Reversible redox switching of magnetic order and electrical conductivity in a 2D manganese benzoquinoid framework
| Autor: | Lujia Liu, T. David Harris, Jordan A. DeGayner, Lei Sun, David Z. Zee |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Materials science Spintronics 010405 organic chemistry Sodium naphthalenide chemistry.chemical_element General Chemistry Manganese Conductivity 010402 general chemistry 01 natural sciences 0104 chemical sciences Metal chemistry.chemical_compound Paramagnetism chemistry Electrical resistivity and conductivity visual_art visual_art.visual_art_medium Physical chemistry Counterion |
| Zdroj: | Chemical Science. 10:4652-4661 |
| ISSN: | 2041-6539 2041-6520 |
| DOI: | 10.1039/c9sc00606k |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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