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Title: Syntheses and structural characterization of non-centrosymmetric Na{sub 2}M{sub 2}M'S{sub 6} (M, M′=Ga, In, Si, Ge, Sn, Zn, Cd) sulfides

Abstract

Seven new non-centrosymmetric Na{sub 2}M{sub 2}M’S{sub 6} sulfides, namely, Na{sub 2}Sn{sub 2}ZnS{sub 6}(1){sub ,} Na{sub 2}Ga{sub 2}GeS{sub 6}(2), Na{sub 2}Ga{sub 2}SnS{sub 6}(3-α), Na{sub 2}Ga{sub 2}SnS{sub 6}(3-β){sub ,} Na{sub 2}Ge{sub 2}ZnS{sub 6}(4){sub ,} Na{sub 2}Ge{sub 2}CdS{sub 6}(5){sub ,} Na{sub 2}In{sub 2}SiS{sub 6}(6) and Na{sub 2}In{sub 2}GeS{sub 6}(7), were synthesized by high temperature solid state reactions and structurally characterized by single crystal X-ray diffraction. They crystallize in non-centrosymmetric Fdd2 and Cc space groups and their three-dimensional [M{sub 2}M′S{sub 6}]{sup 2-}framework structures consist of MS{sub 4} and M′S{sub 4} tetrahedra corner-connected to one another in either orderly or disordered fashion. Sodium ions reside in the tunnels of the anionic framework. Compounds 1, 2 and 3-α have the structure of known Li{sub 2}Ga{sub 2}GeS{sub 6}, whereas compounds 6 and 7 are isostructural with known Li{sub 2}In{sub 2}GeS{sub 6} compound. Isostructural compounds 4 and 5 represent a new structural variant. Compounds 3-α and its new monoclinic structural variant 3-β have disordered structural framework. All of them are wide band gap semiconductors. Na{sub 2}Ga{sub 2}GeS{sub 6}(2), Na{sub 2}Ga{sub 2}SnS{sub 6}(3), Na{sub 2}Ge{sub 2}ZnS{sub 6}(4) and Na{sub 2}In{sub 2}GeS{sub 6}(7) compounds are found to be second-harmonic generation (SHG) active. Compounds 1, 2 and 3-α melt congruently. -more » Graphical abstract: Na{sub 2}Ga{sub 2}GeS{sub 6}, Na{sub 2}Ga{sub 2}SnS{sub 6}, Na{sub 2}Ge{sub 2}ZnS{sub 6}, Na{sub 2}In{sub 2}GeS{sub 6}, Na{sub 2}Sn{sub 2}ZnS{sub 6}, Na{sub 2}Ge{sub 2}CdS{sub 6} and Na{sub 2}In{sub 2}SiS{sub 6} have non-centrosymmetric structures and the first four compounds are SHG active. Display Omitted - Highlights: • Seven new Na{sub 2}M{sub 2}M′S{sub 6} compounds with non-centrosymmetric structures were synthesized. • They are wide band gap semiconductors. • Na{sub 2}Ga{sub 2}GeS{sub 6}, Na{sub 2}Ga{sub 2}SnS{sub 6}, Na{sub 2}Ge{sub 2}ZnS{sub 6} and Na{sub 2}In{sub 2}GeS{sub 6} are SHG active.« less

Authors:
;
Publication Date:
OSTI Identifier:
22584113
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 238; 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; CADMIUM SULFIDES; GALLIUM SULFIDES; GERMANIUM SULFIDES; HARMONIC GENERATION; INDIUM SULFIDES; MONOCLINIC LATTICES; MONOCRYSTALS; ORTHORHOMBIC LATTICES; PETROLEUM RESIDUES; SEMICONDUCTOR MATERIALS; SILICON SULFIDES; SODIUM IONS; SOLIDS; SPACE GROUPS; SYNTHESIS; TIN SULFIDES; X RADIATION; X-RAY DIFFRACTION; ZINC SULFIDES

Citation Formats

Yohannan, Jinu P., and Vidyasagar, Kanamaluru, E-mail: kvsagar@iitm.ac.in. Syntheses and structural characterization of non-centrosymmetric Na{sub 2}M{sub 2}M'S{sub 6} (M, M′=Ga, In, Si, Ge, Sn, Zn, Cd) sulfides. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.03.026.
