Mercury Bismuth Chalcohalides, Hg3Q2Bi2Cl8 (Q = S, Se, Te): Syntheses, Crystal Structures, Band Structures, and Optical Properties

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• 作者：Arief C. Wibowo ; Christos D. Malliakas ; Duck Young Chung ; Jino Im ; Arthur J. Freeman ; Mercouri G. Kanatzidis
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：March 18, 2013
• 年：2013
• 卷：52
• 期：6
• 页码：2973-2979
• 全文大小：416K
• 年卷期：v.52,no.6(March 18, 2013)
• ISSN：1520-510X

文摘

Three quaternary mercury bismuth chalcohalides, Hg₃Q₂Bi₂Cl₈ (Q = S, Se, Te), are reported along with their syntheses, crystal structures, electronic band structures, and optical properties. The compounds are structurally similar with a layer comprised of a hole perforated sheet network of [Hg₃Q₂]²⁺ (Q = S and Te) that forms by fused cyclohexane, chairlike Hg₆Q₆ rings. The cationic charge in the network is balanced by edge-sharing monocapped trigonal-prismatic anions of [Bi₂Cl₈]^{2鈥?/sup> that form a two-dimensional network located between layers. Compound 1, Hg₃S₂Bi₂Cl₈, crystallizes in the monoclinic space group C12/m1 with a = 12.9381(9) 脜, b = 7.3828(6) 脜, c = 9.2606(6) 脜, and 尾 = 116.641(5)掳. Compound 2, Hg₃Te₂Bi₂Cl₈, crystallizes in the monoclinic space group C12/c1 with a = 17.483(4) 脜, b = 7.684(2) 脜, c = 13.415(3) 脜, and 尾 = 104.72(3)掳. The crystals of the Hg₃Se₂Bi₂Cl₈ analogue exhibit complex modulations and structural disorder, which complicated its structural refinement. Compounds 1 and 2 melt incongruently and show band gaps of 3.26 and 2.80 eV, respectively, which are in a good agreement with those from band-structure density functional theory calculations.}