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Title: Synthesis, crystal structure and magnetic properties of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}]

Abstract

Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] was synthesized from the metathesis reaction of Li{sub 3}[BN{sub 2}] and EuCl{sub 3} at 850 °C. Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] crystallizes in the trigonal space group R3{sup ¯}c (No. 167) with a=12.0225(2) Å, c=6.8556(2) Å and Z=6. In the crystal structure, isolated, planar cyclic [B{sub 3}N{sub 6}]{sup 9−} units are charge-balanced by the mixed-valence Eu{sup 3+}/Eu{sup 2+} and Li{sup +} cations. Li{sup +} occupies partially (44%) the Wyckoff site 6b and is sandwiched between the [B{sub 3}N{sub 6}]{sup 9−} anions. Mössbauer spectroscopy results show the resonance lines of Eu{sup 2+} and Eu{sup 3+}, respectively, indicating the heterogeneous mixed valency of the Eu atoms. X-Band ESR investigations between 5 and 300 K reveal an intense signal over the whole temperature range originating from Eu{sup 2+}. Magnetic susceptibility measurements indicate a Curie–Weiss behavior with an experimental effective magnetic moment of μ{sub eff}=8.28 μ{sub B} per formula unit. - Graphical abstract: Single crystals of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] was obtained from the metathesis reaction of Li{sub 3}[BN{sub 2}] and EuCl{sub 3.}{sup 151}Eu Mössbauer, ESR and magnetic susceptibility measurements reveal the heterogeneous mixed valency of the Eu atoms. Display Omitted - Highlights: • Single crystals of Li{submore » 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] was obtained from the metathesis reaction of Li{sub 3}[BN{sub 2}] and EuCl{sub 3} at 850 °C. • Crystal structure is built up by isolated, planar cyclic [B{sub 3}N{sub 6}]{sup 9−} units which are surrounded by mixed valence Eu{sup 3+}/Eu{sup 2+}. • Li{sup +} occupies partially (44%) the site 6b and is sandwiched between the [B{sub 3}N{sub 6}]{sup 9−} anions. • The {sup 151}Eu Mössbauer spectroscopy, electron spin resonance spectroscopy and magnetic susceptibility measurements confirm the heterogeneous mixed valency of Eu.« less

Authors:
 [1];  [1];  [2]; ; ;  [3];  [1]; ;  [3]; ;  [4];  [1]
  1. Koç University, Rumelifeneri Yolu, Sariyer, Istanbul 34450 (Turkey)
  2. (Germany)
  3. Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str.40, Dresden 01187 (Germany)
  4. Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, Münster 48149 (Germany)
Publication Date:
OSTI Identifier:
22274199
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 210; Journal Issue: 1; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; CATIONS; CRYSTAL STRUCTURE; ELECTRON SPIN RESONANCE; EUROPIUM 151; EUROPIUM CHLORIDES; EUROPIUM IONS; LITHIUM IONS; MAGNETIC MOMENTS; MAGNETIC SUSCEPTIBILITY; MONOCRYSTALS; SPECTROSCOPY; SYNTHESIS; TEMPERATURE RANGE

