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dc.contributor.authorJi, Bingheng
dc.contributor.authorWu, Kui
dc.contributor.authorChen, Yunhua
dc.contributor.authorWang, Fei
dc.contributor.authorRossini, Aaron J.
dc.contributor.authorZhang, Bingbing
dc.contributor.authorWang, Jian
dc.identifier.citationInorg. Chem. 2022, 61, 5, 2640–2651 Publication Date:January 26, 2022 Copyright © 2022 American Chemical Societyen_US
dc.descriptionClick on the DOI to access this article (may not be free).en_US
dc.description.abstractSeven acentric sulfides Ba$_6$(Cu$_x$Z$_y$)Sn$_4$S$_{16}$ (Z = Mg, Mn, Zn, Cd, In, Bi, Sn) were grown by a high-temperature salt flux method. The crystal structures of the Ba$_6$(Cu$_x$Z$_y$)Sn$_4$S$_{16}$ (Z = Mg, Mn, Zn, Cd, In, Bi, Sn) compounds were determined by single crystal X-ray diffraction with the aid of solid-state NMR spectroscopy. The Ba$_6$(Cu$_x$Z$_y$)Sn$_4$S$_{16}$ (Z = Mg, Mn, Zn, Cd, In, Bi) compounds are isostructural and crystallize in the Ba$_6$Ag$_4$Sn$_4$S$_{16}$ structure type. The Sn-containing compound exhibits high structural similarity to Ba$_6$(Cu$_x$Z$_y$)Sn$_4$S$_{16}$ (Z = Mg, Mn, Zn, Cd, In, Bi) with the presence of an interstitial atomic position partially occupied by Sn atoms. The chemical bonding characteristics of Ba$_6$(Cu$_{2.9}$Sn$_{0.4}$)Sn$_4$S$_{16}$ were understood with electron localization function calculations coupled with crystal orbital Hamilton population calculations. The Ba−S and Cu−S interactions are dominantly ionic, but the Sn−S interactions consist of strong covalent bonding characteristics in Ba$_6$(Cu$_{2.9}$Sn$_{0.4}$)Sn$_4$S$_{16}$. The monovalent Cu atoms, mixed with certain metals with various oxidation states, significantly shift the optical properties of the Ba$_6$(Cu$_x$Z$_y$)Sn$_4$S$_{16}$ (Z = Mg, Mn, Zn, Cd, In, Bi) compounds. This results in a good balance between the second harmonic generation (SHG) response and laser damage threshold (LDT). Ba$_6$(Cu$_{1.9}$Zn$_{1.1}$)Sn$_4$S$_{16}$ possesses a high SHG response and a high LDT of 2.8 × AGS and 3 × AGS, respectively. A density functional theory calculation revealed that CuS$_4$ and SnS$_4$ tetrahedra significantly contribute to the SHG response in Ba$_6$(Cu$_2$Mg)Sn$_4$S$_{16}$, which also confirmed that CuS$_4$ tetrahedra are crucial for the stability and optical properties of the Ba$_6$(Cu$_x$Z$_y$)Sn$_4$S$_{16}$ (Z = Mg, Mn, Zn, Cd, In, Bi, Sn) compounds revealed by electronic structure analysis.en_US
dc.description.sponsorshipThis research is supported by start-up funds from Wichita State University. Solid-state NMR experiments and data analysis (Y.C. and A.J.R.) were supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. The Ames Laboratory is operated for the U.S. DOE by Iowa State University under Contract DE-AC02-07CH11358.en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesInorganic Chemistry;2022
dc.subjectNonlinear opticsen_US
dc.subjectChemical structureen_US
dc.subjectTransition metalsen_US
dc.subjectNuclear magnetic resonance spectroscopyen_US
dc.titleBa$_6$(Cu$_x$Z$_y$)Sn$_4$S$_{16}$(Z = Mg, Mn, Zn, Cd, In, Bi, Sn): High chemical flexibility resulting in good nonlinear-optical propertiesen_US
dc.rights.holder© 2022 American Chemical Societyen_US

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