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Title: Synthesis and characterization of Er{sub 3}SmQ {sub 6} (Q=S, Se) and Er{sub 1.12}Sm{sub 0.88}Se{sub 3}

Abstract

The interlanthanide compounds Er{sub 3}SmS{sub 6}, Er{sub 3}SmSe{sub 6}, and Er{sub 1.12}Sm{sub 0.88}Se{sub 3} have been synthesized from stoichiometric reactions of the elements in a KI salt flux at 1273, 1173, and 1123 K, respectively. Er{sub 3}SmS{sub 6} and Er{sub 3}SmSe{sub 6}, which are isostructural and ordered, crystallize in space group P2{sub 1}/m in the ScEr{sub 3}S{sub 6} structure type whereas Er{sub 1.12}Sm{sub 0.88}Se{sub 3}, in which the Er and Sm atoms are disordered, crystallizes in space group Pnma in the U{sub 2}S{sub 3} structure type. Er{sub 3}SmS{sub 6} is a paramagnet with a {mu} {sub eff}=11.25(1) {mu}{sub B}/mol. From optical measurements a direct band gap of 2.0 eV for light perpendicular to the (100) crystal face of Er{sub 3}SmSe{sub 6} is derived whereas for isostructural Er{sub 3}SmS{sub 6} an optical transition at 2.2-2.4 eV and a broad absorption peak at lower energies are observed. - Graphical abstract: The structure of Er{sub 3}SmSe{sub 6} viewed approximately down [010].

Authors:
 [1];  [1];  [1];  [1];  [2]
  1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 (United States)
  2. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 (United States), E-mail: ibers@chem.northwestern.edu
Publication Date:
OSTI Identifier:
21015804
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.2007.01.039; PII: S0022-4596(07)00065-5; 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; ABSORPTION; CRYSTALS; ERBIUM COMPOUNDS; EV RANGE; MAGNETISM; MONOCLINIC LATTICES; ORTHORHOMBIC LATTICES; POTASSIUM IODIDES; SAMARIUM COMPOUNDS; SELENIDES; SPACE GROUPS; SULFIDES; SURFACES; SYNTHESIS

Citation Formats

Gray, Danielle L., Rodriguez, Brandon A., Chan, George H., Van Duyne, Richard P., and Ibers, James A. Synthesis and characterization of Er{sub 3}SmQ {sub 6} (Q=S, Se) and Er{sub 1.12}Sm{sub 0.88}Se{sub 3}. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2007.01.039.
Gray, Danielle L., Rodriguez, Brandon A., Chan, George H., Van Duyne, Richard P., & Ibers, James A. Synthesis and characterization of Er{sub 3}SmQ {sub 6} (Q=S, Se) and Er{sub 1.12}Sm{sub 0.88}Se{sub 3}. United States. doi:10.1016/j.jssc.2007.01.039.
Gray, Danielle L., Rodriguez, Brandon A., Chan, George H., Van Duyne, Richard P., and Ibers, James A. Tue . "Synthesis and characterization of Er{sub 3}SmQ {sub 6} (Q=S, Se) and Er{sub 1.12}Sm{sub 0.88}Se{sub 3}". United States. doi:10.1016/j.jssc.2007.01.039.
