Unexpected Coexisting Solid Solutions in the Quasi-Binary Ag(II) F2 /Cu(II) F2 Phase Diagram.

High-temperature solid-state reaction between orthorhombic AgF2 and monoclinic CuF2 (y=0.15, 0.3, 0.4, 0.5) in a fluorine atmosphere resulted in coexisting solid solutions of Cu-poor orthorhombic and Cu-rich monoclinic phases with stoichiometry Ag1-x Cux F2 . Based on X-ray powder diffraction analyses, the mutual solubility in the orthorhombic phase (AgF2 : Cu) appears to be at an upper limit of Cu concentration of 30 mol % (Ag0.7 Cu0.3 F2 ), while the monoclinic phase (CuF2 : Ag) can form a nearly stoichiometric Cu : Ag=1 : 1 solid solution (Cu0.56 Ag0.44 F2 ), preserving the CuF2 crystal structure. Experimental data and DFT calculations showed that AgF2 : Cu and CuF2 : Ag solid solutions deviate from the classical Vegard's law. Magnetic measurements of Ag1-x Cux F2 showed that the Néel temperature (TN ) decreases with increasing Cu content in both phases. Likewise, theoretical DFT+U calculations for Ag1-x Cux F2 showed that the progressive substitution of Ag by Cu decreases the magnetic interaction strength |J2D | in both structures. Electrical conductivity measurements of Ag0.85 Cu0.15 F2 showed a modest increase in specific ionic conductivity (3.71 ⋅ 10-13 ±2.6 ⋅ 10-15  S/cm) as compared to pure AgF2 (1.85 ⋅ 10-13± 1.2 ⋅ 10-15  S/cm), indicating the formation of a vacancy- or F adatom-free metal difluoride sample.

Metal fluoride nanotubes featuring square-planar building blocks in a high-pressure polymorph of AgF2.

At a pressure of ca. 15 GPa, AgF2 transforms to an unprecedented orthorhombic polymorph featuring an array of tubular subunits which are built of corner sharing [AgF4] squares. This seems to be the first type of a metal fluoride nanowire and also the only one showing rigid square planar rather than common hexagonal or octahedral moieties.

Cerium Tetrafluoride: Sublimation, Thermolysis, and Atomic Fluorine Migration.

Saturated vapor pressure p° and enthalpy of sublimation (ΔsH°) of cerium tetrafluoride CeF4 were determined by means of Knudsen effusion mass spectrometry in the range of 750-920 K. It was discovered that sublimation of cerium tetrafluoride from a platinum effusion cell competes with thermal decomposition to CeF3 in the solid phase, but no accompanying release of fluorine to the gas phase occurs. Thus, fluorine atoms migrate within the surface layer of CeF4(s) to the regions of their irreversible drain. We used scanning electron microscopy to study the distribution of the residual CeF3(s) across the inner surface of the effusion cell after complete evaporation of CeF4(s). It was observed that CeF3 accumulates near the edge of the effusion orifice and near the junction of the lid and the body of the cell, that is, in those regions where the fluorine atoms can migrate to a free platinum surface and thus be depleted from the system. Distribution of CeF3(s) solid particles indicates the ways of fluorine atoms migration providing CeF3(s) formation inside the CeF4(s) surface layer.

The former "C60F16" is actually a double-caged adduct: (C60F16)(C60).

X-ray diffraction study of the substance originally believed to be C(60)F(16) reveals a double-caged structure, (C(60)F(16))(C(60)); MALDI mass spectra, 19F NMR spectral data and reasons for stability are discussed.