Selenidostannates and a Silver Selenidostannate Synthesized in Deep Eutectic Solvents: Crystal Structures and Thermochromic Study
Selenidostannates and a Silver Selenidostannate Synthesized in Deep Eutectic Solvents: Crystal Structures and Thermochromic Study
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低共熔溶剂中合成的硒化锡酸盐和硒化锡酸银：晶体结构和热致变色研究
DOI：
10.1021/acs.inorgchem.8b02610
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发表时间：
2019
影响因子：
4.6
通讯作者：
Cheng Wang
中科院分区：
文献类型：
--
作者：
Kai-Yao Wang;Hua-Wei Liu;Shu Zhang;Dong Ding;Lin Cheng;Cheng Wang
低共熔溶剂（DES）已被用作溶剂热合成晶体材料的反应介质。在本工作中，我们通过加入二甲胺、乙胺和三甲胺盐酸盐，扩展了 DES 在硫属金属盐制备中的范围，并合成了一系列新型 Sn-Se 和 Ag-Sn-Se 化合物：即 [NH2(CH3)2]2Sn3Se7·0.5NH(CH3)2 (1)， [NH4]2Sn4Se9 (2)、[NH3C2H5]2Sn3Se7 (3) 和 [NH4]3AgSn3Se8 (4)。化合物 1 和 3 具有蜂窝状层状 [Sn3Se7] n2 n- 结构，具有大的六角形窗口，而化合物 2 具有罕见的 [Sn4Se9] n2 n- 阴离子层，由四聚 {Sn4Se10} 簇组成作为二级结构单元 (SBU)。化合物 4 包含由带有 Ag+ 连接基的 {Sn3Se8} 单元构建的无限 [AgSn3Se8] n3 n- 链，它代表了第一个在 DES 中合成的异金属硫属化物。卤化物盐的有机铵阳离子或由尿素分解原位形成的铵阳离子充当形成无机骨架的模板剂。化合物 4 由于其带隙的负温度依赖性，在可见光范围内表现出显着的热致变色性能（例如，在 100-450 K 范围内，Eg = 2.305-2.119 eV）。金色-深红-金色的颜色变化在五轮加热和冷却中是高度可逆的，材料没有任何相变，这为随后的设备创新提供了线索。
Deep eutectic solvents (DESs) have been adopted as reaction media for solvothermal synthesis of crystal materials. In the present work, we extended the scope of DESs in chalcogenidometalate preparation by including dimethylamine, ethylamine, and trimethylamine hydrochlorides and synthesized a series of novel Sn-Se and Ag-Sn-Se compounds: i.e., [NH2(CH3)2]2Sn3Se7·0.5NH(CH3)2 (1), [NH4]2Sn4Se9 (2), [NH3C2H5]2Sn3Se7 (3), and [NH4]3AgSn3Se8 (4). Compounds 1 and 3 possess honeycomb lamellar [Sn3Se7] n2 n- structures featuring large hexagonal windows, while compound 2 features a rare [Sn4Se9] n2 n- anionic layer consisting of tetrameric {Sn4Se10} clusters as secondary building units (SBUs). Compound 4 comprises infinite [AgSn3Se8] n3 n- chains built by {Sn3Se8} units with Ag+ linkers, and it represents the first heterometallic chalcogenide synthesized in DESs. The organic ammonium cations of halide salts or in situ formed ammonium cations from the decomposition of urea act as templating agents for the formation of the inorganic frameworks. Compound 4 exhibits a marked thermochromic performance in the visible light range owing to the negative temperature dependence of its band gap ( Eg = 2.305-2.119 eV in the range of 100-450 K). The gold-dark red-gold color change is highly reversible in five rounds of heating and cooling, without any phase transition of the material, shedding light on the consequent device innovations.