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Title: Solvothermal syntheses and characterization of three new silver(I)/copper(I)-thioarsenates based on As{sup 2+}/As{sup 3+} ions

Abstract

Three new silver(I)/copper(I)-thioarsenates KAgAs{sup II}S{sub 2} (1), RbCu{sub 2}As{sup III}S{sub 3} (2) and RbCu{sub 4}As{sup III}S{sub 4} (3) have been solvothermally synthesized and structurally characterized. 1 exhibits a two-dimensional anionic network built up by As−As bond connecting the left- and right-handed helical [AgS{sub 2}]{sup 4−} chains, and represents the first examples of thioarsenates(II). The structure of 2 consists of two kinds of helical [Cu{sub 2}S{sub 3}]{sup 4–} chains linked by the arsenic atoms to form double layers with rubidium ions between the layers. Compound 3 is built up of infinite [Cu{sub 2}S{sub 2}]{sup 2–} chain and layered [Cu{sub 6}As{sub 2}S{sub 6}] linked to form a three-dimensional anionic framework, [Cu{sub 4}AsS{sub 4}]{sup –}, and containing channels in which the rubidium cations reside. The optical properties of 1–3 have been investigated by UV–vis spectroscopy. - Graphical abstract: Three new silver(I)/copper(I)-thioarsenates have been solvothermally synthesized and structurally characterized. 1 represents the first examples of thioarsenates(II) while compounds 2 and 3 possess noncondensed pyramidal AsS{sub 3}{sup 3–} unit.

Authors:
 [1];  [2];  [1];  [3]; ; ; ;  [1]
  1. School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Zhongshan 528458 (China)
  2. (China)
  3. Department of Chemistry, Dalian University of Technology, Dalian 116024 (China)
Publication Date:
OSTI Identifier:
22658170
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 246; 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; ARSENIC IONS; COPPER IONS; EXPERIMENTAL DATA; HYDROTHERMAL SYNTHESIS; LAYERS; OPTICAL PROPERTIES; RUBIDIUM IONS; SILVER IONS

