[CH₃NH₃]₂Ag₄Sn^IV₂Sn^IIS₈: An Open-Framework Mixed-Valent Chalcogenidostannate

Abstract

An open-framework chalcogenidostannate, namely, [CHNH]AgSnSnS (1), has been solvothermally synthesized and structurally characterized, which represents the first organically templated three-dimensional (3D) Ag-Sn-S compound containing the mixed valence of Sn(IV)/Sn(II) and displays visible-light-driven photocatalytic activity for degradation of crystal violet (CV).

Syntheses, Crystal Structures, and Optical and Photocatalytic Properties of Four Small-Amine-Molecule-Directed M–Sn–Q (M = Zn, Ag; Q = S, Se) Compounds

“…Although the anionic layer of compound 1 has the same M/ Sn ratio as those of compounds Cs 2 MSn 3 Se 8 (M = Zn, Cd, Hg), 63 Hitherto, although several organically templated M−Sn−Q (M = Mn, Zn, Cd, Hg, Ga, In; Q = S, Se) compounds have been synthesized under mild solvothermal conditions, 23,24,[30][31][32][33][34][35][36][37][38][39][40][41][42][43][44]46 2D M−Sn−Q compounds based on T2 clusters as SBUs have rarely been isolated. Compound 1 represents a rare example of organically templated 2D M−Sn− Q compounds characteristic of T2 cluster as SBUs.…”

“…Mild solvothermal techniques have proven to be very effective routes for the preparation of chalcogenidometalates, in which the amines molecules were often applied as reactive medium and/or SAAs. − In the preparation of M–Sn–Q (M = transition metal ions), the polyamine (e.g., ethylendiamine (en) and diethylenetriamine (dien)) or large organic amine molecules (e.g., N -(2-aminoethyl)­piperazine (AEP) and 1,5-diazabicyclo[4.3.0]­non-5-ene (DBN)) have been widely used as the solvents and/or SAAs. ,− By contrast, the smaller organic amine (e.g., [CH 3 NH 3 ] + and [(Me) 2 NH 2 ] + ) or NH 4 + -directed M–Sn–Q compounds are rarely explored. The limited examples include [CH 3 NH 3 ] 2 x ­Mn x Sn 3– x S 6 ­·0.5H 2 O ( x = 0.5–1.1), [CH 3 NH 3 ] 2 ­Ag 4 Sn IV 2 Sn II S 8 , [NH 4 ] 2 ­Ag 6 Sn 3 S 10 , [NH 4 ] 4­ Ag 12 Sn 7 Se 22 , and [(Me) 2 NH 2 ] 0.75 ­Ag 1.25 SnSe 3 . Since 2008, our group started to explore the solvothermal syntheses of small organic amine-directed heterometallic chalcogenidometalates based on the combination of p-block metal ions, for instance, the integration of Sb­(III) with group 14/13 metal ions (Ge 4+ , Sn 4+ , Ga 3+ , In 3+ ). ,,− Indeed, our attempts resulted in many heterometallic chalcogenidometalates with intriguing architectures that might not be obtained upon the structural direction of the polyamine or large organic amines.…”

Cotemplating Assembly and Structural Variation of Three-Dimensional Open-Framework Sulfides

“…Continual efforts have been devoted to exploring open-framework sulfides because of their fascinating structures , and potential applications in nonlinear-optical properties, , visible-light photocatalysis, , and fast-ion conductivity. , Sulfides have higher covalent frameworks than zeolites owing to the large size of S 2– compared to O 2– . The covalency of sulfides is reflected in the fact that large clusters (such as supertetrahedral clusters − and the icosahedral [Cu 8 S 12 ] 16– cluster , ) can be used as secondary building units, , which have never been found in zeolites.…”

The Role of [BF4]− and [B(CN)4]− Anions in the Ionothermal Synthesis of Chalcogenidometalates

“…Respective solvates were accessible by replacement of traditional solid‐state syntheses, which usually yield dense, solvent‐free structures, by solution reactions or solvothermal/hydrothermal approaches . This way, the synthesis of open framework structures or molecular aggregates including new structural motifs and elemental combinations, such as K 4 [PbSe 4 ] ⋅ en ⋅ NH 3 (en=ethane‐1,2‐diamine), (CH 3 NH 3 ) 2 [Ag 4 Sn IV 2 Sn II S 8 ], (Cat) 12 [In 4 Sn 16 O 10 S 34 ] (Cat=dpp=1,3‐di(4‐pyridyl)propane or eta=ethanolamine), have largely enriched the structural diversity within this class of compounds…”