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@ARTICLE{Kazem:189315,
      author       = {Kazem, Nasrin and Hurtado, Antonio and Klobes, Benedikt and
                      Kauzlarich, Susan M. and Hermann, Raphael},
      title        = {{E}u$_{9}${C}d$_{4–x}${CM}$_{2+x–y□y}${S}b$_{9}$:
                      {C}a$_{9}${M}n$_{4}${B}i$_{9}$-{T}ype {S}tructure {S}tuffed
                      with {C}oinage {M}etals ({C}u, {A}g, and {A}u) and the
                      {C}hallenges with {C}lassical {V}alence {T}heory in
                      {D}escribing {T}hese {P}ossible {Z}intl {P}hases},
      journal      = {Inorganic chemistry},
      volume       = {54},
      number       = {3},
      issn         = {1520-510X},
      address      = {Washington, DC},
      publisher    = {American Chemical Society},
      reportid     = {FZJ-2015-02493},
      pages        = {850 - 859},
      year         = {2015},
      abstract     = {The synthesis, crystal structure, magnetic properties, and
                      europium Mössbauer spectroscopy of the new members of the
                      9–4–9 Zintl family of Eu9Cd4–xCM2+x–y□ySb9 (CM =
                      coinage metal: Au, Ag, and Cu) are reported. These compounds
                      crystallize in the Ca9Mn4Bi9 structure type (9–4–9) with
                      the 4g interstitial site almost half-occupied by coinage
                      metals; these are the first members in the 9–4–9 family
                      where the interstitial positions are occupied by a
                      monovalent metal. All previously known compounds with this
                      structure type include divalent interstitials where these
                      interstitials are typically the same as the transition
                      metals in the anionic framework. Single-crystal magnetic
                      susceptibility data indicate paramagnetic behavior for all
                      three compounds with antiferromagnetic ordering below 10 K
                      (at 100 Oe) that shifts to lower temperature (<7 K) by
                      applying a 3 T magnetic field. 151Eu Mössbauer spectra were
                      collected on polycrystalline powder samples of
                      Eu9Cd4–xCM2+x–y□ySb9 at 50 and 6.5 K in order to
                      evaluate the valence of Eu cations. Although the Zintl
                      formalism states that the five crystallographically distinct
                      Eu sites in Eu9Cd4–xCM2+x–y□ySb9 should bear Eu2+, the
                      Mössbauer spectral isomer shifts are clearly indicative of
                      both 2+ and 3+ valence of the Eu cations with the Cu- and
                      Au-containing compounds showing higher amounts of Eu3+. This
                      electronic configuration leads to an excess of negative
                      charge in these compounds that contradicts the expected
                      valence-precise requirement of Zintl phases. The spectra
                      obtained at 6.5 K reveal magnetic ordering for both Eu2+ and
                      Eu3+. The field dependence of Eu2+ indicates two distinct
                      magnetic sublattices, with higher and lower fields, and of a
                      small field for Eu3+. The site symmetry of the five Eu sites
                      is not distinguishable from the Mössbauer data.},
      cin          = {JCNS-2 / PGI-4 / JARA-FIT},
      ddc          = {540},
      cid          = {I:(DE-Juel1)JCNS-2-20110106 / I:(DE-Juel1)PGI-4-20110106 /
                      $I:(DE-82)080009_20140620$},
      pnm          = {144 - Controlling Collective States (POF3-144) / 524 -
                      Controlling Collective States (POF3-524) / 6213 - Materials
                      and Processes for Energy and Transport Technologies
                      (POF3-621) / 6G4 - Jülich Centre for Neutron Research
                      (JCNS) (POF3-623) / 6212 - Quantum Condensed Matter:
                      Magnetism, Superconductivity (POF3-621)},
      pid          = {G:(DE-HGF)POF3-144 / G:(DE-HGF)POF3-524 /
                      G:(DE-HGF)POF3-6213 / G:(DE-HGF)POF3-6G4 /
                      G:(DE-HGF)POF3-6212},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000348887400021},
      pubmed       = {pmid:25354329},
      doi          = {10.1021/ic502061w},
      url          = {https://juser.fz-juelich.de/record/189315},
}