Ainsworth Chris M, Wang Chun-Hai, Johnston Hannah E, McCabe Emma E, Tucker Matthew G, Brand Helen E A, Evans John S O
†Department of Chemistry, University Science Site, Durham University, South Road, Durham DH1 3LE, U.K.
‡ISIS Neutron and Muon Source, Science and Technology Facilities Council, Rutherford Appleton Laboratory Didcot, Harwell, Oxford OX11 0QX, U.K.
Inorg Chem. 2015 Aug 3;54(15):7230-8. doi: 10.1021/acs.inorgchem.5b00599. Epub 2015 Apr 30.
A number of Ln2O2MSe2 (Ln = La and Ce; M = Fe, Zn, Mn, and Cd) compounds, built from alternating layers of fluorite-like Ln2O2 sheets and antifluorite-like MSe2 sheets, have recently been reported in the literatures. The available MSe4/2 tetrahedral sites are half-occupied, and different compositions display different ordering patterns: MSe2 layers contain MSe4/2 tetrahedra that are exclusively edge-sharing (stripe-like), exclusively corner-sharing (checkerboard-like), or mixtures of both. This paper reports 60 new compositions in this family. We reveal that the transition-metal arrangement can be systematically controlled by either Ln or M doping, leading to an "infinitely adaptive" structural family. We show how this is achieved in La2O2Fe1-xZnxSe2, La2O2Zn1-xMnxSe2, La2O2Mn1-xCdxSe2, Ce2O2Fe1-xZnxSe2, Ce2O2Zn1-xMnxSe2, Ce2O2Mn1-xCdxSe2, La2-yCeyO2FeSe2, La2-yCeyO2ZnSe2, La2-yCeyO2MnSe2, and La2-yCeyO2CdSe2 solid solutions.
近期文献报道了多种Ln2O2MSe2（Ln = La和Ce；M = Fe、Zn、Mn和Cd）化合物，它们由类萤石型Ln2O2层和类反萤石型MSe2层交替堆叠而成。可用的MSe4/2四面体位置被半占据，不同的组成呈现出不同的有序模式：MSe2层包含的MSe4/2四面体要么完全是边共享（条纹状），要么完全是角共享（棋盘状），或者是两者的混合。本文报道了该系列中的60种新组成。我们揭示了过渡金属的排列可以通过Ln或M掺杂进行系统控制，从而形成一个“无限自适应”的结构家族。我们展示了在La2O2Fe1-xZnxSe2、La2O2Zn1-xMnxSe2、La2O2Mn1-xCdxSe2、Ce2O2Fe1-xZnxSe2、Ce2O2Zn1-xMnxSe2、Ce2O2Mn1-xCdxSe2、La2-yCeyO2FeSe2、La2-yCeyO2ZnSe2、La2-yCeyO2MnSe2和La2-yCeyO2CdSe2固溶体中是如何实现这一点的。
