From One-Dimensional Ribbon to Three-Dimensional Microporous Framework: The Syntheses, Crystal Structures, and Properties of a Series of Mercury Antimony Chalcogenides

Abstract

In the presence of various organic amines/alkali metal cations or [TM(amine) m ] n+ complexes as templates or structure-directing agents, a series of mercury antimony chalcogenide compounds have been solvothermally synthesized and structurally characterized. The compound [(Me)2NH2]2HgSb8S14 (1) features a one-dimensional (1D) [HgSb8S14] n 2n− ribbon built from two 1D-[Sb4S7] n 2n− chains bridged by HgS2 units. The compounds [enH2]0.5HgSbS3 (2) (en = ethylenediamine), [tetaH2]0.5HgSbS3 (3) (teta = triethylenetetramine), [1,2-pdaH]HgSbS3 (4) (1,2-pda = 1,2-diaminopropane), and [Ni(en)3]0.5HgSbS3 (5) feature two-dimensional (2D) layers of [HgSbS3] n n− with different structural motifs. The compound [tetaH2]0.25Rb0.5HgSbSe3 (6) exhibits a three-dimensional (3D) microporous framework structure of [HgSbSe3] n n− with cationic [tetaH2]2+ and Rb+ located in the channels. The optical absorption spectra indicate that all the compounds are semiconductors, with estimated bandgaps of 2.03 eV for 1, 2.49 eV for 2, 2.40 eV for 3, 2.55 eV for 4, 2.68 eV for 5, and 1.42 eV for 6, respectively. Thermal stabilities of these compounds have been investigated via thermogravimetric analyses.

Two Mercury Antimony Chalcogenides Cs2HgSb4S8 and Cs2Hg2Sb2Se6 with Cesium Cations as Counterions

“…The Hg–S bond lengths are similar to the HgS 4 tetrahedron of [Ni(en) 3 ] 0.5 HgSbS 3 (Hg–S: 2.456(2)–2.6756(18) Å) (Table S1). 17 In compound 1 appears Sb 3 S 3 six-membered rings, which are composed of three SbS 3 units by corner sharing (Figure 2b), and it is similar to some thioantimonates. 32,33 The [SbHgS 5 ] n chain and Sb 3 S 3 six-membered rings form the [HgSb 4 S 8 ] 2– ribbon by sharing S(1) and S(5) self-assembly (Figure 2c).…”

“…The [Hg 2 Se 6 ] n chains of 2 are connected with tetrahedron SbSe 4 units and trigonal pyramidal SbSe 3 units, forming 2D anionic layers of [Sb 2 Hg 2 Se 6 ] 2– . As far as we know, these compounds, which contain [enH 2 ] 0.5 HgSbS 3 , [tetaH 2 ] 0.5 HgSbS 3 , [1,2-pdaH]HgSbS 3 , [tetaH 2 ] 0.25 Rb 0.5 HgSbSe 3 , [Ni(en) 3 ] 0.5 HgSbS 3 , 17 [Co(en) 3 ]Hg 2 Sb 2 S 6 , 18 [Ni(en) 3 ]Hg 2 Sb 2 Se 6 , [Ni(en)(teta)]Hg 2 Sb 2 Se 6 , 21 KHgSbS 3 , 29 RbHgSbTe 3 , 30 and MHgSbSe 3 (M = K, Rb, Cs), 31 and compound 2 have the same stoichiometry of Hg:Sb:Q (Q = S, Se, Te) (1:1:3). It is different that these compounds are all composed of ring structure.…”

“…15 The transition metal ions contain Co 2+ , Ni 2+ , Fe 2+ , and Mn 2+ , and they are coordinated with organic amine to form [TM(amine) n ] 2+ complex cations acting as counterions, resulting in low-dimensional structural antimony chalcogenides. 16 A large number of A-Hg-Sb-Q (A= [TM(amine) n ] 2+ ) compounds are known in which the transition metal ions are integrated into organic amine frameworks as charge balancing ions, such as [Ni(en) 3 ] 0.5 HgSbS 3 (en = ethylenediamine), 17 [Co(en) 3 ]Hg 2 Sb 2 S 6 , [Ni(1,2-dap) 3 ] 2 HgSb 3 S 7 Cl (1,2-dap = 1,2-diaminopropane), [Ni(1,2-dap) 3 ]HgSb 2 S 5 , [Mn(dien) 2 ]HgSb 2 S 5 (dien = diethylenetriamine), [TM(tren)]HgSb 2 S 5 (TM = Mn, Fe, Co, tren = tris(2-aminoethyl)amine), [TM(dien) 2 ]Hg 3 Sb 4 S 10 (TM = Mn, Co, Ni), 18 [Co(dien) 2 ]HgSb 2 S 5 , [Ni(dien) 2 ]HgSb 2 S 5 , 19 [Mn(phen)] 2 HgSb 2 S 6 (phen = 1,10-phenanthroline), [TM(tren)]HgSb 2 Se 5 (TM = Mn, Fe, Co), 20 [Ni(1,2-pda)]HgSb 2 Se 5 , [Mn(dien) 2 ]HgSb 2 Se 5 , [Ni(en) 3 ]Hg 2 Sb 2 Se 6 , [Ni(en)(teta)]Hg 2 Sb 2 Se 6 , 21 and [TM(1,2-dap) 3 ]HgSb 2 Se 5 (TM = Co, Fe). 22 On the contrary, only a few compounds of antimony chalcogenides with alkali metal ions or alkaline earth metal ions as counterions are known.…”

“…As far as we know, there are only a few compounds of KHgSbS 3 , 29 RbHgSbTe 3 , 30 MHgSbSe 3 (M = K, Rb, Cs), 31 and [tetaH 2 ] 0.25 Rb 0.5 HgSbSe 3 . 17 Although most of the mercury(II)–antimony chalcogenides were synthesized by using organic amines or transition metal complexes as counterions, alkali metal ions or alkaline earth metal ions as counterions are still uncommon. In this article, we obtained two new mercury(II)–antimony chalcogenides Cs 2 HgSb 4 S 8 ( 1 ) and Cs 2 Hg 2 Sb 2 Se 6 ( 2 ).…”

Combination of Metal Coordination Tetrahedra and Asymmetric Coordination Geometries of Sb(III) in the Organically Directed Chalcogenidometalates: Structural Diversity and Ion-exchange Properties

“…Hitherto, the majority of known TM–Sb–Q compounds involved thiophilic metals, such as Hg 2+ , Ag + , and Cu 2+ 26. We synthesized a series of Hg–Sb–S compounds, including 1D‐[(Me) 2 NH 2 ] 2 HgSb 8 S 14 , 2D‐[enH 2 ] 0.5 HgSbS 3 , 2D‐[tetaH 2 ] 0.5 HgSbS 3 , 2D‐[1,2‐pdaH]HgSbS 3 , and 2D‐[Ni(en) 3 ] 0.5 HgSbS 3 ,27 which represents the first examples of Hg–Sb–Q chalcogenidometalates containing organic amines as SDAs. We also successfully prepared a series of organically directed Hg–Sb–Se compounds; namely, 1D‐[Ni(1,2‐dap) 3 ]HgSb 2 Se 5 , 1D‐[Mn(dien) 2 ]HgSb 2 Se 5 , 2D‐[Ni(en) 3 ]Hg 2 Sb 2 Se 6 , 2D‐[Ni(en)(teta)]Hg 2 Sb 2 Se 6 , 3D‐[(Me) 2 NH 2 ][Hg 3 Sb 3 Se 8 ],28 and 3D‐[tetaH 2 ] 0.25 Rb 0.5 HgSbSe 3 27…”