Yohannan, Jinu P., & Vidyasagar, Kanamaluru, E-mail: kvsagar@iitm.ac.in. Syntheses and structural characterization of non-centrosymmetric Na{sub 2}M{sub 2}M'S{sub 6} (M, M′=Ga, In, Si, Ge, Sn, Zn, Cd) sulfides. United States. doi:10.1016/J.JSSC.2016.03.026.
Yohannan, Jinu P., and Vidyasagar, Kanamaluru, E-mail: kvsagar@iitm.ac.in. 2016. "Syntheses and structural characterization of non-centrosymmetric Na{sub 2}M{sub 2}M'S{sub 6} (M, M′=Ga, In, Si, Ge, Sn, Zn, Cd) sulfides". United States. doi:10.1016/J.JSSC.2016.03.026.
@article{osti_22584113,
title = {Syntheses and structural characterization of non-centrosymmetric Na{sub 2}M{sub 2}M'S{sub 6} (M, M′=Ga, In, Si, Ge, Sn, Zn, Cd) sulfides},
author = {Yohannan, Jinu P. and Vidyasagar, Kanamaluru, E-mail: kvsagar@iitm.ac.in},
abstractNote = {Seven new non-centrosymmetric Na{sub 2}M{sub 2}M’S{sub 6} sulfides, namely, Na{sub 2}Sn{sub 2}ZnS{sub 6}(1){sub ,} Na{sub 2}Ga{sub 2}GeS{sub 6}(2), Na{sub 2}Ga{sub 2}SnS{sub 6}(3-α), Na{sub 2}Ga{sub 2}SnS{sub 6}(3-β){sub ,} Na{sub 2}Ge{sub 2}ZnS{sub 6}(4){sub ,} Na{sub 2}Ge{sub 2}CdS{sub 6}(5){sub ,} Na{sub 2}In{sub 2}SiS{sub 6}(6) and Na{sub 2}In{sub 2}GeS{sub 6}(7), were synthesized by high temperature solid state reactions and structurally characterized by single crystal X-ray diffraction. They crystallize in non-centrosymmetric Fdd2 and Cc space groups and their three-dimensional [M{sub 2}M′S{sub 6}]{sup 2-}framework structures consist of MS{sub 4} and M′S{sub 4} tetrahedra corner-connected to one another in either orderly or disordered fashion. Sodium ions reside in the tunnels of the anionic framework. Compounds 1, 2 and 3-α have the structure of known Li{sub 2}Ga{sub 2}GeS{sub 6}, whereas compounds 6 and 7 are isostructural with known Li{sub 2}In{sub 2}GeS{sub 6} compound. Isostructural compounds 4 and 5 represent a new structural variant. Compounds 3-α and its new monoclinic structural variant 3-β have disordered structural framework. All of them are wide band gap semiconductors. Na{sub 2}Ga{sub 2}GeS{sub 6}(2), Na{sub 2}Ga{sub 2}SnS{sub 6}(3), Na{sub 2}Ge{sub 2}ZnS{sub 6}(4) and Na{sub 2}In{sub 2}GeS{sub 6}(7) compounds are found to be second-harmonic generation (SHG) active. Compounds 1, 2 and 3-α melt congruently. - Graphical abstract: Na{sub 2}Ga{sub 2}GeS{sub 6}, Na{sub 2}Ga{sub 2}SnS{sub 6}, Na{sub 2}Ge{sub 2}ZnS{sub 6}, Na{sub 2}In{sub 2}GeS{sub 6}, Na{sub 2}Sn{sub 2}ZnS{sub 6}, Na{sub 2}Ge{sub 2}CdS{sub 6} and Na{sub 2}In{sub 2}SiS{sub 6} have non-centrosymmetric structures and the first four compounds are SHG active. Display Omitted - Highlights: • Seven new Na{sub 2}M{sub 2}M′S{sub 6} compounds with non-centrosymmetric structures were synthesized. • They are wide band gap semiconductors. • Na{sub 2}Ga{sub 2}GeS{sub 6}, Na{sub 2}Ga{sub 2}SnS{sub 6}, Na{sub 2}Ge{sub 2}ZnS{sub 6} and Na{sub 2}In{sub 2}GeS{sub 6} are SHG active.},