@article{osti_21015804,
title = {Synthesis and characterization of Er{sub 3}SmQ {sub 6} (Q=S, Se) and Er{sub 1.12}Sm{sub 0.88}Se{sub 3}},
author = {Gray, Danielle L. and Rodriguez, Brandon A. and Chan, George H. and Van Duyne, Richard P. and Ibers, James A.},
abstractNote = {The interlanthanide compounds Er{sub 3}SmS{sub 6}, Er{sub 3}SmSe{sub 6}, and Er{sub 1.12}Sm{sub 0.88}Se{sub 3} have been synthesized from stoichiometric reactions of the elements in a KI salt flux at 1273, 1173, and 1123 K, respectively. Er{sub 3}SmS{sub 6} and Er{sub 3}SmSe{sub 6}, which are isostructural and ordered, crystallize in space group P2{sub 1}/m in the ScEr{sub 3}S{sub 6} structure type whereas Er{sub 1.12}Sm{sub 0.88}Se{sub 3}, in which the Er and Sm atoms are disordered, crystallizes in space group Pnma in the U{sub 2}S{sub 3} structure type. Er{sub 3}SmS{sub 6} is a paramagnet with a {mu} {sub eff}=11.25(1) {mu}{sub B}/mol. From optical measurements a direct band gap of 2.0 eV for light perpendicular to the (100) crystal face of Er{sub 3}SmSe{sub 6} is derived whereas for isostructural Er{sub 3}SmS{sub 6} an optical transition at 2.2-2.4 eV and a broad absorption peak at lower energies are observed. - Graphical abstract: The structure of Er{sub 3}SmSe{sub 6} viewed approximately down [010].},
doi = {10.1016/j.jssc.2007.01.039},
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}
}
  • Isothermal sections of the quasi-ternary systems Ag{sub 2}S(Se)–Ga{sub 2}S(Se){sub 3}–In{sub 2}S(Se){sub 3} at 820 K were compared. Along the 50 mol% Ag{sub 2}S(Se), both systems feature continuous solid solutions with the chalcopyrite structure. Along the 17 mol% Ag{sub 2}S(Se), the interactions at the AgIn{sub 5}S(Se){sub 8}–'AgGa{sub 5}S(Se){sub 8}' sections are different. In the Ag{sub 2}S–Ga{sub 2}S{sub 3}–In{sub 2}S{sub 3} system the existence of the layered phase AgGa{sub x}In{sub 5–x}S{sub 8}, 2.25≤x≤2.85, was confirmed (S.G. P6{sub 3}mc). The Ag{sub 2}Se–Ga{sub 2}Se{sub 3}–In{sub 2}Se{sub 3} system features the formation of solid solution (up to 53 mol% Ga{sub 2}Se{sub 3}) based on AgIn{submore » 5}Se{sub 8} (S.G. P-42m). Crystal structure, atomic coordinates were determined by powder diffraction method for samples from the homogeneity region of AgIn{sub 5}Se{sub 8}. Specific conductivities of the crystals Ga{sub 6}In{sub 4}Se{sub 15} (1.33·10{sup −6} Ω{sup −1} m{sup −1}), Ga{sub 5.94}In{sub 3.96}Er{sub 0.1}Se{sub 15} (3.17·10{sup −6} Ω{sup −1} m{sup −1}), Ga{sub 5.5}In{sub 4.5}S{sub 15} (7.94·10{sup −6} Ω{sup −1} m{sup −1}), Ga{sub 5.46}In{sub 4.47}Er{sub 0.07}S{sub 15} (1·10{sup −9} Ω{sup −1} m{sup −1}) were measured at room temperature. Optical absorption and photoconductivity spectra were recorded in the range 400–760 nm. The introduction of erbium leads to an increase in the absorption coefficient and to the appearance of absorption bands at 530, 660, 810, 980, 1530 nm. - Highlights: • Nature of solid solutions in Ag{sub 2}S(Se)–Ga{sub 2}S(Se){sub 3}–In{sub 2}S(Se){sub 3} (820 K) were discussed. • Crystal structures of ternary and quaternary compounds were discussed. • Specific conductivity, optical properties of four single crystals were measured. • Photoconductivity of the Ga{sub 5.5}In{sub 4.5}S{sub 15} in the range 400–760 nm were recorded.« less
