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A novel europium (III) nitridoborate Eu3[B3N6]: Synthesis, crystal structure, magnetic properties, and Raman spectra

MPG-Autoren
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Prots,  Yurii
Yuri Prots, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Förster,  Tobias
Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Sichelschmidt,  Jörg
Jörg Sichelschmidt, Physics of Quantum Materials, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Ormeci,  Alim
Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Zitation

Aydemir, U., Kokal, I., Prots, Y., Förster, T., Sichelschmidt, J., Schappacher, F. M., et al. (2016). A novel europium (III) nitridoborate Eu3[B3N6]: Synthesis, crystal structure, magnetic properties, and Raman spectra. Journal of Solid State Chemistry, 239, 75-83. doi:10.1016/j.jssc.2016.04.016.


Zitierlink: https://hdl.handle.net/11858/00-001M-0000-002A-F718-1
Zusammenfassung
A novel europium (III) nitridoborate, Eu-3[B3N6], was successfully synthesized by oxidation of Eu-3(II)[BN2](2) with Br-2 at 1073 K. The compound crystallizes in the trigonal space group R (3) over barc (No:167) with a=11.9370(4) angstrom, c=6.8073(4) angstrom, and Z=6. The crystal structure of Eu-3[B3N6] consists of isolated, planar cyclic [B3N6](9-) units which are charge-balanced by Eu3+ cations. The oxidation state of Eu was investigated by Mossbauer spectroscopy, electron spin resonance (ESR) spectroscopy, and quantum chemical calculations. The Eu-151 Mossbauer spectroscopic measurement at 77 K reveals that the main signal at delta=0.93(7) mm/s is originating from trivalent Europium. Eu-3[B3N6] showed no ESR signal in accordance with a non-magnetic (J=0) F-7(0) ground state of the 4f(6) configuration. Quantum chemical calculations find six electrons in the 4f subshell (4f(6)) of Eu indicating an oxidation state of +3. We present for the first time the vibrational spectra of a compound with cyclic trimer [B3N6](9-) moieties. The Raman spectrum of Eu-3[B3N6] is in good agreement with the predicted number of modes for the spectroscopically relevant cyclic [B3N6](9-) group with D-3h symmetry. (C) 2016 Elsevier Inc. All rights reserved.