doi = {10.1016/J.JSSC.2016.03.026},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 238,
place = {United States},
year = 2016,
month = 6
}
  • The six compounds Ba{sub 2}GaMQ{sub 5} (M=Sb,Bi; Q=Se,Te) and Ba{sub 2}InSbQ{sub 5} (Q=Se,Te) have been synthesized for the first time. Ba{sub 2}GaMQ{sub 5} (M=Sb,Bi; Q=Se,Te) and Ba{sub 2}InSbTe{sub 5} crystallize in the centrosymmetric space group Pnma, while Ba{sub 2}InSbSe{sub 5} belongs to the noncentrosymmetric polar space group Cmc2{sub 1}. The structures of the six new compounds contain infinite {sup 1}{sub {infinity}}[MM'Q{sub 5}]{sub 4-} anionic chains built by MQ{sub 4} (M Prime =Ga,In) tetrahedra and heavily distorted M Prime Q{sub 6} (M Prime =Sb,Bi) octahedra. Ba{sub 2}InSbSe{sub 5} possesses a band gap of 1.92(5) eV and exhibits a weak powder secondmore » harmonic generation signal using the 2090 nm laser as fundamental wavelength. - Graphical abstract: Ba{sub 2}InSbSe{sub 5} contains infinite {sup 1}{sub {infinity}}[InSbSe{sub 5}]{sub 4-} chains which are built by corner-shared InSe{sub 4} tetrahedra chains and edge-shared SbSe{sub 6} octahedra chains connected through edge sharing . Highlights: Black-Right-Pointing-Pointer Ba{sub 2}GaMQ{sub 5} (M=Sb,Bi; Q=Se,Te) and Ba{sub 2}InSbQ{sub 5} (Q=Se,Te) have been synthesized. Black-Right-Pointing-Pointer The structures contain infinite {sup 1}{sub {infinity}}[MM'Q{sub 5}]{sub 4-} (M Prime =Ga,In) anionic chains. Black-Right-Pointing-Pointer The chains are built by distorted MQ{sub 6} (M=Sb,Bi) octahedra and M Prime Q{sub 4} (M Prime =Ga,In) tetrahedra. Black-Right-Pointing-Pointer Ba{sub 2}InSbSe{sub 5} exhibits a weak powder second harmonic generation signal.« less
  • The reaction of Ru/sub 3/(CO)/sub 9/(..mu../sub 3/-S)/sub 2/ (2) with Ru/sub 3/(CO)/sub 12/ under UV irradiation has yielded the higher nuclearity cluster compounds Ru/sub 4/(CO)/sub 9/(..mu..-CO)/sub 2/(..mu../sub 4/-S)/sub 2/ (3), 38%, Ru/sub 5/(CO)/sub 14/(..mu../sub 4/-S)/sub 2/ (4), 20%, and Ru/sub 6/(CO)/sub 17/(..mu../sub 4/-S)/sub 2/ (5), 3%. Thermal decarbonylation of Ru/sub 3/(CO)/sub 9/(..mu../sub 3/-CO)(..mu../sub 3/-S) (1) at 100/sup 0/C has yielded 3, 47%, 5, 10%, and Ru/sub 7/(CO)/sub 20/(..mu../sub 4/-S)/sub 2/ (6), 26%. The large clusters are decomposed to 2 and 3 by reaction with CO at 1 atm. Compounds 4-6 have been characterized by single-crystal X-ray diffraction analyses. For 4:more » space group P2/sub 1//n, a = 8.787 (2) A, b = 14.550 (3) A, c = 19.741 (3) A, ..beta.. = 98.09 (1)/sup 0/, Z = 4, rho/sub calcd/ = 2.56 g/cm/sup 3/. The cluster consists of an approximately square arrangement of four ruthenium atoms with quadruply bridging sulfido ligands on each face. An Ru(CO)/sub 4/ unit bridges one Ru-Ru edge of the cluster. But the EAN rule the molecule is unsaturated, and one of the Ru-Ru bonds was found to be unusually short, 2.704 (1) A. For 5: space group P2/sub 1/2/sub 1/2/sub 1/, a = 