Lu Zhen-Tao, Yang Si-Han, Liu Wenlong, Guo Sheng-Ping
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. China.
Chem Commun (Camb). 2021 Apr 11;57(28):3500-3503. doi: 10.1039/d1cc00351h. Epub 2021 Mar 10.
Inorganic salts with multiple anions have recently received increasing interest in view of their structural diversity and multifunctional properties, and oxysulfides are one type of such salts. Here, three novel oxysulfides YZrSO (1), YHfSO (2), and TmZSO (3) are obtained by high-temperature solid-state reactions. They crystallize with the orthorhombic space group Pbam and their three-dimensional structures featuring MSO (M = Zr, Hf) motifs built an unprecedented {[MSO]} wrinkle layer. Their optical band gaps are determined and 3 shows antiferromagnetic-like behavior. Theoretical calculations suggest their direct band gaps and the electron transfer between the frontier orbitals mainly occurred from S-3p and O-2p, to Y-4d and Zr-4d/Hf-5d orbitals.
鉴于其结构多样性和多功能特性，含有多种阴离子的无机盐近来受到越来越多的关注，氧硫化物就是这类盐中的一种。在此，通过高温固相反应获得了三种新型氧硫化物YZrSO（1）、YHfSO（2）和TmZSO（3）。它们结晶于正交空间群Pbam，其三维结构以MSO（M = Zr，Hf） motif为特征，构建了前所未有的{[MSO]}褶皱层。测定了它们的光学带隙，且3表现出类反铁磁行为。理论计算表明它们的直接带隙以及前沿轨道之间的电子转移主要发生在从S - 3p和O - 2p到Y - 4d以及Zr - 4d/Hf - 5d轨道之间。
