A Topochemical Approach to Synthesize Layered Materials Based on the Redox Reactivity of Anionic Chalcogen Dimers

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 (Q₂ )^2- (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 La₂ O₂ S₂ , Ba₂ F₂ S₂ , and LaSe₂ . Therefore, this work opens up a new synthetic strategy to design layered transition metal compounds from precursors containing polyanionic redox centers.