Two-Dimensional Indium Sulfide Framework Constructed from Pentasupertetrahedral P1 and Supertetrahedral T2 Clusters

A new open-framework indium sulfide ([In12S24H2]10-) constructed from pentasupertetrahedral sulfide clusters
([In8S17H],- P1) and supertetrahedral sulfide clusters ([In4S10H],- T2) has been prepared through hydrothermal
synthesis. Unlike previously reported P1 clusters that require divalent metal cations, the P1 cluster reported here
consists of only trivalent ions (In3+) and is the only known example of tetrahedral clusters with a core sulfur site
bonded to four trivalent ions. Each P1 cluster is joined to three T2 clusters (vice versa) to form an infinite two-dimensional sheet stacked along the crystallographic c-axis. In contrast with known three-dimensional open-framework
indium sulfides in which locations of extraframework amines are rarely known due to disorder, structure-directing
amine molecules are much less disordered as a result of host−guest N−H···S hydrogen bonding. The UV−vis
diffuse reflectance spectrum shows that this material is a wide band gap semiconductor.

一种由五超四面体硫化物簇([In8S17H],- P1)和超四面体硫化物簇([In4S10H],- T2)构建的新型开放式框架硫化铟([In12S24H2]10-)，已通过水热合成法制备成功。与之前报道的需二价金属阳离子的P1簇不同，本报告中所述的P1簇仅由三价离子(In3+)构成，是已知唯一一种其核心硫位点与四个三价离子键合的四面体簇。每个P1簇与三个T2簇（反之亦然）相连，形成沿晶体学c轴堆叠的无限二维片层。与已知的三维开放式框架硫化铟相比，由于无序，其外框架胺的位姿鲜为人知，而本材料中的结构导向胺分子由于宿主-客体N−H···S氢键作用，其无序度显著降低。紫外-可见漫反射光谱显示，该材料是一种宽带隙半导体。