A sulfur coordination polymer with wide bandgap semiconductivity formed from zinc(II) and 5-methylsulfanyl-1,3,4-thiadiazole-2-thione

Abstract

The sulfur coordination polymer catena‐poly[zinc(II)‐μ2‐bis[5‐(methylsulfanyl)‐2‐sulfanylidene‐2,3‐dihydro‐1,3,4‐thiadiazol‐3‐ido‐κ2N3:S]], [Zn(C3H3N2S3)2]n or [Zn2MTT4]n, constructed from Zn2+ ions and 5‐methylsulfanyl‐1,3,4‐thiadiazole‐2‐thione (HMTT), was synthesized successfully and structurally characterized. [Zn2MTT4]n crystallizes in the tetragonal space group I (No. 82). Each MTT− ligand (systematic name: 5‐methylsulfanyl‐2‐sulfanylidene‐2,3‐dihydro‐1,3,4‐thiadiazol‐3‐ide) coordinates to two different ZnII ions, one via the thione group and the other via a ring N atom, with one ZnII atom being in a tetrahedral ZnS4 and the other in a tetrahedral ZnN4 coordination environment. These tetrahedral ZnS4 and ZnN4 units are alternately linked by the organic ligands, forming a one‐dimensional chain structure along the c axis. The one‐dimensional chains are further linked via C—H…N and C—H…S hydrogen bonds to form a three‐dimensional network adopting an ABAB‐style arrangement that lies along both the a and b axes. The three‐dimensional Hirshfeld surface analysis and two‐dimensional (2D) fingerprint plots confirm the major interactions as C—H…S hydrogen bonds with a total of 35.1%, while 7.4% are C—H…N hydrogen‐bond interactions. [Zn2MTT4]n possesses high thermal and chemical stability and a linear temperature dependence of the bandgap from room temperature to 270 °C. Further investigation revealed that the bandgap changes sharply in ammonia, but only fluctuates slightly in other solvents, indicating its promising application as a selective sensor.

Redox-active zinc thiolates for low-cost aqueous rechargeable Zn-ion batteries

“…S5 † ). 35 The crystal structure contains two Zn sites coordinated by either four N atoms (Zn–N distance: 2.036 Å) or four S atoms (Zn–S distance: 2.355 Å) in tetrahedral geometries. The ZnN 4 and ZnS 4 units are arranged alternately to afford a one-dimensional coordination polymer ( Fig.…”

Synthesis, structure and computational study of 5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine (Pesta) and its heterometallic π,σ-complex [Cu2FeCl2(Pesta)4][FeCl4]

“…Coordination of a terminal halide anion (Hal) to the Cu I ion in the presence of Alphtri leads to centrosymmetric [Cu 2 (Hal) 2 (Alphtri) 2 ] dimers (Fig. 4 (Fu et al, 2017;Zhang et al, 2019). The analogue of the Pesta ligand, i.e.…”