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

The sulfur coordination polymer catena ‐poly[zinc(II)‐μ 2 ‐bis[5‐(methylsulfanyl)‐2‐sulfanylidene‐2,3‐dihydro‐1,3,4‐thiadiazol‐3‐ido‐κ 2 N 3 : S ]], [Zn(C 3 H 3 N 2 S 3 ) 2 ] n or [Zn 2 MTT 4 ] n , constructed from Zn 2+ ions and 5‐methylsulfanyl‐1,3,4‐thiadiazole‐2‐thione (HMTT), was synthesized successfully and structurally characterized. [Zn 2 MTT 4 ] 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 Zn II ions, one via the thione group and the other via a ring N atom, with one Zn II atom being in a tetrahedral ZnS 4 and the other in a tetrahedral ZnN 4 coordination environment. These tetrahedral ZnS 4 and ZnN 4 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. [Zn 2 MTT 4 ] 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.