科研之友
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摘要
The syntheses and characterizations of mixed-cation fluorosulfates containing Ag-II ions are reported and add to the moderately well-known chemistry of Ag-II compounds. The compounds synthesized mostly show different structures and compositions. The mixed sodium-silver fluorosulfate is isostructural with Ag-3(SO3F)(4) (monoclinic P2(1)/c, a = 5.2812 angstrom, b = 13.0473 angstrom, c = 19.3557 angstrom, and = 100.970 degrees) and has the composition (Ag0.05Na0.95)(Ag0.65Na0.35)Ag-II(SO3F)(4). The mixed potassium-silver fluorosulfate does not correspond to (K2AgII)-Ag-I(SO3F)(4) but rather to (KAg2AgII)-Ag-I(SO3F)(5) [orthorhombic P222(1), a = 6.4736(3) angstrom, b = 7.3915(4) angstrom, and c = 17.7736(10) angstrom]. Two rubidium-silver fluorosulfates form as a mixture, one corresponds to (RbAg2AgII)-Ag-I(SO3F)(5) [orthorhombic P222(1), a = 6.4828(6) angstrom, b = 7.3551(7) angstrom, c = 18.0262(17) angstrom], and the other corresponds to RbAgII(SO3F)(3) [monoclinic P2(1)/m, a = 15.8152(14) angstrom, b = 15.4861(13) angstrom, c = 17.0211(14) angstrom, and = 101.513(5)degrees]. The cesium fluorosulfate/silver(II) fluorosulfate phase diagram is exemplified by the CsAgII(SO3F)(3) salt [triclinic P (1) over bar, a = 14.9241(5) angstrom, b = 9.7046(3) angstrom, c = 17.8465(7) angstrom, = 109.116(2)degrees, = 84.655(3)degrees, and = 119.171(3)degrees]. The IR and Raman spectra of the compounds were measured, and their thermal stability and magnetic properties have been determined. The (MAg2AgII)-Ag-I(SO3F)(5) systems show antiferromagnetic behavior with absolute superexchange constants of up to 19.1 meV for M = K, and ferromagnetism can be observed below 20-40 K for the MAg(SO3F)(3) derivatives (M = Rb, Cs).
- 出版日期2015-1
