Anion redox as a means to derive layered manganese oxychalcogenides with exotic intergrowth structures

S. Sasaki; S. Giri; S.J. Cassidy; S. Dey; M. Batuk; D. Vandemeulebroucke; G. Cibin; R.I. Smith; P. Holdship; C.P. Grey; J. Hadermann; S.J. Clarke

doi:10.1038/s41467-023-38489-3

Anion redox as a means to derive layered manganese oxychalcogenides with exotic intergrowth structures

S. Sasaki, S. Giri, S.J. Cassidy, S. Dey, M. Batuk, D. Vandemeulebroucke, G. Cibin, R.I. Smith, P. Holdship, C.P. Grey, J. Hadermann, S.J. Clarke

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Abstract

Topochemistry enables step-by-step conversions of solid-state materials often leading to metastable structures that retain initial structural motifs. Recent advances in this field revealed many examples where relatively bulky anionic constituents were actively involved in redox reactions during (de)intercalation processes. Such reactions are often accompanied by anion-anion bond formation, which heralds possibilities to design novel structure types disparate from known precursors, in a controlled manner. Here we present the multistep conversion of layered oxychalcogenides Sr ₂MnO ₂Cu _1.5 Ch ₂ (Ch = S, Se) into Cu-deintercalated phases where antifluorite type [Cu _1.5 Ch ₂] ^2.5- slabs collapsed into two-dimensional arrays of chalcogen dimers. The collapse of the chalcogenide layers on deintercalation led to various stacking types of Sr ₂MnO ₂ Ch ₂ slabs, which formed polychalcogenide structures unattainable by conventional high-temperature syntheses. Anion-redox topochemistry is demonstrated to be of interest not only for electrochemical applications but also as a means to design complex layered architectures.

Original language	English
Article number	2917
Number of pages	11
Journal	Nature Communications
Volume	14
DOIs	https://doi.org/10.1038/s41467-023-38489-3
Publication status	Published - 22 May 2023

Bibliographical note

For the purpose of open access, the author has applied a Creative Commons Attribution (CC BY) licence to any Author Accepted Manuscript version arising. The XRD and XAS measurements were carried out as a part of Diamond Light Source Block Allocations CY25166 on I11 and SP14239 on B18, respectively. Experiments at the ISIS Neutron and Muon Source were supported by a beamtime allocation XB2190055 from the Science and Technology Facilities Council.

Data Availability Statement

Data is available here: https://doi.org/10.5286/ISIS.E.RB2190055-1 . S.G. was supported by a University of Oxford Clarendon scholarship. S.S. thanks Mr. E. Yang and Dr. J. Holter from the University of Oxford for their training on Raman and SEM facilities, respectively.

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title = "Anion redox as a means to derive layered manganese oxychalcogenides with exotic intergrowth structures",

abstract = "Topochemistry enables step-by-step conversions of solid-state materials often leading to metastable structures that retain initial structural motifs. Recent advances in this field revealed many examples where relatively bulky anionic constituents were actively involved in redox reactions during (de)intercalation processes. Such reactions are often accompanied by anion-anion bond formation, which heralds possibilities to design novel structure types disparate from known precursors, in a controlled manner. Here we present the multistep conversion of layered oxychalcogenides Sr 2MnO 2Cu 1.5 Ch 2 (Ch = S, Se) into Cu-deintercalated phases where antifluorite type [Cu 1.5 Ch 2] 2.5- slabs collapsed into two-dimensional arrays of chalcogen dimers. The collapse of the chalcogenide layers on deintercalation led to various stacking types of Sr 2MnO 2 Ch 2 slabs, which formed polychalcogenide structures unattainable by conventional high-temperature syntheses. Anion-redox topochemistry is demonstrated to be of interest not only for electrochemical applications but also as a means to design complex layered architectures.",

author = "S. Sasaki and S. Giri and S.J. Cassidy and S. Dey and M. Batuk and D. Vandemeulebroucke and G. Cibin and R.I. Smith and P. Holdship and C.P. Grey and J. Hadermann and S.J. Clarke",

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AU - Clarke, S.J.

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N2 - Topochemistry enables step-by-step conversions of solid-state materials often leading to metastable structures that retain initial structural motifs. Recent advances in this field revealed many examples where relatively bulky anionic constituents were actively involved in redox reactions during (de)intercalation processes. Such reactions are often accompanied by anion-anion bond formation, which heralds possibilities to design novel structure types disparate from known precursors, in a controlled manner. Here we present the multistep conversion of layered oxychalcogenides Sr 2MnO 2Cu 1.5 Ch 2 (Ch = S, Se) into Cu-deintercalated phases where antifluorite type [Cu 1.5 Ch 2] 2.5- slabs collapsed into two-dimensional arrays of chalcogen dimers. The collapse of the chalcogenide layers on deintercalation led to various stacking types of Sr 2MnO 2 Ch 2 slabs, which formed polychalcogenide structures unattainable by conventional high-temperature syntheses. Anion-redox topochemistry is demonstrated to be of interest not only for electrochemical applications but also as a means to design complex layered architectures.

AB - Topochemistry enables step-by-step conversions of solid-state materials often leading to metastable structures that retain initial structural motifs. Recent advances in this field revealed many examples where relatively bulky anionic constituents were actively involved in redox reactions during (de)intercalation processes. Such reactions are often accompanied by anion-anion bond formation, which heralds possibilities to design novel structure types disparate from known precursors, in a controlled manner. Here we present the multistep conversion of layered oxychalcogenides Sr 2MnO 2Cu 1.5 Ch 2 (Ch = S, Se) into Cu-deintercalated phases where antifluorite type [Cu 1.5 Ch 2] 2.5- slabs collapsed into two-dimensional arrays of chalcogen dimers. The collapse of the chalcogenide layers on deintercalation led to various stacking types of Sr 2MnO 2 Ch 2 slabs, which formed polychalcogenide structures unattainable by conventional high-temperature syntheses. Anion-redox topochemistry is demonstrated to be of interest not only for electrochemical applications but also as a means to design complex layered architectures.

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Anion redox as a means to derive layered manganese oxychalcogenides with exotic intergrowth structures

Abstract

Bibliographical note

Data Availability Statement

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