European Journal of Inorganic Chemistry p. 2499 - 2507 (2011)
Update date:2022-08-11
Topics:
Malinowski, Przemyslaw J.
Derzsi, Mariana
Mazej, Zoran
Jaglicic, Zvonko
Leszczyanski, Piotr J.
Michalowski, Tomasz
Grochala, Wojciech
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) A, c = 8.9366(4) A, β = 117.867(2)° [V = 643.88(5) A3, Z = 4, dcalcd. = 3.15 gcm-3] in a structure type related to that of AgF2. Puckered [Ag(SO3F)2] sheets are present in the crystal structure with two oxygen atoms of the fluorosulfate anions utilized for bonding within the sheet; the third oxygen atom serves as a linker to the adjacent sheet. Terminal fluorine atoms form small cavities in the structure. The S-O stretching region of the vibrational (IR and Raman) spectra is rich in bands, thus confirming the structural complexity of Ag(SO 3F)2. Ag(SO3F)2 is a soft ferromagnet with a Curie temperature of 24.8 K and it shows a single broad electron spin resonance (ESR) with g = 2.183 at T = 293 K. The intrasheet magnetic superexchange constant, J, derived from magnetization measurements, equals +1.0 meV per formula unit. Density functional theory calculations suggest that the superexchange occurs through the OO moiety of the Ag-O-S-O-Ag bridge while omitting the S atom, and the yield is J = +1.1 meV. The Coulomb-corrected local spin density approximation (LSDA+U) calculations predict a direct electronic band gap at the Fermi level of 1.05 eV. Large magnetic moments reside on O atoms attached to AgII; in consequence, Ag(SO 3F)2 is thermally unstable; at room temperature or in the presence of strong acids its dark brown crystals slowly decompose at the surface to a black mixed-valence Ag3(SO3F)4. Very fast exothermic decomposition of Ag(SO3F)2 with emission of a fluorosulfuryl radical (SO3F′·) occurs above 120 °C as confirmed by simultaneous thermogravimetric, calorimetric and evolved gas analyses. Ag(SO3F)2 exhibits a puckered sheet structure and it shows 2D ferromagnetism below 25 K; DFT methods predict it to be a magnetic semiconductor with the band gap at the Fermi level of approximately 1.05 eV.Magnetic superexchange take place through the OO moiety of the structural O-S-O bridge while omitting the sulfur atom, similarly as for related AgSO4.
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