Ru2(hedp)(hedpH)]·H2O (4), [H3N(CH2)4NH3][Ru2(hedpH0.5)2]·2H2O (5), and [H3N(CH2)5NH3]2{[Ru2(hedp)2][Ru2(hedpH)2]} (6) [hedp = 1-hydroxyethylidenediphosphonate, CH3C(OH)(PO3)2] have been synthesized under hydrothermal conditions. Compounds 13 contain homovalent paddlewheel cores of Ru2II,II(hedp)24- that are connected through edge-sharing of the {RuO5Ru} octahedra, resulting in infinite linear chains. Compounds 46 contain mixed-valent diruthenium(II,III) phosphonate paddlewheel cores of Ru2II,III(hedpHn)2(3-2n)- that are connected by phosphonate oxygen atoms, forming distorted square-grid layers in 4 and 6 or a kagomé lattice in 5. Both the templates and the pH values are found to play important roles in directing the final products with particular topologies and oxidation states of the diruthenium unit. The magnetic studies show that weak antiferromagentic interactions are propagated between the homovalent diruthenium units in compounds 13. For compounds 46, weak ferromagnetic interactions are observed.