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Crystal structure and magnetic properties of K5.5Na1.5[PW10Cu2(H 2O)2O38]·13H2O. Substituted Keggin heteropolytungstates of the type PW10Cu2 containing exchange-coupled copper pairs

AutorGómez-García, C. J.; Coronado, Eugenio; Gómez-Romero, P. ; Casañ Pastor, Nieves
Fecha de publicación1993
EditorAmerican Chemical Society
CitaciónInorganic Chemistry 32(1): 89-93 (1993)
ResumenWe report the structural and magnetic characterization of the crystalline product obtained from a solution containing Δ-(PW9O34)9- and Cu2+ ions (molar ratio 1/2) after standing a long period of time at room temperature. Three complementary techniques were used: X-ray diffraction, magnetic susceptibility measurements, and EPR spectroscopy. The crystals (space group Fm3m, a = 21.329 (4) Å, Z = 8) consist primarily of the potassium-sodium salt of the two cocrystallized heteropoly complexes, each formulated [PW10Cu2(H2O)2O38] 7-, in both of which two Cu2+ ions have replaced the two W atoms of the well-known 12-tungsten α-Keggin structure. The compound can be formulated as K5.5NaL1.5[PW10Cu2(H 2O)2O38]·13H2O. Although in the crystals the sites of the two Cu atoms are disordered over the 12 possible locations in each anion's structure, magnetic techniques (susceptibility measurements and EPR spectroscopy) show that in each disubstituted Kegg n complex, the two copper ions are preferentially occupying neighboring sites, giving rise to two isomers wherein the CuO6 octahedra share a corner or an edge. These exchange-coupled pairs are characterized by two different exchange interactions and two different anisotropies. The best fit of the magnetic data indicates that only a small proportion of Keggin units contain nonadjacent Cu's (∼8.5%). © 1993 American Chemical Society.
Identificadoresdoi: 10.1021/ic00053a015
issn: 0020-1669
e-issn: 1520-510X
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