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Title: Pr{sub 4}B{sub 10}O{sub 21}: A new composition of rare-earth borates by high-pressure/high-temperature synthesis

Abstract

High-pressure chemistry led to the synthesis of the rare-earth borate Pr{sub 4}B{sub 10}O{sub 21} using a Walker-type multianvil apparatus at 3.5 GPa and 1050 deg. C. The tetra-praseodymium(III)-decaborate crystallizes monoclinicly with four formula units in the space group P2{sub 1}/n and lattice parameters of a=710.2(2), b=1948.8(4), c=951.6(2) pm, and {beta}=93.27(3){sup o}. The boron-oxygen network consists of [BO{sub 4}]{sup 5-} tetrahedra and [BO{sub 3}]{sup 3-} groups; however, the [BO{sub 4}]{sup 5-} groups represent the major part (80%) due to the high-pressure conditions during the synthesis. The praseodymium ions are coordinated by 10 and 12 oxygen atoms. Along with a detailed description of the crystal structure, temperature programmed X-ray powder diffraction data are shown, demonstrating the metastable character of this compound. - Graphical abstract: Synthesis of Pr{sub 4}B{sub 10}O{sub 21} via the multianvil high-pressure/high-temperature technique representing a new composition of rare-earth borates.

Authors:
 [1];  [1];  [2]
  1. Department Chemie und Biochemie, Ludwig-Maximilians-Universitaet Muenchen, Butenandtstrasse 5-13, D-81377 Munich (Germany)
  2. Department Chemie und Biochemie, Ludwig-Maximilians-Universitaet Muenchen, Butenandtstrasse 5-13, D-81377 Munich (Germany), E-mail: huh@cup.uni-muenchen.de
Publication Date:
OSTI Identifier:
21015814
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 5; Other Information: DOI: 10.1016/j.jssc.2007.02.021; PII: S0022-4596(07)00095-3; Copyright (c) 2007 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; BORATES; LATTICE PARAMETERS; MONOCLINIC LATTICES; PRASEODYMIUM COMPOUNDS; PRASEODYMIUM IONS; PRESSURE RANGE GIGA PA; SPACE GROUPS; SYNTHESIS; TEMPERATURE RANGE 1000-4000 K; X-RAY DIFFRACTION

