Silver(II) Fluorosulfate: A Thermally Fragile Ferromagnetic Derivative of Divalent Silver in an Oxa-Ligand Environment
作者： Przemysław J. Malinowski , Mariana Derzsi , Zoran Mazej , Zvonko Jagličić , Piotr J. Leszczyński
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摘要: Several synthetic pathways and characterization of silver(II) fluorosulfate are reported. The title compound crystallizes in the monoclinic space group, P21/c, with a = 10.5130(4) A, b 7.7524(3) c 8.9366(4) β 117.867(2)° [V 643.88(5) A3, Z 4, dcalcd. 3.15 g cm–3] structure type related to that AgF2. Puckered [Ag(SO3F)2] sheets present crystal two oxygen atoms anions utilized for bonding within sheet; third atom serves as linker adjacent sheet. Terminal fluorine form small cavities structure. S–O stretching region vibrational (IR Raman) spectra is rich bands, thus confirming structural complexity Ag(SO3F)2. Ag(SO3F)2 soft ferromagnet Curie temperature 24.8 K it shows single broad electron spin resonance (ESR) g 2.183 at T 293 K. intrasheet magnetic superexchange constant, J, derived from magnetization measurements, equals +1.0 meV per formula unit. Density functional theory calculations suggest occurs through OO moiety Ag–O–S–O–Ag bridge while omitting S atom, yield J +1.1 meV. Coulomb-corrected local density approximation (LSDA+U) predict direct electronic band gap Fermi level 1.05 eV. Large moments reside on O attached AgII; consequence, thermally unstable; room or presence strong acids its dark brown crystals slowly decompose surface black mixed-valence Ag3(SO3F)4. Very fast exothermic decomposition emission fluorosulfuryl radical (SO3F·) above 120 °C confirmed by simultaneous thermogravimetric, calorimetric evolved gas analyses.
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