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Synthesis, crystal and electronic structure, physical properties and 121Sb and 151Eu Mössbauer spectroscopy of the Eu14AlPn11 series (Pn = As, Sb)

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Abstract

The pnictides Eu14AlAs11 and Eu14AlSb11 were synthesized from the elements in sealed niobium ampoules. They crystallize in the tetragonal crystal system (Eu14AlAs11: a = 1627.6(2), c = 2180.0(4) pm; Eu14AlSb11: a = 1725.6(2), c = 2289.7(7) pm) with space group I41/acd, isostructural to Ca14AlSb11 and can be described as Zintl phases. The Al atoms are surrounded by four pnictogen atoms, forming [AlPn4]9− tetrahedra. Additionally isolated Pn3− anions and linear Pn37− trimers can be found in the crystal structure. The compounds can be described according to (Eu2+)14(AlPn9−)(Pn3−)4(Pn37−). Eu14AlAs11 and Eu14AlSb11 both exhibit an antiferromagnetic transition at TN = 10.5(1) K and 12.5(1) K, respectively. For the antimonide, the magnetic transition has been confirmed by additional heat capacity measurements. Resistivity investigations indicate that Eu14AlSb11 is a semiconductor with a band gap of Eg = 0.28(5) eV close to room temperature. According to the Zintl formalism, the Eu atoms are divalent, which has been confirmed by magnetic susceptibility and additional 151Eu Mössbauer spectroscopic studies. The measurements conducted at 6 K, below the magnetic ordering temperature, show a full hyperfine field splitting with complex spectra underlining the recorded magnetic data. Furthermore, 121Sb Mössbauer spectroscopic studies have been conducted to study the different antimonide entities in the title compounds.

Graphical abstract: Synthesis, crystal and electronic structure, physical properties and 121Sb and 151Eu Mössbauer spectroscopy of the Eu14AlPn11 series (Pn = As, Sb)

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Publication details

The article was received on 11 Oct 2018, accepted on 11 Nov 2018 and first published on 16 Nov 2018


Article type: Research Article
DOI: 10.1039/C8QI01099D
Citation: Inorg. Chem. Front., 2018, Advance Article
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    Synthesis, crystal and electronic structure, physical properties and 121Sb and 151Eu Mössbauer spectroscopy of the Eu14AlPn11 series (Pn = As, Sb)

    M. Radzieowski, T. Block, S. Klenner, Y. Zhang, B. P. T. Fokwa and O. Janka, Inorg. Chem. Front., 2018, Advance Article , DOI: 10.1039/C8QI01099D

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