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首页> 外文期刊>Acta Crystallographica, Section B. Structural science, crystal engineering and materials >The structure-directing amine changes everything: structures and optical properties of two-dimensional thiostannates
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The structure-directing amine changes everything: structures and optical properties of two-dimensional thiostannates

机译：结构指导胺改变了一切：二维Thiostannates的结构和光学性质

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摘要

Two different two-dimensional thiostannates (SnS) were synthesized using tris(2-aminoethyl)amine (tren) or 1-(2-aminoethyl)piperidine (1AEP) as structure-directing agents. Both structures consist of negatively charged thiostannate layers with charge stabilizing cations sandwiched in-between. The fundamental building units are Sn_3S_4 broken-cube clusters connected by double sulfur bridges to form polymeric (Sn_3S_7~(2-))_n honeycomb hexagonal layers. The compounds are members of the R-SnS-1 family of structures, where R indicates the type of cation. Despite consisting of identical structural units, the band gaps of the two semiconducting compounds were found to differ substantially at 2.96 eV (violet-blue light) and 3.21 eV (UV light) for tren- SnS-1 and 1AEP-SnS-1, respectively. Aiming to explain the observed differences in optical properties, the structures of the two thiostannates were investigated in detail based on combined X-ray diffraction, solid-state ~(13)C and ~(119)Sn MAS NMR spectroscopy and scanning electron microscopy studies. The compound tren-SnS-1 has a hexagonal structure consisting of planar SnS layers with regular hexagonal pores and disordered cations, whereas 1AEP-SnS-1 has an orthorhombic unit cell with ordered cations, distorted hexagonal pores and non-planar SnS layers. In the formation of 1AEP-SnS-1, an intramolecular reaction of the structure-directing piperidine takes place to form an Nheterobicyclic cation through in situ C-H activation. Hirshfeld surface analysis was used to investigate the interaction between the SnS layers and cations in 1AEP-SnS-1 and revealed that the most nucleophilic part of the SnS sheets is one of the two crystallographically distinct double sulfur bridges.
机译：使用Tris（2-氨基乙基）胺（Tren）或1-（2-氨基乙基）哌啶（1AEP）作为结构引导剂合成两种不同的二维Thiostannate（Sn。这两个结构由带负电荷的Thiostannate层组成，带有电荷稳定阳离子夹在一起。基本建筑单位是SN_3S_4破碎的立方体簇，由双硫桥连接形成聚合物（SN_3S_7〜（2 - ））_ n蜂窝六角形层。该化合物是R-SNS-1系列结构的成员，其中R表示阳离子的类型。尽管由相同的结构单元组成，但发现两个半导体化合物的带间隙分别在2.96eV（紫色 - 蓝光）和3.21eV（UV光）中分别不同，分别为3.21eV（UV光） 。旨在解释观察到的光学性质的差异，基于组合的X射线衍射，固态〜（13）C和〜（119）SN MAS NMR光谱和扫描电子显微镜研究详细研究了两种Thiostannates的结构。该复合Tren-SNS-1具有六边形结构，该六边形结构包括具有常规六边形孔隙和阳离子的平面SNS层，而1AEP-SNS-1具有具有有序阳离子的正晶间单位细胞，扭曲的六边形孔和非平面SNS层。在1AEP-SNS-1的形成中，通过原位C-H激活进行结构引导哌啶的分子内反应以形成Nhieterbodclic阳离子。 HIRSHFELD表面分析用于研究SNS层和阳离子在1AEP-SNS-1之间的相互作用，并显示SNS片材的最亲核部分是两个晶形上不同的双硫桥中的一种。

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