Citation Formats

Kokal, I., Aydemir, U., E-mail: uaydemir@ku.edu.tr, Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str.40, Dresden 01187, Prots, Yu., Förster, T., Sichelschmidt, J., Yahyaoglu, M., Auffermann, G., Schnelle, W., Schappacher, F., Pöttgen, R., and Somer, M., E-mail: msomer@ku.edu.tr. Synthesis, crystal structure and magnetic properties of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}]. United States: N. p., 2014. Web. doi:10.1016/J.JSSC.2013.11.001.
Kokal, I., Aydemir, U., E-mail: uaydemir@ku.edu.tr, Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str.40, Dresden 01187, Prots, Yu., Förster, T., Sichelschmidt, J., Yahyaoglu, M., Auffermann, G., Schnelle, W., Schappacher, F., Pöttgen, R., & Somer, M., E-mail: msomer@ku.edu.tr. Synthesis, crystal structure and magnetic properties of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}]. United States. doi:10.1016/J.JSSC.2013.11.001.
Kokal, I., Aydemir, U., E-mail: uaydemir@ku.edu.tr, Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str.40, Dresden 01187, Prots, Yu., Förster, T., Sichelschmidt, J., Yahyaoglu, M., Auffermann, G., Schnelle, W., Schappacher, F., Pöttgen, R., and Somer, M., E-mail: msomer@ku.edu.tr. Sat . "Synthesis, crystal structure and magnetic properties of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}]". United States. doi:10.1016/J.JSSC.2013.11.001.
@article{osti_22274199,
title = {Synthesis, crystal structure and magnetic properties of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}]},
author = {Kokal, I. and Aydemir, U., E-mail: uaydemir@ku.edu.tr and Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str.40, Dresden 01187 and Prots, Yu. and Förster, T. and Sichelschmidt, J. and Yahyaoglu, M. and Auffermann, G. and Schnelle, W. and Schappacher, F. and Pöttgen, R. and Somer, M., E-mail: msomer@ku.edu.tr},
abstractNote = {Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] was synthesized from the metathesis reaction of Li{sub 3}[BN{sub 2}] and EuCl{sub 3} at 850 °C. Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] crystallizes in the trigonal space group R3{sup ¯}c (No. 167) with a=12.0225(2) Å, c=6.8556(2) Å and Z=6. In the crystal structure, isolated, planar cyclic [B{sub 3}N{sub 6}]{sup 9−} units are charge-balanced by the mixed-valence Eu{sup 3+}/Eu{sup 2+} and Li{sup +} cations. Li{sup +} occupies partially (44%) the Wyckoff site 6b and is sandwiched between the [B{sub 3}N{sub 6}]{sup 9−} anions. Mössbauer spectroscopy results show the resonance lines of Eu{sup 2+} and Eu{sup 3+}, respectively, indicating the heterogeneous mixed valency of the Eu atoms. X-Band ESR investigations between 5 and 300 K reveal an intense signal over the whole temperature range originating from Eu{sup 2+}. Magnetic susceptibility measurements indicate a Curie–Weiss behavior with an experimental effective magnetic moment of μ{sub eff}=8.28 μ{sub B} per formula unit. - Graphical abstract: Single crystals of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] was obtained from the metathesis reaction of Li{sub 3}[BN{sub 2}] and EuCl{sub 3.}{sup 151}Eu Mössbauer, ESR and magnetic susceptibility measurements reveal the heterogeneous mixed valency of the Eu atoms. Display Omitted - Highlights: • Single crystals of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] was obtained from the metathesis reaction of Li{sub 3}[BN{sub 2}] and EuCl{sub 3} at 850 °C. • Crystal structure is built up by isolated, planar cyclic [B{sub 3}N{sub 6}]{sup 9−} units which are surrounded by mixed valence Eu{sup 3+}/Eu{sup 2+}. • Li{sup +} occupies partially (44%) the site 6b and is sandwiched between the [B{sub 3}N{sub 6}]{sup 9−} anions. • The {sup 151}Eu Mössbauer spectroscopy, electron spin resonance spectroscopy and magnetic susceptibility measurements confirm the heterogeneous mixed valency of Eu.},
doi = {10.1016/J.JSSC.2013.11.001},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 210,
place = {United States},
year = {Sat Feb 15 00:00:00 EST 2014},
month = {Sat Feb 15 00:00:00 EST 2014}
}
  • The organo-templated iron(III) borophosphate (C{sub 3}H{sub 12}N{sub 2})Fe{sup III} {sub 6}(H{sub 2}O){sub 4}[B{sub 4}P{sub 8}O{sub 32}(OH){sub 8}] was prepared under mild hydrothermal conditions (at 443 K) and the crystal structure was determined from single crystal X-ray data at 295 K (monoclinic, P2{sub 1}/c (No. 14), a=5.014(2) A, b=9.309(2) A, c=20.923(7) A, beta=110.29(2){sup o}, V=915.9(5) A{sup 3}, Z=2, R1=0.049, wR2=0.107 for all data, 2234 observed reflections with I>2sigma(I)). The title compound contains a complex inorganic framework of borophosphate trimers [BP{sub 2}O{sub 8}(OH){sub 2}]{sup 5-} together with FeO{sub 4}(OH)(H{sub 2}O)- and FeO{sub 4}(OH){sub 2}-octahedra forming channels with ten-membered ring apertures in whichmore » the diaminopropane cations are located. The magnetization measurements confirm the Fe(III)-state and show an antiferromagnetic ordering at T{sub N}{approx}14.0(1) K. - Graphical abstract: The complex inorganic open-framework of (C{sub 3}H{sub 12}N{sub 2})Fe{sup III} {sub 6}(H{sub 2}O){sub 4}[B{sub 4}P{sub 8}O{sub 32}(OH){sub 8}] consists of borophosphate trimers and iron(III) coordination octahedra arranged to form channels with ten-membered ring apertures in which the organic 1,3-diaminopropane cations are located.« less
