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A One-Dimensional Coordination Polymer Assembled from a Macrocyclic Mn(III) Single-Molecule Magnet and Terephthalate

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    A One-Dimensional Coordination Polymer Assembled from a Macrocyclic Mn(III) Single-Molecule Magnet and Terephthalate
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    • Sébastien Dhers
      Sébastien Dhers
      Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, P.O. Box 56, Dunedin 9054, New Zealand
      More by Sébastien Dhers
    • Rajni K. Wilson
      Rajni K. Wilson
      Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, P.O. Box 56, Dunedin 9054, New Zealand
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    • Mathieu Rouzières
      Mathieu Rouzières
      Université de Bordeaux, CNRS, Centre de Recherche Paul Pascal, UMR 5031, 33600 Pessac, France
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    • Rodolphe Clérac*
      Rodolphe Clérac
      Université de Bordeaux, CNRS, Centre de Recherche Paul Pascal, UMR 5031, 33600 Pessac, France
      *(R.C.) Email: [email protected]
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      Orcidhttp://orcid.org/0000-0001-5429-7418
    • Sally Brooker*
      Sally Brooker
      Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, P.O. Box 56, Dunedin 9054, New Zealand
      *(S.B) Email: [email protected]
      More by Sally Brooker
      Orcidhttp://orcid.org/0000-0002-5878-8238
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    Crystal Growth & Design

    Cite this: Cryst. Growth Des. 2020, 20, 3, 1538–1542
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    https://doi.org/10.1021/acs.cgd.9b01269
    Published January 13, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Herein the strategy of deliberate assembly of stable soluble macrocyclic single-molecule magnets (SMMs), using appropriately chosen linkers to bridge the axial sites, as a controlled way of forming single-chain magnets (SCMs) is tested. First, the manganese(III) macrocyclic complex, [MnIII(LPr)(NCS)2] (1), of the monoanionic tetradentate equatorial-N4-donor macrocyclic (LPr)− ligand (formed from [1 + 1] Schiff base condensation of 2,2′-iminobisbenzaldehyde and dipropylenetriamine) is shown to be an SMM. Then, the 1:1 reaction of SMM 1 with sodium terephthalate linkers in H2O/DMF is shown, by X-ray structure determination, to form dark red single crystals of the desired one-dimensional (1D) coordination polymer, [MnIII(LPr)(tpa)]n·nH2O·0.5nDMF (2), of alternating dicationic macrocycles [MnIII(LPr)]2+ (from 1) linked by the bridging dianionic linkers [tpa]2–. Despite having the desired structural features, magnetic measurements show that 2 is an SMM, not an SCM, as the coupling along the 1D coordination polymer is negligible (with Δeff/kB = 13.7(5) K and τ0 = 1.4(5) × 10–7 s). Future attempts to use this strategy of linking macrocyclic SMMs together to access SCMs will clearly require the use of linkers that are able to more efficiently relay the magnetic information along the resulting chain.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.cgd.9b01269.

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    CCDC 1939797 (for 2) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Crystal Growth & Design

    Cite this: Cryst. Growth Des. 2020, 20, 3, 1538–1542
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.cgd.9b01269
    Published January 13, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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