Solvothermal Syntheses of Two New Thiostannates and an In‐Situ Energy Dispersive X‐ray Scattering Study of Their Formation

Abstract

Two new thiostannates (DBNH) 2 Sn 3 S 6 (1) and (DBNH) 2 Cu 6 Sn 2 S 8 (2) were synthesized under solvothermal conditions applying Cu, Sn, S and DBN (DBN = 1,5-diazabicyclo[4.3.0]non-7-ene). Compound 1 is a rare example of a mixed-valent thiostannate. The Sn(II) species appears in the rare trigonal-pyramidal environment whereas Sn(IV) is in a tetrahedral coordination. The chain-anion is composed of alternating Sn 3 S 4 semi-cubes and Sn 2 S 2 rings. The structure of 2 consists of undulated anionic layers and amine molecules between the layers. The layers may be viewed as a heteroatom 6 3 graphene layer constructed by condensed CuS 3 triangles and SnS 4 tetrahedra. The two thiostannates coexist which was investigated with in-situ energy dispersive X-ray scattering under real solvothermal conditions. Prior to the formation of 1 and 2 a crystalline intermediate appears which disappears after 60 min.Then reflections of 2 start to grow and reflections of 1 occur some time later. The appearance of a thiostannate(IV) followed by the crystallization of a mixed-valent thiostannate(II,IV) suggests complex redox reactions occurring under the solvothermal conditions. Syntheses without Cu in the reaction slurry lead to the formation of 1 within a very short time. The results of the in-situ studies clearly indicate that the presence of Cu species in solution retards the nucleation and crystallization of 1. The crystalline intermediate was quenched with ex-situ experiments. All syntheses performed with this intermediate do not lead to the crystallization of 1 or 2, i.e., there is no direct relation between these three crystalline compounds. The spectroscopic and thermal properties of 1 and 2 are also discussed.

Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

“…The compounds (DBUH)-CuSnS 3 [113], (DBNH) 2 Cu 6 Sn 2 S 8 [102], (1,4-dabH)-2 Cu 2 SnS 4 [113] and the isostructural compound (1,4-dabH) 2 Ag 2 SnS 4 [114] were the first examples confirming the chalcophilic character of the two elements. In (DBUH)CuSnS 3 one-dimensional (Fig.…”

“…The great potential of this method was recently demonstrated studying the solvothermal synthesis using Sn, Cu, S, and DBN [102]. The two thiostannates (DBNH) 2 Sn 3 S 6 and (DBNH) 2 Cu 6 Sn 2 S 8 coexist under the chosen reaction conditions, and interestingly (DBNH) 2 Sn 3 S 6 is a Cu-free mixed-valent product with Sn(II) and Sn(IV).…”

Formation and characterisation of Mn-MIL-100

“…Thus, two dominating mechanisms are taking place during the crystallisation of Mn-MIL-100, which was already reported in other studies. 33 Therefore, the Sharp-Hancock analysis was 5 carried out for both linear sections. The final values are summarized in Tab.…”

Solvothermal syntheses of three new one-dimensional ternary selenidostannates: [DBNH][M1/2Sn1/2Se2] (M=Mn, Zn, Hg)

“…On the other hand, hybridize transition metals with group 13 and 14 metals may regulate the chemical and physical properties of 1D chain. 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) has been frequently used in the solvothermal syntheses of metal chalcogenides [66,67], mostly because protonated DBNH + cations can act as templates or structure directing-agents in the constructions of chalcogenides, and moreover, DBN can provides strongly alkaline environment in the synthesis procedure. In this paper, we report the solvothermal syntheses, crystal structures, and characterizations of three one-dimensional chain-like mixed-metal ternary selenidostannates: [DBNH][M 1/2 Sn 1/2 Se 2 ] (M¼Mn (1), Zn (2), Hg (3)); DBN¼ 1,5-diazabicyclo[4.3.0] non-5-ene).…”