  • {alpha}-CsPbBi{sub 3}Se{sub 6} (I), {beta}-CsPbBi{sub 3}Se{sub 6} (II), RbPbBi{sub 3}Se{sub 6} (III), KPbBi{sub 3}Se{sub 6} (IV), CsPbBi{sub 3}S{sub 6} (V), and RbPbBi{sub 3}S{sub 6} (VI) were synthesized by the polychalcogenide flux method. {alpha}-CsPbBi{sub 3}Se{sub 6} was obtained at 720 C and crystallizes in the space group Pnma (No. 62) with a = 23.564(6) {angstrom}, b = 4.210(2) {angstrom}, c = 13.798(3) {angstrom} at room temperature. Final R/R{sub w} = 3.0/3.6%. In this compound, parallel NaCl-type Pb/Bi/Se columns with rectangularly shaped cross-sections are interconnected by edge sharing to build a 3-D tunnel framework with Cs atoms located inside the tunnels. Themore » hexagonal plates of {beta}-CsPbBi{sub 3}Se{sub 6} were obtained at 400 C and crystallize in the space group P6{sub 3}/mmc (No. 194) with a = 4.213(2) {angstrom}, c = 25.22(1) {angstrom}, {gamma} = 120 at {minus}100 C. Final R/R{sub w} = 4.2/4.7%. APbBi{sub 3}Se{sub 6} (A = Rb, K) and APbBi{sub 3}S{sub 6} (A = Cs, Rb) are isostructural with {beta}-CsPbBi{sub 3}Se{sub 6} and their hexagonal cell parameters were obtained at room temperature. The structure is composed of negatively charged Bi{sub 2}Te{sub 3}-type bilayers separated by alkali metals, which are distributed over two different crystallographic sites. The alkali metal ions are loosely packed in the interlayer space making them mobile. Topotactic ion-exchange reactions of two compounds, {beta}-CsPbBi{sub 3}Se{sub 6} and RbPbBi{sub 3}Se{sub 6}, were examined with LiI and NaI in the solid state and in aqueous solution. Prolonged water contact of the hexagonal compounds leads to decomposition and leaching of alkali metal and Pb{sup 2+} ions. Electrical conductivity and thermopower measurements for single crystals of I, II, and III show n-type semiconductor behavior with 0.6, 0.3, and 0.3 S/cm and {minus}730, {minus}550, and {minus}560 {micro}V/K at room temperature, respectively. The optical band gaps of all compounds range from 0.27 to 0.89 eV. Thermal properties of the compounds are reported.« less
  • The reactions of ammonium perrhenate, HCl(aq), and the phosphinothiol ligands (2-HSC{sub 6}H{sub 4})P(C{sub 6}H{sub 4}X){sub 2}, where X = H or SH [abbreviated P-(SH){sub x} (x = 1, 3)], in alcohol have led to the isolation of a series of rhenium complexes containing the [M(P{minus}S{sub x}){sub 2}] core, represented by [Re[P(C{sub 6}H{sub 4}S){sub 3}] [P(C{sub 6}H{sub 4}S){sub 2}(C{sub 6}H{sub 4}SH)]] (1), [ReOCl-[OP(C{sub 6}H{sub 5}){sub 2}(C{sub 6}H{sub 4}S)][P(C{sub 6}H{sub 5}){sub 2}(C{sub 6}H{sub 4}S)]] (3), and [ReOCl[OP(C{sub 6}H{sub 5}){sub 2}(2-SC{sub 6}H{sub 3}-3-SiMe{sub 3})]{sub 2}] (5). The reaction of 1 with NEt{sub 3}results in the formation of [HNEt{sub 3}][Re[P(C{sub 6}H{sub 4}S){sub 3}]{sub 2}]more » (2) by deprotonation of a thiol ligand. The reaction of ammonium perrhenate with P-(SH) also led to the isolation of the binuclear species [ReOCl[OP(C{sub 6}H{sub 5}){sub 2}(2-SC{sub 6}H{sub 3}-3-SiMe{sub 3})]{sub 2}] (4). Crystal data are given.« less
