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Title: Oxygen trapped by rare earth tetrahedral clusters in Nd 4FeOS 6: Crystal structure, electronic structure, and magnetic properties

Abstract

Single crystals of Nd 4FeOS 6 were grown from an Fe-S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd 4MnOSe 6-type structure (P6 3mc, a = 9.2693(1) Å, c = 6.6650(1) Å, V = 495.94(1) Å 3, Z = 2), featuring parallel chains of face-sharing [FeS 6x1/2] 4- trigonal antiprisms and interlinked [Nd 4OS 3] 4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd 4 clusters in the [Nd 4OS 3] 4+ chains. Structural differences among Nd 4MnOSe 6-type Nd 4FeOS 6 and the related La 3CuSiS 7- and Pr 8CoGa 3-type structures have been described. Magnetic susceptibility measurements on Nd 4FeOS 6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.

Authors:
 [1];  [2];  [3];  [2];  [2];  [2];  [2];  [4]
  1. Ames Lab., Ames, IA (United States). Div. of Materials Sciences and Engineering
  2. Ames Lab., Ames, IA (United States). Div. of Materials Sciences and Engineering; Iowa State Univ., Ames, IA (United States). Dept. of Physics and Astronomy
  3. Ames Lab., Ames, IA (United States). Dept. of Chemistry
  4. Ames Lab., Ames, IA (United States). Div. of Materials Sciences and Engineering and Dept. of Chemistry
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Advanced Manufacturing Office (EE-5A); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1221923
Alternate Identifier(s):
OSTI ID: 1252532
Report Number(s):
IS-J-8765
Journal ID: ISSN 0022-4596; PII: 3028
Grant/Contract Number:
AC02-07CH11358; DMR-12-09135
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 229; Journal Issue: C; Journal ID: ISSN 0022-4596
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lin, Qisheng, Taufour, Valentin, Zhang, Yuemei, Wood, Max, Drtina, Thomas, Bud’ko, Sergey L., Canfield, Paul C., and Miller, Gordon J. Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties. United States: N. p., 2015. Web. doi:10.1016/j.jssc.2015.05.020.
Lin, Qisheng, Taufour, Valentin, Zhang, Yuemei, Wood, Max, Drtina, Thomas, Bud’ko, Sergey L., Canfield, Paul C., & Miller, Gordon J. Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties. United States. doi:10.1016/j.jssc.2015.05.020.
Lin, Qisheng, Taufour, Valentin, Zhang, Yuemei, Wood, Max, Drtina, Thomas, Bud’ko, Sergey L., Canfield, Paul C., and Miller, Gordon J. Fri . "Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties". United States. doi:10.1016/j.jssc.2015.05.020. https://www.osti.gov/servlets/purl/1221923.
@article{osti_1221923,
title = {Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties},
author = {Lin, Qisheng and Taufour, Valentin and Zhang, Yuemei and Wood, Max and Drtina, Thomas and Bud’ko, Sergey L. and Canfield, Paul C. and Miller, Gordon J.},
abstractNote = {Single crystals of Nd4FeOS6 were grown from an Fe-S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd4MnOSe6-type structure (P63mc, a = 9.2693(1) Å, c = 6.6650(1) Å, V = 495.94(1) Å3, Z = 2), featuring parallel chains of face-sharing [FeS6x1/2]4- trigonal antiprisms and interlinked [Nd4OS3]4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd4 clusters in the [Nd4OS3]4+ chains. Structural differences among Nd4MnOSe6-type Nd4FeOS6 and the related La3CuSiS7- and Pr8CoGa3-type structures have been described. Magnetic susceptibility measurements on Nd4FeOS6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.},
doi = {10.1016/j.jssc.2015.05.020},
journal = {Journal of Solid State Chemistry},
number = C,
volume = 229,
place = {United States},
year = {Fri May 22 00:00:00 EDT 2015},
month = {Fri May 22 00:00:00 EDT 2015}
}

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Cited by: 2works
