Syntheses, structures, and magnetic properties of mixed-valent diruthenium(II,III) diphosphonates with discrete and one-dimensional structures

Yi XY; Liu B; Jimenez-Aparicio R; Urbanos FA; Gao S; Xu W; Chen JS; Song Y; Zheng LM

Inorganic Chemistry, Vol.44, No.12, 4309-4314, 2005

Yi XY, Liu B, Jimenez-Aparicio R, Urbanos FA, Gao S, Xu W, Chen JS, Song Y, Zheng LM

Four mixed-valent ruthenium diphosphonates, namely, Na-4[Ru-2(hedP)(2)X]center dot 16H(2)O [X = Cl (1), Br (2)], K-3[Ru-2(hedP)(2)-(H2O)(2)]center dot 6H(2)O (3), and Na-7[Ru-2(hedP)(2)Fe(CN)(6)]center dot 24H(2)O (4), where hedp represents 1-hydroxyethylidenediphosphonate [CH3C(OH)(PO3)(2)](4-), were synthesized and structurally characterized. Compounds 1, 2, and 4 show linear chain structures in which the mixed-valent [Ru-2(hedP)(2)](3-) climers are linked by X- or [Fe(CN)(6)](4-) bridges. Compound 3 contains discrete species of [Ru-2(hedP)(2)(H2O)(2)](3-) where the axial positions of [Ru-2(hedP)(2)](3-) paddlewheel are terminated by water molecules. Magnetic studies show that significant antiferromagnetic exchanges are mediated between the [Ru-2(hedP)(2)](3-) (S = 3/2) units through halide bridges in compounds 1 and 2.