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Zeuner, Martin; Pagano, Sandro; Matthes, Philipp; Bichler, Daniel; Johrendt, Dirk; Harmening, Thomas; Pöttgen, Rainer; Schnick, Wolfgang (2009): Mixed Valence Europium Nitridosilicate Eu2SiN3. In: Journal of the American Chemical Society, Vol. 131, Nr. 31: S. 11242-11248
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Abstract

The mixed valence europium nitridosilicate Eu2SiN3 has been synthesized at 900°C in welded tantalum ampules starting from europium and silicon diimide Si(NH)2 in a lithium flux. The structure of the black material has been determined by single-crystal X-ray diffraction analysis (Cmca (no. 64), a=542.3(11) pm, b=1061.0(2) pm, c=1162.9(2) pm, Z=8, 767 independent reflections, 37 parameters, R1=0.017, wR2=0.032). Eu2SiN3 is a chain-type silicate comprising one-dimensional infinite nonbranched zweier chains of corner-sharing SiN4 tetrahedra running parallel [100] with a maximum stretching factor fs=1.0. The compound is isostructural with Ca2PN3 and Rb2TiO3, and it represents the first example of a nonbranched chain silicate in the class of nitridosilicates. There are two crystallographically distinct europium sites (at two different Wyckoff positions 8f) being occupied with Eu2+ and Eu3+, respectively. 151Eu Mössbauer spectroscopy of Eu2SiN3 differentiates unequivocally these two europium atoms and confirms their equiatomic multiplicity, showing static mixed valence with a constant ratio of the Eu2+ and Eu3+ signals over the whole temperature range. The Eu2+ site shows magnetic hyperfine field splitting at 4.2 K. Magnetic susceptibility measurements exhibit Curie-Weiss behavior above 24 K with an effective magnetic moment of 7.5 μB/f.u. and a small contribution of Eu3+, in accordance with Eu2+ and Eu3+ in equiatomic ratio. Ferromagnetic ordering at unusually high temperature is detected at TC=24 K. DFT calculations of Eu2SiN3 reveal a band gap of ∼0.2 eV, which is in agreement with the black color of the compound. Both DFT calculations and lattice energetic calculations (MAPLE) corroborate the assignment of two crystallographically independent Eu sites to Eu2+ and Eu3+.