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  • Single crystals of Nd{sub 4}FeOS{sub 6} were grown from an Fe–S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd{sub 4}MnOSe{sub 6}-type structure (P6{sub 3}mc, a=9.2693(1) Å, c=6.6650(1)Å, V=495.94(1) Å{sup 3}, Z=2), featuring parallel chains of face-sharing [FeS{sub 6×1/2}]{sup 4−} trigonal antiprisms and interlinked [Nd{sub 4}OS{sub 3}]{sup 4+} cubane-like clusters. Oxygen atoms were found to be trapped by Nd{sub 4} clusters in the [Nd{sub 4}OS{sub 3}]{sup 4{sub +}} chains. Structural differences among Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6} and the related La{sub 3}CuSiS{sub 7}− and Pr{sub 8}CoGa{sub 3}-type structures have been described. Magnetic susceptibility measurements on Nd{sub 4}FeOS{sub 6}more » suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions. - Graphical abstract: Trapping of oxygen in Nd{sub 4} tetrahedral clusters results in the formation of the Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6}, in contrast to the La{sub 3}CuSiS{sub 7}-type oxygen-free Nd{sub 4}FeS{sub 7} and related Pr{sub 8}CoGa{sub 3}-type structures. Complex magnetic frustration inhibits magnetic ordering at low temperature. - Highlights: • Single crystals of Nd{sub 4}FeOS{sub 6} were grown using self-flux method. • Oxygen was found trapped by Nd{sub 4} tetrahedral clusters. • Comparison with two closely related structural types were discussed. • Magnetic measurements revealed antiferromagnetic (AFM) interaction. • VASP calculations confirmed strong magnetic frustration in AFM model.« less
  • Cited by 2
  • The ternary rare-earth metal boride carbides RE{sub 15}B{sub 6}C{sub 20} (RE=Pr, Nd) were synthesized by co-melting the elements. They exist above 1270 K. Their crystal structures were determined from single-crystal X-ray diffraction data. Both crystallize in the space group P1-bar , Z=1, a=8.3431(8) A, b=9.2492(9) A, c=8.3581(8) A, {alpha}=84.72(1){sup o}, {beta}=89.68(1){sup o}, {gamma} =84.23(1){sup o} (R1=0.041 (wR2=0.10) for 3291 reflections with I{sub o}>2{sigma}(I{sub o})) for Pr{sub 15}B{sub 6}C{sub 20}, and a=8.284(1) A, b=9.228(1) A, c=8.309(1) A, {alpha}=84.74(1){sup o}, {beta}=89.68(1){sup o}, {gamma}=84.17(2){sup o} (R1=0.033 (wR2=0.049) for 2970 reflections with I{sub o}>2{sigma}(I{sub o})) for Nd{sub 15}B{sub 6}C{sub 20}. Their structure consists ofmore » a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with unprecedented B{sub 2}C{sub 4} finite chains, disordered C{sub 3} entities and isolated carbon atoms, respectively. Structural and theoretical analyses suggest the ionic formulation (RE{sup 3+}){sub 15}([B{sub 2}C{sub 4}]{sup 6-}){sub 3}([C{sub 3}]{sup 4-}){sub 2}(C{sup 4-}){sub 2}.11e. Accordingly, density functional theory calculations indicate that the compounds are metallic. Both structural arguments as well as energy calculations on different boron vs. carbon distributions in the B{sub 2}C{sub 4} chains support the presence of a CBCCBC unit. Pr{sub 15}B{sub 6}C{sub 18} exhibits antiferromagnetic order at T{sub N}=7.9 K, followed by a meta-magnetic transition above a critical external field B>0.03 T. On the other hand, Nd{sub 15}B{sub 6}C{sub 18} is a ferromagnet below T{sub C}{approx}40 K. - Graphical abstract: The ternary rare-earth metal boride carbides RE{sub 15}B{sub 6}C{sub 20} (RE=Pr, Nd) were synthesized by co-melting the elements. They exist above 1270 K. Their structure consists of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with unprecedented B{sub 2}C{sub 4} finite chains, disordered C{sub 3} entities and isolated carbon atoms, respectively. Structural and theoretical analyses suggest the ionic formulation (RE{sup 3+}){sub 15}([B{sub 2}C{sub 4}]{sup 6-}){sub 3}([C{sub 3}]{sup 4-}){sub 2}(C{sup 4-}){sub 2} 11e. Pr{sub 15}B{sub 6}C{sub 18} exhibits antiferromagnetic order at T{sub N}=7.9 K, followed by a meta-magnetic transition above a critical external field B>0.03 T. On the other hand, Nd{sub 15}B{sub 6}C{sub 18} is ferromagnetic below T{sub C}{approx}40 K.« less
