Re‐investigation of Barium‐Gold(I)‐Tetra‐Thiostannate(IV), Ba[Au₂SnS₄], with Short Au^I···Au^I Separation Showing Luminescence Properties

Abstract

New investigations combining single crystal-and synchrotron-based powder X-ray diffraction data revealed that Ba[Au 2 SnS 4 ] crystallizes in the orthorhombic crystal system in space group C222 1 instead of P2 1 2 1 2 as reported earlier. While the principle crystal structure is not altered, there are significant differences of the interatomic distances Au-S and Sn-S. A salient property of this crystal structure is the partial framework composed of AuS 2 dumbbells and SnS 4 tetrahedra to form chains [(Au 2 SnS 4) 2-] ϱ propagating in the [100] direction. Within the chains a short Au•••Au separation of 2.9538(13) Å is ob

Directed Dehydration of Na4Sn2S6 ⋅ 5H2O Generates the New Compound Na4Sn2S6: Crystal Structure and Selected Properties

“…[23][24][25][26][27] Several thiostannates or tin sulfides exhibit interesting and promising properties like nonlinear optical behavior, [28] the selective capture of hazardous or radioactive metal cations, [29][30][31] as absorber layers in thin film solar cells, [32][33][34] as photocatalyst for light-driven hydrogen evolution, [35] or as luminescent material. [36] In the last few years, tin-based sulfides came into focus of research in the area of energy storage materials [37] as well as solid electrolytes for applications in all-solid-state batteries, because some exhibit superionic conduction properties. For example, the mixed quaternary compounds Na 11 Sn 2 PS 12 (σ RT = 3.7 mS cm À 1 and E a = 0.39 eV; σ RT = 1.4 mS cm À 1 and E a = 0.25 eV), [38,39] Na 10 SnP 2 S 12 (σ RT = 0.4 mS cm À 1 , E a = 0.36 eV), [40] Na 11 Sn 2 SbS 12 (σ RT = 0.6 mS cm À 1 , E a = 0.34 eV), [41] Na 11.25 Sn 2.25 Sb 0.75 S 12 (σ RT = 0.5 mS cm À 1 , E a = 0.39 eV) [42] have promisingly high room-temperature (RT) conductivities σ RT and low activation energies E a for ionic conduction.…”

“…There are also some reports that thiostannates can be prepared under even milder reaction conditions in liquid media [23–27] . Several thiostannates or tin sulfides exhibit interesting and promising properties like non‐linear optical behavior, [28] the selective capture of hazardous or radioactive metal cations, [29–31] as absorber layers in thin film solar cells, [32–34] as photocatalyst for light‐driven hydrogen evolution, [35] or as luminescent material [36] . In the last few years, tin‐based sulfides came into focus of research in the area of energy storage materials [37] as well as solid electrolytes for applications in all‐solid‐state batteries, because some exhibit superionic conduction properties.…”

Directed Dehydration as Synthetic Tool for Generation of a New Na4SnS4 Polymorph: Crystal Structure, Na+ Conductivity, and Influence of Sb‐Substitution

“…In addition, Sn occurs mainly in the oxidation state IV, but compounds with different oxidation states like II/IV or III/IV were also reported [10–12] . Thiostannates with metal cations as counter ions were mainly synthesized using the molten‐flux approach, [13, 14] or via high‐temperature syntheses [15–19] . Thiostannates with protonated amine molecules, transition metal cations, or transition metal complexes as counter ions compensating the negative charge of the [Sn x S y ] n − anions were mostly prepared under solvothermal conditions [9, 20–35] .…”

“…[10][11][12] Thiostannates with metal cations as counter ions were mainly synthesized using the molten-flux approach, [13,14] or via high-temperature syntheses. [15][16][17][18][19] Thiostannates with protonated amine molecules, transition metal cations, or transition metal complexes as counter ions compensating the negative charge of the [Sn x S y ] nÀ anions were mostly prepared under solvothermal conditions. [9,[20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] Applying suitable precursors, the preparation of thiostannates at room temperature was also reported.…”

Gezielte Dehydratisierung als Synthesewerkzeug zur Herstellung eines neuen Na4SnS4‐Polymorphs: Kristallstruktur, Na+‐Leitfähigkeit und Einfluss der Sb‐Substitution

“…Sn kommt hauptsächlich in der Oxidationsstufe IV vor, allerdings sind auch Verbindungen mit anderen Oxidationsstufen wie II/IV oder III/IV bekannt [10–12] . Thiostannate mit Metallkationen als Gegenionen wurden überwiegend mit dem Schmelzflussverfahren [13, 14] oder über Hochtemperatursynthesen [15–19] dargestellt. Thiostannate mit protonierten Aminmolekülen, Übergangsmetallkationen oder Übergangsmetallkomplexen als Gegenionen, die die negative Ladung der [Sn x S y ] n − ‐Anionen kompensieren, wurden meist unter solvothermalen Bedingungen hergestellt [9, 20–35] .…”