Synthesis and Crystal Structures of New Antimony Polysulfido Complexes: [P(C6H5)4]3Sb3S25 and [P(C6H5)4]2Sb2S15 · 2(C3N2H6)

Mixed-Valent Selenidoantimonates(III,V) with Transition-Metal Complexes as Counterions: Solvothermal Syntheses and Characterization of [M(dien)2]2Sb4Se9 (M = Mn, Fe), [Co(dien)2]2Sb2Se6, and [Ni(dien)2]2Sb2Se5

“…The structures of these thioantimonates(III) are characterized by the condensation of the Sb III S m ( m = 3−6) 2b building units to form a series of Sb III x S y z - polyanions. It is believed that the rich structural diversity of thioantimonates(III) is due to the stereochemically active lone pair . We note that the similar architectural feature is observed in thiosalts of As. 2a-d However, the thioantimonates(V) are seldom interconnected to form a polyanion and always exist as an isolated tetrahedral [Sb V S 4 ] 3- anion 6 except that in some cases [Sb V S 4 ] 3- is bound to metal cations .…”

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

“…The sole , , and anions tend to undergo a variety of self‐condensation to form polyanion units, such as oligomeric chains or rings, as SBUs 1b,4c,5a. When only metal tetrahedra exist, they easily form the supertetrahedral clusters (T n , P n , C n ) as SBUs, or as discrete anions.…”

“…The typical PBUs are metal‐chalcogenide tetrahedra MQ 4 (Q = S, Se) of group 13 (Ga, In), group 14 (Ge, Sn), and some transition metal (TM) ions. These tetrahedral PBUs are apt to form supertetrahedral clusters (T n , P n , C n ), with tunable compositions and sizes, as SBUs for chalcogenidometalates,2a,3 whereas the Sb(III) ion of group 15, with stereochemically active lone pair electrons, tends to adopt asymmetric coordination geometries, such as pseudo‐tetrahedral (also known as trigonal pyramidal) ψ‐Sb III Q 3 and pseudo‐trigonal bipyramidal ψ‐Sb III Q 4 when combining with chalcogen ions, which often undergo self‐condensation to form oligomeric chains or rings 1a,1b,4. So far, the chalcogenidometalates based on sole metal tetrahedra (MT) or asymmetric coordination geometries (ACG) of Sb(III) as PBUs have been extensively studied.…”

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

“…2−9 Very recently, a number of antimony chalcogenides have been continuously prepared because the stereochemical effect of lone electron pairs and the various coordinations of stibium by chalcogen atoms can give rise to large structural and compositional diversities. 10,11 In other words, the stibium atom is coordinated with chalcogen atoms to form pyramidal [Sb III Q 3 ] 3– or tetrahedral [Sb V Q 4 ] 4– (Q = S, Se) primary units. The pyramidal [SbQ 3 ] 3– unit has a powerful tendency of a variety of condensations to form polynuclear anions which can link by sharing corners or edges to come into being rings or chains structure.…”

“…Since Bedard et al reported the solvothermally synthesized open-framework structure of tin­(IV) sulfides in 1989, a significant method has been developed in the synthesis of chalcogenides. Meanwhile, chalcogenides also have been attracting extensive research interest due to their excellent performance in the fields of semiconductor, ion exchange, and nonlinear optics. − Very recently, a number of antimony chalcogenides have been continuously prepared because the stereochemical effect of lone electron pairs and the various coordinations of stibium by chalcogen atoms can give rise to large structural and compositional diversities. , In other words, the stibium atom is coordinated with chalcogen atoms to form pyramidal [Sb III Q 3 ] 3– or tetrahedral [Sb V Q 4 ] 4– (Q = S, Se) primary units. The pyramidal [SbQ 3 ] 3– unit has a powerful tendency of a variety of condensations to form polynuclear anions which can link by sharing corners or edges to come into being rings or chains structure.…”