11.211 (2) A, b = 14.666 (4) A, c = 17.611 (4) A, Z = 4, rho/sub calcd/ = 2.63 g/cm/sup 3/. Compound 5 is isomorphous and isostructural with the know osmium homologue. The molecule consists of a pentagonal-bypyramidal cluster of five ruthenium atoms with two sulfido ligands. A Ru(CO)/sub 4/ group bridges one apical-equatorial edge of the cluster. For 6: space group P2/sub 1/2/sub 1/2/sub 1/, a = 11.226 (3) A, b = 14.320 (4) A, c = 21,217 (5) A, Z = 4, rho/sub calcd/ = 2.59 g/cm/sup 3/. Compound 6 is isomorphous and isostructural with the known osmium homologue. The molecule consists of a pentagonal-bipyramidal cluster of five ruthenium atoms and two sulfido ligands. Two Ru(CO)/sub 4/ groups bridge symmetrically adjacent apical-equatorial edges of the cluster.« less
  • Two new vanadium tellurites, VTeO{sub 4}(OH) (1) and Ba{sub 2}V{sub 4}O{sub 8}(Te{sub 3}O{sub 10}) (2), have been synthesized successfully with the use of hydrothermal reactions. The crystal structures of the two compounds were determined by single-crystal X-ray diffraction. Compound 1 crystallizes in the polar space group Pca2{sub 1} (No. 29) while compound 2 crystallizes in the centrosymmetric space group C2/c (No. 15). The topography of compound 1 reveals a two-dimensional, layered structure comprised of VO{sub 6} octahedral chains and TeO{sub 3}(OH) zig-zag chains. Compound 2, on the contrary, features a three-dimensional [V{sub 4}O{sub 8}(Te{sub 3}O{sub 10})]{sup 4-} anionic framework withmore » Ba{sup 2+} ions filled into the 10-member ring helical tunnels. The [V{sub 4}O{sub 8}(Te{sub 3}O{sub 10})]{sup 4-} anionic network is the first 3D vanadium tellurite framework to be discovered in the alkaline-earth vanadium tellurite system. Powder second harmonic generation (SHG) measurements indicate that compound 1 shows a weak SHG response of about 0.3×KDP (KH{sub 2}PO{sub 4}) under 1064 nm laser radiation. Infrared spectroscopy, elemental analysis, thermal analysis, and dipole moment calculations have also been carried out. - Graphical abstract: VTeO{sub 4}(OH) (1) crystallizes in the noncentrosymmetric space group Pca2{sub 1} (No. 29) while Ba{sub 2}V{sub 4}O{sub 8}(Te{sub 3}O{sub 10}) (2) crystallizes in the centrosymmetric space group C2/c (No. 15). - Highlights: • VTeO{sub 4}(OH) (1) and Ba{sub 2}V{sub 4}O{sub 8}(Te{sub 3}O{sub 10}) (2) have been synthesized successfully with the use of hydrothermal reactions. • VTeO{sub 4}(OH) (1) crystallizes in the noncentrosymmetric space group Pca2{sub 1} and displays a weak SHG response. • VTeO{sub 4}(OH) (1) represents only the fourth SHG-active material found in vanadium tellurite systems. • Ba{sub 2}V{sub 4}O{sub 8}(Te{sub 3}O{sub 10}) (2) exhibits a novel three-dimensional [V{sub 4}O{sub 8}(Te{sub 3}O{sub 10})]{sup 4-} anionic framework.« less
