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Title: Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra

Abstract

The synthesis, structure, and characterization of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra are reported. Pb{sub 2}O[BO{sub 2}(OH)] crystallizes in monoclinic space group C2/m with a=12.725(7) Å, b=5.698(3) Å, c=7.344(4) Å, β=116.277(6)°. The electronic band structure and density of states of Pb{sub 2}O[BO{sub 2}(OH)] have been calculated via the density functional theory (DFT). Electron density difference calculation indicates that lone-pair electrons of Pb{sup 2+} cation should be stereoactive. - Graphical abstract: An indirect gap compound of Pb{sub 2}O[BO{sub 2}(OH)] with 2D inorganic layers motif based on OPb{sub 4} tetrahedra has been synthesized and full characterized by crystallographic, IR, TG, UV–vis-NIR Diffuse Reflectance, and theoretical calculations. Display Omitted - Highlights: • A centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] was synthesized and characterized. • The crystalstructure, electronic band and density states was analyzed. • The lone-pair electrons of Pb{sup 2+} were proved to be stereoactive.

Authors:
 [1];  [1];  [2]
  1. College of Chemistry and Chemical Engineering, Xinjiang Normal University, Urumqi 830054 (China)
  2. Department of Chemistry, Northwestern University, Evanston, IL 60208 (United States)
Publication Date:
OSTI Identifier:
22584179
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 240; Other Information: Copyright (c) 2016 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; BORATES; CATIONS; CRYSTALLOGRAPHY; DENSITY FUNCTIONAL METHOD; DENSITY OF STATES; ELECTRON DENSITY; ELECTRONIC STRUCTURE; HYDROTHERMAL SYNTHESIS; LAYERS; MONOCLINIC LATTICES; SPACE GROUPS

