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Reversible redox switching of magnetic order and electrical conductivity in a 2D manganese benzoquinoid framework

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posted on 11.10.2020 by Lujia Liu
© 2019 The Royal Society of Chemistry. Materials with switchable magnetic and electrical properties may enable future spintronic technologies, and thus hold the potential to revolutionize how information is processed and stored. While reversible switching of magnetic order or electrical conductivity has been independently realized in materials, the ability to simultaneously switch both properties in a single material presents a formidable challenge. Here, we report the 2D manganese benzoquinoid framework (Me4N)2[MnII2(L2-)3] (H2L = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone), as synthesized via post-synthetic counterion exchange. This material is paramagnetic above 1.8 K and exhibits an ambient-temperature electrical conductivity of σ295 K = 1.14(3) × 10-13 S cm-1 (Ea = 0.74(3) eV). Upon soaking in a solution of sodium naphthalenide and 1,2-dihydroacenaphthylene, this compound undergoes a single-crystal-to-single-crystal (SC-SC) reduction to give Na3(Me4N)2[Mn2L3]. Structural and spectroscopic analyses confirm this reduction to be ligand-based, and as such the anionic framework is formulated as [MnII2(L3-)3]5-. Magnetic measurements confirm that this reduced material is a permanent magnet below Tc = 41 K and exhibits a conductivity value of σ295 K = 2.27(1) × 10-8 S cm-1 (Ea = 0.489(8) eV), representing a remarkable 200 000-fold increase over the parent material. Finally, soaking the reduced compound in a solution of [Cp2Fe]+ affords Na(Me4N)[MnII2(L2-)3] via a SC-SC process, with magnetic and electrical properties similar to those observed for the original oxidized material. Taken together, these results highlight the ability of metal benzoquinoid frameworks to undergo reversible, simultaneous redox switching of magnetic order and electrical conductivity.
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Liu, L. (2019). Reversible redox switching of magnetic order and electrical conductivity in a 2D manganese benzoquinoid framework. Chemical Science, 10(17), 4652-4661. https://doi.org/10.1039/c9sc00606k

Journal title

Chemical Science

Volume

10

Issue

17

Publication date

01/01/2019

Pagination

4652-4661

Publisher

Royal Society of Chemistry (RSC)

Publication status

Published

Online publication date

01/01/2019

ISSN

2041-6520

eISSN

2041-6539

Language

en

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