Highly fluorinated cuprate Ruddlesden–Popper oxyfluorides La2Cu0.8Ni0.2O3F2 and La2CuO3F2 were obtained by topochemical reaction between poly(vinylidene fluoride) (PVDF) and the corresponding oxides La2Cu0.8Ni0.2O4 and La2CuO4 prepared by citrate-based soft chemistry synthesis. The crystal structures of both oxyfluorides were investigated by powder diffraction techniques. The structure of La2Cu0.8Ni0.2O3F2 was solved based on combined neutron and X-ray powder diffraction. It crystallizes in a new monoclinic distorted version [C2/c a = 13.1880(3) Å, b = 5.7244(1) Å, c = 5.6007(1) Å, and β = 90.85(1)°] of the anionic ordered structure lately reported for La2NiO3F2. For La2CuO3F2, an even less symmetrical triclinic structure was derived from X-ray powder diffraction data [P1̅ a = 5.6180(5) Å, b = 5.7316(6) Å, c = 7.1978(9) Å, α = 113.32(1)°, β = 90.89(9)°, and γ = 90.16(11)°]. For both compounds, an additional tilt component of the partially Jahn-Teller elongated (Cu,Ni)O4F2 octahedra was found as the origin for the lowered symmetry. The formation reaction of La2CuO3F2 was studied by in situ XRD measurements. In these investigations, two new reaction intermediates were identified. The magnetic properties of both oxyfluorides La2Cu0.8Ni0.2O3F2 and La2CuO3F2 were characterized by field- and temperature-dependent measurements. An antiferromagnetic ordering with T N = 240 K was found for La2Cu0.8Ni0.2O3F2. In La2CuO3F2, additional weak ferrimagnetism was observed, resulting in a pronounced hysteresis but a weak saturation moment, which was attributed to result from a canted antiferromagnetic spin arrangement.

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We report on the new Ruddlesden–Popper (RP) oxyfluoride La2NiO2.5F3 containing an unprecedented high amount of fluorine and Ni2+. This oxyfluoride was prepared by topochemical low-temperature fluorination of La2NiO4, which was obtained by a soft chemistry synthesis, with poly­(vinylidene difluoride) (PVDF) as fluorinating agent. La2NiO2.5F3 is the first n = 1 RP compound crystallizing in the tetragonal space group P42/nnm (a = 5.7297(6) Å and c = 13.0106(2) Å). The crystal structure shows a unique tilting scheme of the NiO4F2 octahedra that has so far been only theoretically predicted. Combined neutron and X-ray powder diffraction experiments together with bond-valence-sum and DFT+U calculations reveal an unusual anion ordering with fluoride being located on the apical anion sites of the NiO4F2 octahedra. Excess fluorine ions were found to populate two of the four interstitial anion sites in an ordered fashion. A third interstitial anion position is occupied by oxygen ions while the fourth site remains unoccupied. This hitherto unobserved ordering scenario in RP oxyfluorides promotes a strong layerwise alternating tilting of the NiO4F2 octahedra. Magnetic measurements show strong antiferromagnetic interactions with a high Néel temperature of about 225 K and a pronounced ZFC/FC splitting most likely as the result of a small ferromagnetic moment arising from spin canting. The electronic structure was characterized by DFT and UV–vis spectroscopy, and a strong increase of E g was found compared to La2NiO4 (3.4 eV vs 1.3 eV).

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Three perovskite oxynitride solid solutions Ca1–xSrxNbO2N, CaNb1–xTaxO2N, and SrNb1–xTaxO2N were prepared by low temperature ammonolysis of soft‐chemistry precursors. In particular, we present for the first time a way to synthesize the substitution series Ca1–xSrxNbO2N, which cannot be prepared by ammonolysis of classical solid state precursors. All samples were phase‐pure and exhibit bandgaps in the visible light range that can be tailored by substitutions both of the A‐ and B‐type cations. Rietveld analysis was applied to determine cell parameters and crystal structures. In the case of Ca1–xSrxNbO2N a structural change from orthorhombic to tetragonal was found. After loading with CoOx the photocatalytic activities in the solution‐based methyl orange degradation were investigated and for SrNb1–xTaxO2N a considerable activity was found.