Citation Formats

Sun, Feng, Wang, Li, E-mail: wangliresearch@163.com, and Stoumpos, Constantinos C. Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.05.018.
Sun, Feng, Wang, Li, E-mail: wangliresearch@163.com, & Stoumpos, Constantinos C. Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra. United States. doi:10.1016/J.JSSC.2016.05.018.
Sun, Feng, Wang, Li, E-mail: wangliresearch@163.com, and Stoumpos, Constantinos C. 2016. "Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra". United States. doi:10.1016/J.JSSC.2016.05.018.
@article{osti_22584179,
title = {Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra},
author = {Sun, Feng and Wang, Li, E-mail: wangliresearch@163.com and Stoumpos, Constantinos C.},
abstractNote = {The synthesis, structure, and characterization of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra are reported. Pb{sub 2}O[BO{sub 2}(OH)] crystallizes in monoclinic space group C2/m with a=12.725(7) Å, b=5.698(3) Å, c=7.344(4) Å, β=116.277(6)°. The electronic band structure and density of states of Pb{sub 2}O[BO{sub 2}(OH)] have been calculated via the density functional theory (DFT). Electron density difference calculation indicates that lone-pair electrons of Pb{sup 2+} cation should be stereoactive. - Graphical abstract: An indirect gap compound of Pb{sub 2}O[BO{sub 2}(OH)] with 2D inorganic layers motif based on OPb{sub 4} tetrahedra has been synthesized and full characterized by crystallographic, IR, TG, UV–vis-NIR Diffuse Reflectance, and theoretical calculations. Display Omitted - Highlights: • A centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] was synthesized and characterized. • The crystalstructure, electronic band and density states was analyzed. • The lone-pair electrons of Pb{sup 2+} were proved to be stereoactive.},
doi = {10.1016/J.JSSC.2016.05.018},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 240,
place = {United States},
year = 2016,
month = 8
}
  • A novel non-centrosymmetric borate, BiCd{sub 3}(AlO){sub 3}(BO{sub 3}){sub 4}, has been prepared by solid state reaction methods below 750 {sup o}C. Single-crystal XRD analysis showed that it crystallizes in the hexagonal group P6{sub 3} with a=10.3919(15) A, c=5.7215(11) A, Z=2. In its structure, AlO{sub 6} octahedra share edges to form 1D {sup 1}{sub {infinity}}[AlO{sub 4}]{sup 5-} chains that are bridged by BO{sub 3} groups through sharing O atoms to form the 3D {sup 3}{sub {infinity}}[AlBO{sub 4}]{sup 2-} framework. The 3D framework affords two kinds of channels that are occupied by Bi{sup 3+}/Cd{sup 2+} atoms only or by Bi{sup 3+}/Cd{sup 2+}more » atoms together with BO{sub 3} groups. The IR spectrum further confirmed the presence of BO{sub 3} groups. Second-harmonic-generation measurements displayed a response of about 0.5xKDP (KH{sub 2}PO{sub 4}). UV-vis diffuse reflectance spectrum showed a band gap of about 3.19 eV. Solid-state fluorescence spectrum exhibited the maximum emission peak at around 390.6 nm. Band structure calculations indicated that it is an indirect semiconductor. -- Graphical abstract: BiCd{sub 3}(AlO){sub 3}(BO{sub 3}){sub 4} has a 3D network formed by stitching 1D chains of edge-sharing AlO{sub 6} octahedra via BO{sub 3} groups. There are channels occupied by Bi{sup 3+}/Cd{sup 2+} only or by Bi{sup 3+}/Cd{sup 2+} with BO{sub 3} groups. Display Omitted« less
  • Two related non-centrosymmetric, cubic, quaternary chalcogenides, containing europium have been synthesized employing the molten flux method and by the reaction of europium halides with the ternary seleno-germanate, Na{sub 6}Ge{sub 2}Se{sub 6}. The reactions of Eu, Ge and Se were accomplished in a molten Na{sub 2}Se{sub 2} flux at 800 deg. C for 150 h in an evacuated fused silica ampoule and yielded Na{sub 2}EuGeSe{sub 4} (I). Similarly, Na{sub 0.75}Eu{sub 1.625}GeSe{sub 4} (II), could be synthesized at slightly lower temperature (750 deg. C) with a different starting ratio of Eu, Ge, Se and Na{sub 2}Se{sub 2}. A reaction between EuCl{sub 3}more » and Na{sub 6}Ge{sub 2}Se{sub 6} in 1:2 ratio at 650 deg. C for 96 h in an evacuated fused silica ampoule yielded Na{sub 2}EuGeSe{sub 4} (I), while the reaction between EuI{sub 2} and Na{sub 6}Ge{sub 2}Se{sub 6} in 1:1 ratio under similar conditions yielded Na{sub 0.75}Eu{sub 1.625}GeSe{sub 4} (II). Crystal data for these compounds are as follows: I, cubic, space group I4-bar3m (no. 217), a=7.3466(3), Z=2; II, cubic, space group I4-bar3d (no. 220), a=14.7065(8), Z=16. The crystal structures of I and II are closely related and can be compared to a CsCl-type and its ordered superstructure, respectively. These compounds are semiconductors with optical band gaps around 2 eV. The temperature dependence of the magnetic susceptibility indicated that both compounds are paramagnetic with {mu} {sub eff.}=7.6 and 7.73 {mu} {sub B}, for I and II, respectively, close to the theoretical value of 7.94 {mu} {sub B} for Eu{sup 2+}. Raman spectroscopic characterization of the compounds is also reported. - Graphical abstract: Related quaternary chalcogenides, Na{sub 2}EuGeSe{sub 4} (I) and its ordered superstructure Na{sub 0.75}Eu{sub 1.625}GeSe{sub 4} (II), have been synthesized employing solid-state reactions. The structures of these compounds contain isolated GeSe{sub 4} trerahedra and are related to the CsCl-type structure. These compounds are semiconducting with optical band gaps around 2 eV.« less
