Sasaki Shunsuke, Driss Dalel, Grange Elodie, Mevellec Jean-Yves, Caldes Maria Teresa, Guillot-Deudon Catherine, Cadars Sylvian, Corraze Benoît, Janod Etienne, Jobic Stéphane, Cario Laurent
Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322, Nantes Cedex 3, France.
Angew Chem Int Ed Engl. 2018 Oct 8;57(41):13618-13623. doi: 10.1002/anie.201807927. Epub 2018 Sep 13.
Layered transition metal compounds represent a major playground to explore unconventional electric or magnetic properties. In that framework, topochemical approaches that mostly preserve the topology of layered reactants have been intensively investigated to tune properties and/or design new materials. Topochemical reactions often involve the insertion or deinsertion of a chemical element accompanied by a change of oxidation state of the cations only. Conversely, cases where anions play the role of redox centers are very scarce. Here we show that the insertion of copper into two dimensional precursors containing chalcogen dimers (Q ) (Q=S, Se) can produce layered materials with extended (CuQ) sheets. The reality of this topochemical reaction is demonstrated here for different pristine materials, namely La O S , Ba F S , and LaSe . Therefore, this work opens up a new synthetic strategy to design layered transition metal compounds from precursors containing polyanionic redox centers.
层状过渡金属化合物是探索非常规电学或磁学性质的主要研究对象。在此框架下，人们对主要保留层状反应物拓扑结构的拓扑化学方法进行了深入研究，以调控材料性能和/或设计新材料。拓扑化学反应通常涉及化学元素的插入或脱插，且仅伴随着阳离子氧化态的变化。相反，阴离子作为氧化还原中心的情况非常罕见。在此，我们表明将铜插入含有硫族二聚体（Q）（Q = S，Se）的二维前驱体中，可以制备出具有扩展（CuQ）层的层状材料。本文针对不同的原始材料，即La₂O₂S₂、Ba₂F₂S₂和LaSe₂，证明了这种拓扑化学反应的实际可行性。因此，这项工作开辟了一种新的合成策略，可从前体中含有多阴离子氧化还原中心的材料来设计层状过渡金属化合物。
