Zhang Jun, Ma Xiaofan, Kong Weili, Xie Fazhi, Yuan Shizhen, Song Xiaojie, Lu Zhansheng, Xuan Xiaopeng
School of Materials and Chemical Engineering, Anhui Jianzhu University, Hefei 230601, People's Republic of China.
School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical, Media and Reactions, Ministry of Education, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Henan Normal University, Xinxiang, Henan, People's Republic of China.
Acta Crystallogr C Struct Chem. 2019 Sep 1;75(Pt 9):1243-1249. doi: 10.1107/S2053229619010945. Epub 2019 Aug 9.
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.
由锌离子和5-甲基硫烷基-1,3,4-噻二唑-2-硫酮（HMTT）构建的硫配位聚合物链状聚[锌（II）-μ-双[5-（甲基硫烷基）-2-硫亚基-2,3-二氢-1,3,4-噻二唑-3-亚氨基-κN:S]]，即[Zn(CHNS)]或[ZnMTT]，已成功合成并进行了结构表征。[ZnMTT]结晶于四方晶系空间群I-4（编号82）。每个MTT配体（系统名称：5-甲基硫烷基-2-硫亚基-2,3-二氢-1,3,4-噻二唑-3-负离子）与两个不同的锌离子配位，一个通过硫酮基团，另一个通过环氮原子，其中一个锌原子处于四面体ZnS配位环境，另一个处于四面体ZnN配位环境。这些四面体ZnS和ZnN单元通过有机配体交替连接，沿c轴形成一维链状结构。一维链通过C-H...N和C-H...S氢键进一步连接，形成沿a轴和b轴呈ABAB式排列的三维网络。三维Hirshfeld表面分析和二维（2D）指纹图谱证实主要相互作用为C-H...S氢键，占比共35.1%，而C-H...N氢键相互作用占7.4%。[ZnMTT]具有高热稳定性和化学稳定性，并且从室温到270 °C带隙呈线性温度依赖性。进一步研究表明，其带隙在氨中变化剧烈，但在其他溶剂中仅略有波动，表明它作为选择性传感器具有广阔的应用前景。