  • New layered Co oxides of nominal formula Sr{sub 2}(Ln{sub 0.8}Ca{sub 0.2})Co{sub 2}O{sub 6} (Ln = Sm, Eu, Gd, Tb, Dy, Ho, and Y) are reported. Single-phase polycrystalline samples were obtained at compositions Sr{sub 2}Y{sub 1{minus}x}Ca{sub x}Co{sub 2}{sup 2.5+}O{sub 6{minus}{delta}} (0.2 {le} x {le} 0.5; 0 {le} {delta} {le} 0.24), Sr{sub 2}Y{sub 1{minus}x}Ca{sub x}Co{sub 2}{sup 3.4+}O{sub 6+{delta}{prime}} (0.2 {le} x {le} 0.5; 0.62 {le} {delta}{prime} {le} 0.79), and Sr{sub 2}Dy{sub 0.8}Ca{sub 0.2}Co{sub 2}O{sub 6.09}. Powder X-ray and neutron diffraction, thermogravimetric analysis, magnetic susceptibility, and ac resistivity measurements were used to characterize the samples. The tetragonal unit cell for Sr{sub 2}Y{sub 0.8}Ca{submore » 0.2}Co{sub 2}O{sub 6.00} (I4/mmm; a = 3.82765(6) {angstrom}, and c = 19.5795(3) {angstrom}) is comparable to that of the double layer superconducting copper oxide La{sub 2{minus}x}Sr{sub x}CaCu{sub 2}O{sub 6}. A long-range antiferromagnetic (AF) ordered state below about 300 K is found for Sr{sub 2}Y{sub 1{minus}x}Ca{sub x}Co{sub x}{sup 2.5+}O{sub 6{minus}{delta}}, and a magnetically glassy state below about 40 K for the oxidized AF phases. All materials are electrically insulating.« less
  • The compounds A{sub 3}A{prime}RuO{sub 6} (A = Ca, Sr; A{prime} = Li, Na) have been synthesized by solid state reactions and studied by x-ray powder diffraction and magnetometry. They all adopt the K{sub 4}CdCl{sub 6} (Sr{sub 4}PtO{sub 6}) structure with the cations A{prime} and Ru occupying the trigonal prismatic and octahedral sites respectively. Infinite chains of octahedra and trigonal prisms sharing faces run parallel to the c axis, the chains being separated by the cations A (Ca, Sr). The validity of this description of the structure is discussed in the light of magnetic susceptibility data which suggest that these phasesmore » all transform to a magnetically ordered state in the temperature range 70 < T/K < 120. Preliminary results of powder neutron diffraction experiments confirm the presence of long-range magnetic order in the low temperature phase.« less
  • Ca{sub 3}BMnO{sub 6} (B = Ni, Zn) and Ca{sub 3}ZnCoO{sub 6} were synthesized and studied by X-ray powder diffraction, neutron powder diffraction, and SQUID magnetometry. All these compounds were found to crystallize in the K{sub 4}CdCl{sub 6} structure containing alternate chains made of face-sharing B(II)O{sub 6} trigonal prisms and B{prime}(IV)O{sub 6} octahedra (B{prime} = Mn, Co). Ca{sub 3}NiMnO{sub 6} (CNMO) and Ca{sub 3}ZnMnO{sub 6} (CZMO) were found to be antiferromagnets with a T{sub N} of 19 and 25.5 K, respectively. CNMO showed a pronounced one-dimensional antiferromagnetic character like a broad susceptibility maximum at 100 K due to short range ordering,more » while CZMO behaved as a three-dimensional system since the presence of nonmagnetic Zn{sup 2+} ions suppressed the intrachain exchange interaction. A simple collinear antiferromagnetic structure with an ordered moment of 2.43(15) {mu}{sub B}/Mn was found in CZMO, while CNMO showed a spiral structure with ordered moments of 2.2(2) {mu}{sub B}/Mn and 1.4(2) {mu}{sub B}/Ni. Ca{sub 3}ZnCoO{sub 6}, on the other hand, showed a ferromagnetic, nonlinear field dependence of magnetization below 90 K, with a hysteresis appearing just below 25 K, and a spontaneous moment measured at 5 K was 0.6 {mu}{sub B}/Co, suggesting the Co{sup 4+} ions being in low spin state. 15 refs., 6 figs., 2 tabs.« less
  • A novel noncentrosymmetric (NCS) gallium-organic framework material, [N(C{sub 3}H{sub 7}){sub 4}]{sub 3}Ga{sub 3}[C{sub 6}H{sub 3}(CO{sub 2}){sub 3}]{sub 4} (CAUMOF-11) has been synthesized by a solvothermal reaction using Ga(NO{sub 3}){sub 3}{center_dot}xH{sub 2}O, 1,3,5-C{sub 6}H{sub 3}(CO{sub 2}H){sub 3}, N(C{sub 3}H{sub 7}){sub 4}Cl, HNO{sub 3}, and HCON(CH{sub 3}){sub 2} at 180 Degree-Sign C. The structure of the reported material has been determined by single-crystal X-ray diffraction. CAUMOF-11 has an anionic three-dimensional framework with aligned four-coordinate GaO{sub 4} tetrahedra and 1,3,5-benzenetricarboxylate groups. Tetrapropylammonim cations reside within the channel and maintain the charge balance. Detailed structural analyses with full characterization including infrared spectroscopy, thermogravimetric analysis,more » elemental analysis, ion-exchange reactions, topotactic decomposition, and gas adsorption experiments are reported. Powder second-harmonic generating (SHG) measurements on CAUMOF-11, using 1064 nm radiation, exhibit SHG efficiency of 15 times that of {alpha}-SiO{sub 2} and the material is phase-matchable (type-1). - Graphical Abstract: Second-order nonlinear optical measurements on CAUMOF-11 reveal that the material is phase-matchable (type-1) with SHG efficiency of 15 times that of {alpha}-SiO{sub 2}. Highlights: Black-Right-Pointing-Pointer A new NCS Ga-organic framework was solvothermally synthesized. Black-Right-Pointing-Pointer CAUMOF-11 exhibits SHG efficiency of 15 times that of {alpha}-SiO{sub 2}. Black-Right-Pointing-Pointer Thermal decomposition of CAUMOF-11 crystal maintains the original morphology.« less