  • The new borate hydrate Co{sub 7}B{sub 24}O{sub 42}(OH){sub 2}{center_dot}2 H{sub 2}O was synthesized under high-pressure/high-temperature conditions of 6 GPa and 880 Degree-Sign C in a Walker-type multianvil apparatus. The compound crystallizes in the orthorhombic space group Pbam (Z=2) with the lattice parameters a=819.0(2), b=2016.9(4), c=769.9(2) pm, V=1.2717(4) nm{sup 3}, R{sub 1}=0.0758, wR{sub 2}=0.0836 (all data). The new structure type of Co{sub 7}B{sub 24}O{sub 42}(OH){sub 2}{center_dot}2 H{sub 2}O is built up from corner-sharing BO{sub 4} tetrahedra forming corrugated layers, that are interconnected among each other by two edge-sharing BO{sub 4} tetrahedra (B{sub 2}O{sub 6} units) forming Z-shaped channels. Interestingly, the heremore » presented structure of Co{sub 7}B{sub 24}O{sub 42}(OH){sub 2}{center_dot}2 H{sub 2}O is closely related to the structures of M{sub 6}B{sub 22}O{sub 39}{center_dot}H{sub 2}O (M=Fe, Co), which exhibit BO{sub 4} tetrahedra in an intermediate state on the way to edge-sharing BO{sub 4} tetrahedra. - Graphical Abstract: The new high-pressure borate hydrate Co{sub 7}B{sub 24}O{sub 42}(OH){sub 2}{center_dot}2 H{sub 2}O is built up from corner-sharing BO{sub 4} tetrahedra forming corrugated layers, that are interconnected among each other by two edge-sharing BO{sub 4} tetrahedra (B{sub 2}O{sub 6} units). In this paper we report on synthesis, structural details, and properties of the new compound Co{sub 7}B{sub 24}O{sub 42}(OH){sub 2}{center_dot}2 H{sub 2}O. Highlights: Black-Right-Pointing-Pointer High-pressure/high-temperature synthesis of the new borate hydrate Co{sub 7}B{sub 24}O{sub 42}(OH){sub 2}{center_dot}2 H{sub 2}O. Black-Right-Pointing-Pointer In the structure of Co{sub 7}B{sub 24}O{sub 42}(OH){sub 2}{center_dot}2 H{sub 2}O, two B{sub 2}O{sub 6} units are connected to 'vierer' rings. Black-Right-Pointing-Pointer Pressure favours the formation of edge-sharing BO{sub 4} tetrahedra in the chemistry of borates.« less
  • [C{sub 6}H{sub 21}N{sub 4}][Sb{sub 9}S{sub 14}O] represents the first known oxo-thioantimonate with an organic ion acting as structure director. The compound crystallizes in the non-centrosymmetric space group Cmc2{sub 1} with a=29.679(2), b=9.9798(6), c=11.7155(7)A, V=3470.1(4)A{sup 3}, Z=4. The structure contains the hitherto unknown [SbS{sub 2}O] unit as a structural motif. The [SbS{sub 3}] trigonal pyramids and [SbS{sub 2}O] units are joined to form a 10-membered ring with large pores having a diameter of 7.7Ax8.3A. The organic template molecule acts like a tetra-dentate ligand around the O atom of the [SbS{sub 2}O] group. Depending on the value chosen for the Sb-S bondmore » lengths, the material contains a 1-, 2- or 3-dimensional anion. The optical band gap of 2.03eV demonstrates that the material is an optical semi-conductor. Upon heating, the compound decomposes in two steps yielding finally a mixture of Sb and Sb{sub 2}S{sub 3}. The {sup 121}Sb Mossbauer spectrum shows a relative large line width in accordance with the superposition of the five signals.« less
  • New ternary beta-LaGaS{sub 3} has been synthesized from the stoichiometric mixture of elements by a conventional solid-state reaction at 1100 deg. C and annealed at 820 deg. C. This compound represents a new structure type that crystallizes in a non-centrosymmetric orthorhombic space group Pna2{sub 1} (No.33) with a=10.405(1) A, b=21.984(2) A, c=6.0565(5) A, and Z=12, and features the wavy GaS{sub 4} tetrahedron chains that are separated by La{sup 3+} cations. Detailed structural differences between the title compound and its isomer, monoclinic alpha-LaGaS{sub 3}, are discussed. With the aid of WIEN2k package, the absorption spectra and electronic structures as well asmore » the refractive indexes, absorption coefficients and reflectivities of two types of LaGaS{sub 3} have been calculated. The calculated band gap and the absorption edge of beta-LaGaS{sub 3} agree well with the experimental measurements. And a weak NLO response of beta-LaGaS{sub 3} has been detected. - Graphical abstract: New non-centrosymmeteic ternary lanthanum gallium sulfide, beta-LaGaS{sub 3}, features the wavy GaS{sub 4} tetrahedron chains that are separated by La{sup 3+} cations has been synthesized by a solid state reaction. Such an orthorhombic beta-LaGaS{sub 3} is isomeric with the monoclinic alpha-LaGaS{sub 3}. Detailed structural differences between the title compound and its isomer, monoclinic alpha-LaGaS{sub 3}, are discussed. The absorption spectra and electronic structures of both types of LaGaS{sub 3} have been calculated with the aid of WIEN2k package as well as the refractive indexes, absorption coefficients and reflectivities. The calculated band gap and absorption edge of beta-LaGaS{sub 3} agree well with the experimental measurements. And a weak NLO response of beta-LaGaS{sub 3} has been detected.« less