Citation Formats

Haberer, Almut, Heymann, Gunter, and Huppertz, Hubert. Pr{sub 4}B{sub 10}O{sub 21}: A new composition of rare-earth borates by high-pressure/high-temperature synthesis. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2007.02.021.
Haberer, Almut, Heymann, Gunter, & Huppertz, Hubert. Pr{sub 4}B{sub 10}O{sub 21}: A new composition of rare-earth borates by high-pressure/high-temperature synthesis. United States. doi:10.1016/j.jssc.2007.02.021.
Haberer, Almut, Heymann, Gunter, and Huppertz, Hubert. Tue . "Pr{sub 4}B{sub 10}O{sub 21}: A new composition of rare-earth borates by high-pressure/high-temperature synthesis". United States. doi:10.1016/j.jssc.2007.02.021.
@article{osti_21015814,
title = {Pr{sub 4}B{sub 10}O{sub 21}: A new composition of rare-earth borates by high-pressure/high-temperature synthesis},
author = {Haberer, Almut and Heymann, Gunter and Huppertz, Hubert},
abstractNote = {High-pressure chemistry led to the synthesis of the rare-earth borate Pr{sub 4}B{sub 10}O{sub 21} using a Walker-type multianvil apparatus at 3.5 GPa and 1050 deg. C. The tetra-praseodymium(III)-decaborate crystallizes monoclinicly with four formula units in the space group P2{sub 1}/n and lattice parameters of a=710.2(2), b=1948.8(4), c=951.6(2) pm, and {beta}=93.27(3){sup o}. The boron-oxygen network consists of [BO{sub 4}]{sup 5-} tetrahedra and [BO{sub 3}]{sup 3-} groups; however, the [BO{sub 4}]{sup 5-} groups represent the major part (80%) due to the high-pressure conditions during the synthesis. The praseodymium ions are coordinated by 10 and 12 oxygen atoms. Along with a detailed description of the crystal structure, temperature programmed X-ray powder diffraction data are shown, demonstrating the metastable character of this compound. - Graphical abstract: Synthesis of Pr{sub 4}B{sub 10}O{sub 21} via the multianvil high-pressure/high-temperature technique representing a new composition of rare-earth borates.},
doi = {10.1016/j.jssc.2007.02.021},
journal = {Journal of Solid State Chemistry},
number = 5,
volume = 180,
place = {United States},
year = {Tue May 15 00:00:00 EDT 2007},
month = {Tue May 15 00:00:00 EDT 2007}
}
  • Three optically uniaxial non-centrosymmetric potassium compounds, iodate K[IO{sub 3}] and two borates K{sub 3}[B{sub 6}O{sub 10}]Br, KTa[B{sub 4}O{sub 6}(OH){sub 4}](OH){sub 2}{center_dot}1.33H{sub 2}O have been synthesized and characterized by single-crystal X-ray diffraction. The materials were synthesized through hydrothermal techniques using initial reagents and mineralizers. All the compounds are trigonal-hexagonal: the space groups are R3 (K[IO{sub 3}]), R3m (K[B{sub 6}O{sub 10}]Br) and P-62m (KTa[B{sub 4}O{sub 6}(OH){sub 4}](OH){sub 2}{center_dot}1.33H{sub 2}O). Powder second-harmonic generation (SHG) measurements on crystals, using 1064 nm Nd:YAG laser radiation, indicate the materials are all phase-matchable and have strong second-order nonlinearities. The correlation with the perovskite structure has been foundmore » and described for K,Br-borate and K-iodate. Structure-properties relation is discussed and attributed to stereo-active lone-pair on I{sup 5+} and asymmetrical bonds in the compounds. The role of K atoms is pronounced from crystal chemistry point of view, contributing optical nonlinearities. - Graphical abstract: Structure-properties relation is attributed to stereo-active lone-pair on I{sup 5+} and asymmetrical bonds in the compounds with the crucial role of K atoms, K[IO{sub 3}] structure along 3-fold axis with umbrella-like IO{sub 3}-group and with octahedral coordination-analog with perovskite. Highlights: Black-Right-Pointing-Pointer Syntheses in hydrothermal conditions trigonal KIO{sub 3}, K{sub 3}[B{sub 6}O{sub 10}]Br and KTa[B{sub 4}O{sub 6}(OH){sub 4}](OH){sub 2}. Black-Right-Pointing-Pointer Correlation with the perovskite, found for K-iodate and K,Br-borate. Black-Right-Pointing-Pointer Structure-properties relation, attributed to I{sup 5+} lone-pair and asymmetric bonds including K-atoms. Black-Right-Pointing-Pointer The compounds are phase matchable and strongly nonlinear from powder SHG measurements. Black-Right-Pointing-Pointer Averaged second-order nonlinear coefficients Left-Pointing-Angle-Bracket d Right-Pointing-Angle-Bracket are 24, 2.8 and 1.9 pm/V.« less
  • Several new borate compounds, Ba{sub 11}B{sub 26}O{sub 44}(PO{sub 4}){sub 2}(OH){sub 6} (1), Li{sub 9}BaB{sub 15}O{sub 27}(CO{sub 3}) (2), and Ba{sub 3}Si{sub 2}B{sub 6}O{sub 16} (3) were synthesized containing other hetero-oxyanion building blocks in addition to the borate frameworks. They were all prepared under hydrothermal conditions and characterized by single crystal and powder X-ray diffraction, and IR spectroscopy. Crystal data: For 1; space group P2{sub 1}/c, a=6.8909 (14) Å, b=13.629 (3) Å, c=25.851 (5) Å, β=90.04 (3)°; For 2; space group P-31c, a=8.8599 (13) Å, c=15.148 (3) Å; For 3; space group P-1, a=5.0414 (10) Å, b=7.5602 (15) Å, c=8.5374 (17)more » Å, α=77.15 (3)°, β=77.84 (3)°, γ=87.41 (3)° for 3. Compounds 1 and 2 contain isolated oxyanions [PO{sub 4}]{sup 3−} and [CO{sub 3}]{sup 2−} respectively, sitting in channels created by the borate framework, while structure 3 has the [SiO{sub 4}]{sup 4−} groups directly bonded to the borate groups creating a B–O–Si framework. - Highlights: • Hydrothermal syntheses of three new mixed oxyanion borates are presented. • Ba{sub 11}B{sub 26}O{sub 44}(PO{sub 4}){sub 2}(OH){sub 6} contains isolated [PO{sub 4}]{sup 3−} in voids of the borate framework. • Li{sub 9}BaB{sub 15}O{sub 27}(CO{sub 3}) contains isolated [CO{sub 3}]{sup 2−} in channels created by the framework. • Ba{sub 3}Si{sub 2}B{sub 6}O{sub 16} has direct bonding of [SiO{sub 4}]{sup 4−} and borates creating a B–O–Si framework.« less
  • The new monoclinic cerium borogermanate Ce{sub 6}(BO{sub 4}){sub 2}Ge{sub 9}O{sub 22} was synthesized under high-pressure and high-temperature conditions in a Walker-type multianvil apparatus at 10.5GPa and 1200 deg. C. Ce{sub 6}(BO{sub 4}){sub 2}Ge{sub 9}O{sub 22} crystallizes with two formula units in the space group P2{sub 1}/n with lattice parameters a=877.0(2), b=1079.4(2), c=1079.1(2) pm, and {beta}=95.94(3){sup o}. As the parameter pressure favours the formation of compounds with cations possessing high coordination numbers, it was possible to produce simultaneously BO{sub 4}-tetrahedra and GeO{sub 6}-octahedra in one and the same borogermanate for the first time. Furthermore, the cerium atoms show high coordination numbersmore » (C.N.: 9 and 11), and one oxygen site bridges one boron and two germanium atoms (O{sup [3]}), which is observed here for the first time. Besides a structural discussion, temperature-dependent X-ray powder diffraction data are presented, demonstrating the metastable character of this high-pressure phase.« less
  • The first lanthanum fluoride borate La{sub 4}B{sub 4}O{sub 11}F{sub 2} was obtained in a Walker-type multianvil apparatus at 6 GPa and 1300 {sup o}C. La{sub 4}B{sub 4}O{sub 11}F{sub 2} crystallizes in the monoclinic space group P2{sub 1}/c with the lattice parameters a=778.1(2) pm, b=3573.3(7) pm, c=765.7(2) pm, {beta}=113.92(3){sup o} (Z=8), and represents a new structure type in the class of compounds with the composition RE{sub 4}B{sub 4}O{sub 11}F{sub 2}. The crystal structure contains BO{sub 4}-tetrahedra interconnected with two BO{sub 3}-groups via common vertices, B{sub 2}O{sub 5}-pyroborate units, and isolated BO{sub 3}-groups. The structure shows a wave-like modulation along the b-axis.more » The crystal structure and properties of La{sub 4}B{sub 4}O{sub 11}F{sub 2} are discussed and compared to Gd{sub 4}B{sub 4}O{sub 11}F{sub 2}. - Graphical abstract: A new structure type of RE{sub 4}B{sub 4}O{sub 11}F{sub 2}: high-pressure synthesis and crystal structure of La{sub 4}B{sub 4}O{sub 11}F{sub 2}.« less