Ca4Fe3-xMnxO8-δCl2: A new n=3 Ruddlesden-Popper oxychloride

被引:5
|
作者
Yang, Tao [1 ]
Sun, Junliang [2 ]
Croft, Mark [3 ]
Nowik, Israel [4 ]
Ignatov, Alexander [5 ]
Cong, Rihong [6 ]
Greenblatt, Martha [1 ]
机构
[1] Rutgers State Univ, Dept Chem & Chem Biol, Piscataway, NJ 08854 USA
[2] Stockholm Univ, SE-10691 Stockholm, Sweden
[3] Rutgers State Univ, Dept Phys & Astron, Piscataway, NJ 08854 USA
[4] Hebrew Univ Jerusalem, Racah Inst Phys, IL-91904 Jerusalem, Israel
[5] Rutgers State Univ, Dept Mat Sci & Engn, Piscataway, NJ 08854 USA
[6] Peking Univ, Coll Chem & Mol Engn, Beijing 100871, Peoples R China
基金
美国国家科学基金会;
关键词
Ruddlesden-Popper; Oxychloride; Iron; Manganese; Structure; MAGNETIC-PROPERTIES; CRYSTAL-STRUCTURES; OXIDE HALIDES; COMPOUND; SR3FE2O5CL2; DIFFRACTION; CA3CU2O4CL2; OXYHALIDES; CA4MN3O10;
D O I
10.1016/j.jssc.2010.03.019
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Solid state solutions of Ca4Fe3-xMnxO8-delta Cl2 (0 92 <= x <= 1.79 (delta similar to 0.1) single crystals were synthesized in CaCl2-flux in air. The structure, determined by single-crystal X-ray diffraction, is related to the n = 3 Ruddlesden-Popper phase in space group I4/mmm with strong deviations from the ideal structure Mn and Fe are disordered over two transition metal sites. Due to the positional disordering of the equatorial oxygen atoms in the MO6 octahedra in Ca4Fe3-xMnxO8-delta Cl2 both tilting (similar to 9 degrees) along the c-axis and rotation (similar to 10 5 degrees) within the ab-plane are observed All the Fe ions are trivalent, as confirmed by Fe-57 Mossbauer spectroscopy and X-ray absorption near edge spectroscopy (XAS), while the formal valence state of Mn varies from very close to 4+ in the x = 0.92 to mix-valent 3+/4+ in the x = 179 member, as indicated by XAS Magnetic investigations evidence short-range antiferromagnetic ordering already at room temperature and spin-glass behavior at low temperature due to the structural disordering of Mn/Fe. (C) 2010 Elsevier Inc All rights reserved
引用
收藏
页码:1215 / 1220
页数:6
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