  • Suitable reactions of KI, La, LaI{sub 3}, and Os in niobium tubes at 800--850 C result in black, air- and moisture-sensitive crystals of the quaternary title phase. Isostructural K{sub 4}Pr{sub 6}I{sub 14}Z also exist for Z = Fe, Ru. The title phase was characterized by single-crystal X-ray diffraction (tetragonal, P4/ncc (No. 130), Z = 4; a = 13.117(3), c = 25.17(1) {angstrom} at 23 C). The important structural feature is the constitution (K{sub 4}I){sup 3+}(La{sub 6}I{sub 13}Os{sup 3{minus}}) with a new type of 3D anion network of [(La{sub 6}Os)I{sub 8}{sup i}I{sub 4/2}{sup i{minus}a}I{sub 4/2}{sup a{minus}i}I{sub 2/2}{sup a{minus}a}] clusters that aremore » connected into puckered layers through I{sup i{minus}a} and I{sup a{minus}i} atom pairs that bridge diagonally in the a-b plane. These cluster layers are further interlinked along {rvec c} at trans-vertexes through simple bridging I{sup a{minus}a}. The 14th iodine atom occurs in the unique K{sub 4}I{sup 3+} ions which lie in columns that interpenetrate the La{sub 6}OsI{sub 13} network along c. The present 16-e{sup {minus}} clusters, in contrast with the optimal 18-e{sup {minus}} octahedral cluster configuration, exhibit an uncommon tetragonal elongation and evidently become closed shell, with only a small temperature-independent (van Vleck-like) paramagnetism, {approximately}4 x 10{sup {minus}4} emu mol{sup {minus}1}.« less
  • The ternary rare-earth boride carbides R{sub 15}B{sub 4}C{sub 14} (R=Y, Gd-Lu) were prepared from the elements by arc-melting followed by annealing in silica tubes at 1270 K for 1 month. The crystal structures of Tb{sub 15}B{sub 4}C{sub 14} and Er{sub 15}B{sub 4}C{sub 14} were determined from single crystal X-ray diffraction data. They crystallize in a new structure type in space group P4/mnc (Tb{sub 15}B{sub 4}C{sub 14}: a=8.1251(5) A, c=15.861(1) A, Z=2, R{sub 1}=0.041 (wR{sub 2}=0.088) for 1023 reflections with I{sub o}>2{sigma}(I{sub o}); Er{sub 15}B{sub 4}C{sub 14}: a=7.932(1) A, c=15.685(2) A, Z=2, R{sub 1}=0.037 (wR{sub 2}=0.094) for 1022 reflections with I{submore » o}>2{sigma}(I{sub o})). The crystal structure contains discrete carbon atoms and bent CBC units in octahedra and distorted bicapped square antiprisms, respectively. In both structures the same type of disorder exists. One R atom position needs to be refined as split atom position with a ratio 9:1 indicative of a 10% substitution of the neighboring C{sup 4-} by C{sub 2}{sup 4-}. The actual composition has then to be described as R{sub 15}B{sub 4}C{sub 14.2}. The isoelectronic substitution does not change the electron partition of R{sub 15}B{sub 4}C{sub 14} which can be written as (R{sup 3+}){sub 15}(C{sup 4-}){sub 6}(CBC{sup 5-}){sub 4{center_dot}}e{sup -}. The electronic structure was studied with the extended Hueckel method. The investigated compounds Tb{sub 15}B{sub 4}C{sub 14}, Dy{sub 15}B{sub 4}C{sub 14} and Er{sub 15}B{sub 4}C{sub 14} are hard ferromagnets with Curie temperatures T{sub C}=145, 120 and 50 K, respectively. The coercive field B{sub C}=3.15 T for Dy{sub 15}B{sub 4}C{sub 14} is quite remarkable. - Graphical abstract: The ternary rare earth boride carbides R{sub 15}B{sub 4}C{sub 14} (R=Y, Gd-Lu) were prepared from the elements by arc-melting followed by annealing in silica tubes at 1270 K for 1 month. Tb{sub 15}B{sub 4}C{sub 14} is a new member of the rare-earth metal boride carbide series in which the finite quasi-molecular CBC entities as well as isolated C atoms are embedded in the voids of the metal atom matrix. The structure of Tb{sub 15}B{sub 4}C{sub 14} contains two types of slabs: one slab contains finite bent CBC units and isolated carbon atoms whereas another is formed only from octahedral coordinated single carbon atoms. The electronic structure for the idealized composition corresponds to an electron partitioning according to (Tb{sup 3+}){sub 15}(C{sup 4-}){sub 6}(CBC{sup 5-}){sub 4{center_dot}}e{sup -} giving rise to a single electron per formula for Tb-Tb framework bonding. The magnetism of the ternary rare earth boride carbides R{sub 15}B{sub 4}C{sub 14} (R=Tb, Dy, Er) is characterized by the onset of ferromagnetic order below T<150 K.« less