Syntheses,structures and magnetic properties of the alkali oxonickelates(I) A3NiO2 (A = K,Rb, Cs) |
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| Institution: | 1. Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China;2. High Magnetic Field Laboratory, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China;3. University of Science and Technology of China, Hefei 230026, People’s Republic of China;1. Geodynamics Research Center, Ehime University, Matsuyama 790-8577, Japan;2. Institute for Solid State Physics, University of Tokyo, Kashiwa 277-8581, Japan;3. Department of Natural History Sciences, Hokkaido University, Sapporo 060-0810, Japan;4. Department of Earth and Planetary Sciences, Kobe University, Kobe 657-8501, Japan;5. Mineral Physics Institute, Stony Brook University, Stony Brook, NY 11794-2100, USA;6. Earth-Life Science Institute, Tokyo Institute of Technology, Tokyo 152-8550, Japan;1. Department of Chemistry, Yeungnam University, Gyeongsan, Gyeongbuk 38541, Republic of Korea;2. School of Materials Science and Engineering, Chonnam National University, Gwangju 61186, Republic of Korea;1. Electron Microscopy for Materials Research (EMAT), University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium;2. Department of Chemistry, Moscow State University, 119991 Moscow, Russia |
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| Abstract: | New oxonickelates(I), Rb3NiO2 and Cs3NiO2, were prepared via the azide/nitrate route, starting from stoichiometric mixtures of azides, nitrates and NiO as precursors. The mixtures were heated steadily in a controlled heating regime up to 723 K and annealed at this temperature for 50 h (30 h for cesium compound) in specially designed containers with silver inlays. The crystal structures of Rb3NiO2 and Cs3NiO2 were solved and refined by X-ray powder methods. Room temperature α-Rb3NiO2 (P41212, Z = 4, a = 6.2651(2) Å, b = 14.7438(3) Å; Rwp = 6.30%) and high temperature β-Rb3NiO2 (at 523 K P42/mnm, Z = 2, a = 6.2750(2) Å, b = 7.5088(3) Å; Rwp = 7.85%) were found to be isostructural to room and high temperature α- and β-K3NiO2, respectively. Cs3NiO2 crystallizes at room temperature isostructural with the β-K3NiO2 (P42/mnm, Z = 2, a = 6.4336(3) Å, b = 8.0844(4) Å; Rwp = 5.21%). A3NiO2 (A = K, Rb, Cs) are paramagnetic in the whole temperature range investigated. The magnetic susceptibility data have been evaluated by the Curie–Weiss law, where the calculated magnetic moments are as expected for a d9 system (μ = 1.73–2.20μB). Negative values of Weiss constants are indicative for antiferromagnetic interactions in this family of compounds. |
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