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

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ID: 64107
2019
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Abstract
The sulfur coordination polymer catena-poly[zinc(II)-μ-bis[5-(methylsulfanyl)-2-sulfanylidene-2,3-dihydro-1,3,4-thiadiazol-3-ido-κN:S]], [Zn(CHNS)] or [ZnMTT], constructed from Zn ions and 5-methylsulfanyl-1,3,4-thiadiazole-2-thione (HMTT), was synthesized successfully and structurally characterized. [ZnMTT] crystallizes in the tetragonal space group I-4 (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 ions, one via the thione group and the other via a ring N atom, with one Zn atom being in a tetrahedral ZnS and the other in a tetrahedral ZnN coordination environment. These tetrahedral ZnS and ZnN 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. [ZnMTT] 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.
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Authors Zhang, Jun;Ma, Xiaofan;Kong, Weili;Xie, Fazhi;Yuan, Shizhen;Song, Xiaojie;Lu, Zhansheng;Xuan, Xiaopeng;
Journal acta crystallographica section c, structural chemistry
Year 2019
DOI
10.1107/S2053229619010945
URL
Keywords
crystal structure thermal stability Zinc(II) chemical stability 1,3,4-thiadiazole-2-thione ammonia sensor bandgap linear temperature dependence one-dimensional coordination polymer

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