Citation Formats

Yao, Hua-Gang, E-mail: hgyao@gdpu.edu.cn, Guangdong Cosmetics Engineering & Technology Research Center, Zhongshan 528458, Tang, Cheng-Fei, An, Yong-Lin, Ou, Zi-Jian, Wu, Guo-Hao, Lan, Pei, and Zheng, Yi-Long. Solvothermal syntheses and characterization of three new silver(I)/copper(I)-thioarsenates based on As{sup 2+}/As{sup 3+} ions. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2016.11.014.
Yao, Hua-Gang, E-mail: hgyao@gdpu.edu.cn, Guangdong Cosmetics Engineering & Technology Research Center, Zhongshan 528458, Tang, Cheng-Fei, An, Yong-Lin, Ou, Zi-Jian, Wu, Guo-Hao, Lan, Pei, & Zheng, Yi-Long. Solvothermal syntheses and characterization of three new silver(I)/copper(I)-thioarsenates based on As{sup 2+}/As{sup 3+} ions. United States. doi:10.1016/J.JSSC.2016.11.014.
Yao, Hua-Gang, E-mail: hgyao@gdpu.edu.cn, Guangdong Cosmetics Engineering & Technology Research Center, Zhongshan 528458, Tang, Cheng-Fei, An, Yong-Lin, Ou, Zi-Jian, Wu, Guo-Hao, Lan, Pei, and Zheng, Yi-Long. Wed . "Solvothermal syntheses and characterization of three new silver(I)/copper(I)-thioarsenates based on As{sup 2+}/As{sup 3+} ions". United States. doi:10.1016/J.JSSC.2016.11.014.
@article{osti_22658170,
title = {Solvothermal syntheses and characterization of three new silver(I)/copper(I)-thioarsenates based on As{sup 2+}/As{sup 3+} ions},
author = {Yao, Hua-Gang, E-mail: hgyao@gdpu.edu.cn and Guangdong Cosmetics Engineering & Technology Research Center, Zhongshan 528458 and Tang, Cheng-Fei and An, Yong-Lin and Ou, Zi-Jian and Wu, Guo-Hao and Lan, Pei and Zheng, Yi-Long},
abstractNote = {Three new silver(I)/copper(I)-thioarsenates KAgAs{sup II}S{sub 2} (1), RbCu{sub 2}As{sup III}S{sub 3} (2) and RbCu{sub 4}As{sup III}S{sub 4} (3) have been solvothermally synthesized and structurally characterized. 1 exhibits a two-dimensional anionic network built up by As−As bond connecting the left- and right-handed helical [AgS{sub 2}]{sup 4−} chains, and represents the first examples of thioarsenates(II). The structure of 2 consists of two kinds of helical [Cu{sub 2}S{sub 3}]{sup 4–} chains linked by the arsenic atoms to form double layers with rubidium ions between the layers. Compound 3 is built up of infinite [Cu{sub 2}S{sub 2}]{sup 2–} chain and layered [Cu{sub 6}As{sub 2}S{sub 6}] linked to form a three-dimensional anionic framework, [Cu{sub 4}AsS{sub 4}]{sup –}, and containing channels in which the rubidium cations reside. The optical properties of 1–3 have been investigated by UV–vis spectroscopy. - Graphical abstract: Three new silver(I)/copper(I)-thioarsenates have been solvothermally synthesized and structurally characterized. 1 represents the first examples of thioarsenates(II) while compounds 2 and 3 possess noncondensed pyramidal AsS{sub 3}{sup 3–} unit.},
doi = {10.1016/J.JSSC.2016.11.014},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 246,
place = {United States},
year = {Wed Feb 15 00:00:00 EST 2017},
month = {Wed Feb 15 00:00:00 EST 2017}
}
  • Two new copper(I)-thioarsenates(III), CsCu{sub 2}AsS{sub 3}(1) and KCu{sub 4}AsS{sub 4}(2), have been synthesized solvothermally in the presence of copper powder. Compound 1 is built up of trigonal AsS{sub 3} pyramid, tetrahedral CuAsS{sub 3} and CuS{sub 3} moieties forming 4-membered, 5-membered and 6-membered rings. The fusion of these rings produces layered anions [Cu{sub 2}AsS{sub 3}]{sup -}, and cesium cations are located between metal-sulfide layers. The structure of 2 consists of infinite [Cu{sub 2}S{sub 2}]{sup 2-} chain and layered [Cu{sub 6}As{sub 2}S{sub 6}] linked to form a three-dimensional anionic framework, [Cu{sub 4}AsS{sub 4}]{sup -}, and containing channels in which the potassium cationsmore » reside. - Graphical abstract: Qne layered CsCu{sub 2}AsS{sub 3} and one framework KCu{sub 4}AsS{sub 4} possessing noncondensed [AsS{sub 3}]{sup 3-} unit have been synthesized solvothermally. The optical band gaps of the two compounds are 2.3 and 1.8 eV, respectively. Highlights: Black-Right-Pointing-Pointer We obtained two new copper(I)-thioarsenate(III), CsCu{sub 2}AsS{sub 3} and KCu{sub 4}AsS{sub 4}. Black-Right-Pointing-Pointer Both compounds possess noncondensed [AsS{sub 3}]{sup 3-} unit and represent new structure types. Black-Right-Pointing-Pointer The optical band gaps of the two compounds are 2.3 eV and 1.8 eV, respectively.« less
  • The hydrothermal reactions of As, Mn, S, phen (phen=1,10-phenanthroline), and en (en=ethylenediamine) yield two manganese As(III) and As(V) thioarsenates, [Mn{sub 2}(phen)(As{sup III}{sub 2}S{sub 5})]{sub n} (1) and [Mn{sub 3}(phen){sub 3}(As{sup V}S{sub 4}){sub 2}]{sub n}.nH{sub 2}O (2), respectively. Single-crystal X-ray diffraction analyses reveal that compound 1 is a two-dimensional (2D) layer of (6,3) topology. The 18-membered rings within the 2D porous layers are formed by corner-, edge-, and face-sharing cubane-like [Mn{sub 2}As{sub 2}S{sub 4}] units along the [100] direction. Whereas compound 2 is a one-dimensional (1D) chain structure. They are both characterized by IR, elemental analysis, EDS, and X-ray powder diffraction.more » The thermogravimetric analysis of 1 and 2 are discussed. Both the compounds are semiconductors with the band gap of E{sub g} (compound 1)=2.01 eV (617 nm) and E{sub g} (compound 2)=1.97 eV (629 nm), respectively. In addition, the variable-temperature magnetic susceptibility data suggest weak antiferromagnetic interactions between the Mn{sup 2+} ions in these two compounds. - Graphical abstract: Two manganese As(III) and As(V) thioarsenates, namely, [Mn{sub 2}(phen)(As{sup III}{sub 2}S{sub 5})]{sub n} (1) (top structure) and [Mn{sub 3}(phen){sub 3}(As{sup V}S{sub 4}){sub 2}]{sub n}.nH{sub 2}O (2) (bottom structure), have been isolated under hydrothermal conditions. Compound 1 is a 2D layer of (6,3) topology, while that of 2 is a 1D chain structure. The oxidation-state of arsenic might be related to the molar ratio of the reactants. They are both characterized by IR, elemental analysis, X-ray powder diffraction, and EDS. The thermogravimetric analysis and magnetism of 1 and 2 are discussed. Both the compounds are semiconductors.« less