  • The compounds Sr{sub 3}MRhO{sub 6} (M = Sm, Eu, Tb, Dy, Ho, Er, and Yb) have been synthesized and structurally characterized by Rietveld refinement of powder X-ray diffraction data in the space group R{bar 3}c; Z = 6. The lattice parameters for the series were found to be a = 9.78570(7) and c = 11.4811(1) {angstrom}, a = 9.7837(1) and c = 11.4421(2) {angstrom}, a = 9.7662(2) and c = 11.3812(4) {angstrom}, a = 9.7627(2) and c = 11.3451(2) {angstrom}, a = 9.7591(2) and c = 11.3159(2) {angstrom}, a = 9.7557(2) and c = 11.2919(3) {angstrom}, and a = 9.7390(2)more » and c = 11.2501(3) {angstrom}, for Sr{sub 3}SmRhO{sub 6}, Sr{sub 3}EuRhO{sub 6}, Sr{sub 3}TbRhO{sub 6}, Sr{sub 3}DyRhO{sub 6}, Sr{sub 3}HoRhO{sub 6}, Sr{sub 3}ErRhO{sub 6}, and Sr{sub 3}YbRhO{sub 6}, respectively. These compounds are isostructural with K{sub 4}CdCl{sub 6}. The structure consists of infinite one-dimensional chains of alternating face-shared RhO{sub 6} octahedra and MO{sub 6} trigonal prisms (M = Sm, Eu, Tb, Dy, Ho, Er, and Yb). The strontium cations are located in a distorted square antiprismatic environment. Magnetic susceptibility data for the compounds Sr{sub 3}MRhO{sub 6} (M = Tb, Dy, Ho, Er, and Yb) obey the Curie law, with the expected {mu}{sub eff} values consistent with an oxidation state of +3 for both Rh and M.« less
  • The electrochemical oxidation of a metallic anode (zinc or cadmium) in an acetonitrile solution of a series of arenephosphinothiol ligands, 2-(Ph{sub 2}P)C{sub 6}H{sub 4}SH, 2-(Ph{sub 2}P)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}SH, 2-(Ph{sub 2}PO)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}SH, and PhP-(C{sub 6}H{sub 4}SH-2){sub 2} [abbreviated RP-(SH){sub x}, x = 1 or 2], affords [M(RP-S){sub 2}] and [M(RP-S{sub 2})], M = Zn, Cd. Adducts of several of these compounds with 1,10-phenanthroline and 2,2{prime}-bipyridine have also been obtained by addition of these coligands to the electrolysis phase. The compounds obtained have been characterized by microanalysis, IR, UV-visible, FAB spectrometry and {sup 1}H, {sup 31}P NMR spectroscopic studies.more » The compounds [Cd{sub 2}{l{underscore}brace}2-(Ph{sub 2}PO)-C{sub 6}H{sub 4}S{r{underscore}brace}{sub 4}]CH{sub 3}CN (1), [Zn{l{underscore}brace}2-(Ph{sub 2}P)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}S{r{underscore}brace}{sub 2}] (2), [Cd{l{underscore}brace}2-(Ph{sub 2}PO)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}S{r{underscore}brace}{sub 2}(CH{sub 3}OH)] (3), and [Zn{l{underscore}brace}PhPO(C{sub 6}H{sub 4}S-2){sub 2}{r{underscore}brace}(bipy)] (4), have been also characterized by single-crystal X-ray diffraction. Compound 1 is binuclear with a {l{underscore}brace}Cd{sub 2}S{sub 2}{r{underscore}brace} core and distorted trigonal bipyramidal {l{underscore}brace}CdO{sub 2}S{sub 3}{r{underscore}brace} geometry about the Cd sites. Compounds 2, 3, and 4 are mononuclear with distorted tetrahedral {l{underscore}brace}ZnP{sub 2}S{sub 2}{r{underscore}brace}, distorted square pyramidal {l{underscore}brace}CdO{sub 3}S{sub 2}{r{underscore}brace}, and distorted trigonal bipyramidal {l{underscore}brace}ZnON{sub 2}S{sub 2}{r{underscore}brace} geometries, respectively.« less