Synthesis, structure, and characterization of a mixed amines thiogermanate [NH4](2)[NH2(CH3)(2)](2)Ge2S6
Synthesis, structure, and characterization of a mixed amines thiogermanate [NH4](2)[NH2(CH3)(2)](2)Ge2S6
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混合胺硫锗酸盐[NH4](2)[NH2(CH3)(2)](2)Ge2S6的合成、结构和表征
DOI：
10.1016/j.poly.2020.114486
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发表时间：
2020
期刊：
影响因子：
2.6
通讯作者：
Ying Shao-Ming
中科院分区：
文献类型：
--
作者：
Zhang Jian-Han;Su Zhi-Zhong;Luo Ju-Xiang;Zhao Yi;Wang Hong-Gang;Ying Shao-Ming
采用溶剂热法合成了混合胺硫代锗酸盐（NH_4）_2 [NH_2（CH_3）_2]_2Ge_2S_6。X射线单晶衍射表明该化合物属单斜晶系，空间群为P21/c，晶胞参数为：a = 6.9647（14）B = 15.719（3），c = 7.2042（14），β = 92.76（3）°。该结构具有零维[Ge 2S 6]4−阴离子，由NH 4+和[NH 2（CH 3）2]+分开。氢键相互作用在其结构形成中起着至关重要的作用。采用X射线粉末衍射和热重-差示扫描量热法（TG-DSC）研究了其物相纯度和热稳定性。UV-Vis漫反射光谱结合Urbach拟合表明间接光学过渡半导体的带隙值为3.50 eV。电子结构的第一性原理计算结果支持了间接光学跃迁的实验结果，但其值被低估为3.061 eV。态密度和布居分析也被计算，以揭示其结构形成的带隙和键相互作用的起源。
A mixed amines thiogermanate, namely (NH4)2[NH2(CH3)2]2Ge2S6has been successfully synthesized by solvothermal reaction. Single crystal X-ray diffraction indicates the compound crystallizes in monoclinic space groupP21/cwith the lattice parameters: a = 6.9647(14) Å, b = 15.719(3) Å, c = 7.2042(14) Å, β = 92.76(3)°. The structure features a zero-dimensional [Ge2S6]4−anions which are separated by NH4+and [NH2(CH3)2]+. Hydrogen bond interactions play a crucial role in its structure formation. X-ray powder diffraction and TG-DSC measurements were performed to study its phase purity and thermal stability. UV–Vis diffuse reflectance spectroscopy coupled with Urbach fitting indicates an indirect optical transition semiconductor with a bandgap value of 3.50 eV. The result of first-principles electronic structure calculation supported the experimental indirect optical transition but the value was under estimated as 3.061 eV. Density of states and population analysis were also calculated to reveal the origin of the bandgap and bond interaction for its structure formation.