Anionic Redox Topochemistry for Materials Design: Chalcogenides and Beyond

Abstract

Topochemistry refers to a generic category of solidstate reactions in which precursors and products display strong filiation in their crystal structures. Various low-dimensional materials are subject to this stepwise structure transformation by accommodating guest atoms or molecules in between their 2D slabs or 1D chains loosely bound by van der Waals (vdW) interactions. Those processes are driven by redox reactions between guests and the host framework, where transition metal cations have been widely exploited as the redox center. Topochemistry coupled with this cationic redox not only enables technological applications such as Li-ion secondary batteries but also serves as a powerful tool for structural or electronic fine-tuning of layered transition metal compounds. Over recent years, we have been pursuing materials design beyond this cationic redox topochemistry that was mostly limited to 2D or 1D vdW systems. For this, we proposed new topochemical reactions of non-vdW compounds built of 2D arrays of anionic chalcogen dimers alternating with redox-inert host cationic layers. These chalcogen dimers were found to undergo redox reaction with external metal elements, triggering either (1) insertion of these metals to construct 2D metal chalcogenides or (2) deintercalation of the constituent chalcogen anions. As a whole, this topochemistry works like a "zipper", where reductive cleavage of anionic chalcogen−chalcogen bonds opens up spaces in non-vdW materials, allowing the formation of novel layered structures. This Perspective briefly summarizes seminal examples of unique structure transformations achieved by anionic redox topochemistry as well as challenges on their syntheses and characterizations.

Sr2MnO2Na1.6Se2: A Metamagnetic Layered Oxychalcogenide Synthesized by Reductive Na Intercalation to Break [Se2]2– Perselenide Dimer Units

“…Sasaki et al recently proposed compounds containing these [Ch 2 ] 2– (Ch = S, Se) dimers as intercalation hosts, which differ from traditional intercalation hosts such as 2D or 1D van der Waals systems . They can operate as a “zipper”.…”

“…Sasaki et al recently proposed compounds containing these [Ch 2 ] 2– (Ch = S, Se) dimers as intercalation hosts, which differ from traditional intercalation hosts such as 2D or 1D van der Waals systems. 22 They can operate as a “zipper”. When reducing guest A is intercalated, the zipper opens via the reduction of dichalcogenide ions and the breaking of the Ch–Ch bonds, and the inserted A + cations balance the charge.…”