Infinitely Adaptive Transition-Metal Ordering in Ln2O2MSe2-Type Oxychalcogenides

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• 作者：Chris M. Ainsworth ; Chun-Hai Wang ; Hannah E. Johnston ; Emma E. McCabe ; Matthew G. Tucker ; Helen E. A. Brand ; John S. O. Evans
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：August 3, 2015
• 年：2015
• 卷：54
• 期：15
• 页码：7230-7238
• 全文大小：646K
• ISSN：1520-510X

文摘

A number of Ln₂O₂MSe₂ (Ln = La and Ce; M = Fe, Zn, Mn, and Cd) compounds, built from alternating layers of fluorite-like [Ln₂O₂]²⁺ sheets and antifluorite-like [MSe₂]^{2鈥?/sup> sheets, have recently been reported in the literatures. The available MSe_4/2 tetrahedral sites are half-occupied, and different compositions display different ordering patterns: [MSe₂]2鈥?/sup> layers contain MSe_4/2 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 鈥渋nfinitely adaptive鈥?structural family. We show how this is achieved in La₂O₂Fe_1鈥?i>xZn_xSe₂, La₂O₂Zn_1鈥?i>xMn_xSe₂, La₂O₂Mn_1鈥?i>xCd_xSe₂, Ce₂O₂Fe_1鈥?i>xZn_xSe₂, Ce₂O₂Zn_1鈥?i>xMn_xSe₂, Ce₂O₂Mn_1鈥?i>xCd_xSe₂, La_2鈥?i>yCe_yO₂FeSe₂, La_2鈥?i>yCe_yO₂ZnSe₂, La_2鈥?i>yCe_yO₂MnSe₂, and La_2鈥?i>yCe_yO₂CdSe₂ solid solutions.}