  • Solvothermal reactions of Ln{sub 2}O{sub 3}, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln{sub 2}O{sub 3} oxides were converted to [Ln(dien){sub 2}]{sup 3+} complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS{sub 4} unit. In 1−3, the AsS{sub 4} units interconnect the [Ln(dien){sub 2}]{sup 3+} cations via Ln−S bonds as tridentate μ-1κ,2κ{sup 2}-AsS{sub 4} bridging ligands, resulting in themore » neutral coordination polymers [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln1). In 4−6, the AsS{sub 4} units coordinate with the Ln{sup 3+} ion of [Ln(dien){sub 2}]{sup 3+} as 1κ{sup 2}-AsS{sub 4} chelating ligands to form neutral coordination compounds [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln2). The Ln{sup 3+} ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln{sup 3+} ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] were prepared by solvothermal methods and the soft Lewis basic AsS{sub 4}{sup 3–} ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS{sub 4} ligand coordinate Ln{sup 3+} ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential semiconductors with optical band gaps in the range 2.18−3.21 eV.« less
  • A new silver organodiphosphonate, [Ag{sub 4}(O{sub 3}PCH{sub 2}CH{sub 2}PO{sub 3})] (1), has been synthesized and characterized by X-ray diffraction, IR, TGA-DSC, electricity measurement and element analysis. 1 crystallizes in the monoclinic space group P2(1)/n (a=6.0115(16)A, b=8.630(2)A, c=8.462(2)A, {beta}=97.693(4){sup o}, Z=2, R{sub 1}=0.0604, wR{sub 2}=0.1450). 1 contains one-dimensional channels and a three-dimensional Ag...Ag interacted substructural net. TGA and XRD indicate little weight loss up to 300 deg. C and little structure change after heated at 170{sup o}C for 2h, respectively. The grain interior conductivity of 1 increases continuously from 50 to 170 deg. C. Results of EHT calculations show that undermore » thermal or optical excitation the conductivity of 1 is mainly due to transfer of {pi} antibonding electrons of -PO{sub 3} group through O atom to Ag 5s orbital, which also leads to enhancement of Ag...Ag interactions and promotes formation of Ag...Ag substructural net.« less
  • The novel silver(I)thioantimonates(III) [C{sub 4}N{sub 2}H{sub 14}][Ag{sub 3}Sb{sub 3}S{sub 7}] (I) (C{sub 4}N{sub 2}H{sub 12}=1,4-diaminobutane) and [C{sub 2}N{sub 2}H{sub 9}]{sub 2}[Ag{sub 5}Sb{sub 3}S{sub 8}] (II) (C{sub 2}N{sub 2}H{sub 8}=ethylenediamine) were synthesized under solvothermal conditions using AgNO{sub 3}, Sb, S and the amines as structure directing molecules. Both compounds crystallize as orange needles with lattice parameters a=6.669(1) A, b=30.440(3) A, c=9.154(1) A for I (space group Pnma), and a=6.2712(4) A, b=15.901(1) A, c=23.012(2) A, {beta}=95.37(1){sup o} for II (space group P2{sub 1}/n). In both compounds the primary building units are trigonal SbS{sub 3} pyramids, AgS{sub 3} triangles and AgS{sub 4} tetrahedra.more » In I the layered [Ag{sub 3}Sb{sub 3}S{sub 7}]{sup 2-} anion is constructed by two different chains. An [Sb{sub 2}S{sub 4}] chain running along [100] is formed by vertex sharing of SbS{sub 3} pyramids. The second chain contains a Ag{sub 3}SbS{sub 5} group composed of the AgS{sub 4} tetrahedron, two AgS{sub 3} units and one SbS{sub 3} pyramid. The Ag{sub 3}SbS{sub 5} units are joined via S atoms to form the second chain which is also directed along [100]. The layered anion is then obtained by condensation of the two individual chains. The organic structure director is sandwiched by the inorganic layers and the shortest inter-layer distance is about 6.4 A. In II the primary building units are linked into different six-membered rings which form a honeycomb-like layer. Two such layers are connected via Ag-S bonds of the AgS{sub 4} tetrahedra giving the final undulated double layer anion. The structure directing ethylenediamine cations are located in pairs between the layers and a sandwich-like arrangement of alternating anionic layers and organic cations is observed. The inter-layer separation is about 5.4 A. Both compounds decompose in a more or less complex manner when heated in an argon atmosphere. The optical band gaps of about 1.9 eV for the two compounds proof the semiconducting behavior. For II the conductivity was measured with impedance spectroscopy and amounts to {sigma} {sub 295K}=7.6x10{sup -7} {omega}{sup -1} cm{sup -1}. At 80 deg. C the conductivity is significantly larger by one order of magnitude. - Graphical abstract: In the new silver thioantimonate, [C{sub 4}N{sub 2}H{sub 14}][Ag{sub 3}Sb{sub 3}S{sub 7}], the layered [Ag{sub 3}Sb{sub 3}S{sub 7}]{sup 2-} anion is constructed by two different chains. An [Sb{sub 2}S{sub 4}] chain is formed by vertex sharing of SbS{sub 3} pyramids. The second chain contains Ag{sub 3}SbS{sub 5} group which are connected by S atoms. The layered anion is obtained by condensation of the two individual chains. The organic structure director is sandwiched by the inorganic layers and the shortest inter-layer distance is about 6.4 A.« less