  • Ten AInM′S{sub 4} (A=alkali metals, Tl; M′= Ge, Sn) compounds with diverse structure types have been synthesized and characterized by single crystal and powder X-ray diffraction and a variety of spectroscopic methods. They are wide band gap semiconductors. KInGeS{sub 4}(1-β), RbInGeS{sub 4}(2), CsInGeS{sub 4}(3-β), TlInGeS{sub 4}(4-β), RbInSnS{sub 4}(8-β) and CsInSnS{sub 4}(9) compounds with three-dimensional BaGa{sub 2}S{sub 4} structure and CsInGeS{sub 4}(3-α) and TlInGeS{sub 4}(4-α) compounds with a layered TlInSiS{sub 4} structure have tetrahedral [InM′S{sub 4}]{sup −} frameworks. On the other hand, LiInSnS{sub 4}(5) with spinel structure and NaInSnS{sub 4}(6), KInSnS{sub 4}(7), RbInSnS{sub 4}(8-α) and TlInSnS{sub 4}(10) compounds with layered structuremore » have octahedral [InM′S{sub 4}]{sup −} frameworks. NaInSnS{sub 4}(6) and KInSnS{sub 4}(7) compounds undergo facile topotactic ion-exchange, at room temperature, with various mono-, di- and tri-valent cations in aqueous medium to give rise to metastable layered phases. - Graphical abstract: NaInSnS{sub 4} and KInSnS{sub 4} compounds undergo, in aqueous medium at room temperature, facile topotactic ion-exchange with mono, di and trivalent cations. Display Omitted - Highlights: • Ten AInM′S{sub 4} compounds with diverse structure types were synthesized. • They are wide band gap semiconductors. • NaInSnS{sub 4} and KInSnS{sub 4} compounds undergo facile topotactic ion-exchange at room temperature.« less
  • Four new quaternary vanado-tellurites and vanadyl-selenites, namely, SrVTeO{sub 5}(OH)(1), Cd{sub 2}V{sub 2}Te{sub 2}O{sub 11}(2), Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O(3) and Ba{sub 2}VSe{sub 3}O{sub 10}(4) have been synthesized and structurally characterized by single crystal X-ray diffraction. The oxidation state of vanadium is +5 in tellurites 1 and 2 and +4 in selenites 3 and 4. The structures of SrVTeO{sub 5}(OH)(1) and Cd{sub 2}V{sub 2}Te{sub 2}O{sub 11}(2) compounds consist of (VTeO{sub 5}(OH)){sup 2-} and (V{sub 2}Te{sub 2}O{sub 11}){sup 4-}anionic chains respectively, which are built from tetrahedral VO{sub 4} and disphenoidal TeO{sub 4} moieties. Similarly the structures of Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O(3)more » and Ba{sub 2}VSe{sub 3}O{sub 10}(4) respectively contain (VSe{sub 2}O{sub 7}){sup 2-} and (VSe{sub 3}O{sub 10}){sup 4-} anionic chains, which are made up of octahedral VO{sub 6} and pyramidal SeO{sub 3} units. Compounds 1 and 3 have been characterized by thermogravimetric and infrared spectroscopic methods. Compounds 1 and 2 are wide band gap semiconductors. - Graphical abstract: Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O and Ba{sub 2}VSe{sub 3}O{sub 10} compounds contain (VSe{sub 2}O{sub 7}){sup 2-} and (VSe{sub 3}O{sub 10}){sup 4-} chains. - Highlights: • Four new vanado-tellurites and vanadyl-selenites are synthesized. • Their structural features are different. • The vanado-tellurites are wide band gap semiconductors.« less