Issue 17, 2019

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

Abstract

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
02 Feb 2019
Accepted
13 Mar 2019
First published
14 Mar 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 4652-4661

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

L. Liu, J. A. DeGayner, L. Sun, D. Z. Zee and T. D. Harris, Chem. Sci., 2019, 10, 4652 DOI: 10.1039/C9SC00606K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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