Jump to main content
Jump to site search


High-temperature magnetic blocking and magneto-structural correlations in a series of dysprosium(III) metallocenium single-molecule magnets

Author affiliations

Abstract

A series of dysprosium(III) metallocenium salts, [Dy(CpiPr4R)2][B(C6F5)4] (R = H (1), Me (2), Et (3), iPr (4)), was synthesized by reaction of DyI3 with the corresponding known NaCpiPr4R (R = H, iPr) and novel NaCpiPr4R (R = Me, Et) salts at high temperature, followed by iodide abstraction with [H(SiEt3)2][B(C6F5)4]. Variation of the substituents in this series results in substantial changes in molecular structure, with more sterically-encumbering cyclopentadienyl ligands promoting longer Dy–C distances and larger Cp–Dy–Cp angles. Dc and ac magnetic susceptibility data reveal that these structural changes have a considerable impact on the magnetic relaxation behavior and operating temperature of each compound. In particular, the magnetic relaxation barrier increases as the Dy–C distance decreases and the Cp–Dy–Cp angle increases. An overall 45 K increase in the magnetic blocking temperature is observed across the series, with compounds 2–4 exhibiting the highest 100 s blocking temperatures yet reported for a single-molecule magnet. Compound 2 possesses the highest operating temperature of the series with a 100 s blocking temperature of 62 K. Concomitant increases in the effective relaxation barrier and the maximum magnetic hysteresis temperature are observed, with 2 displaying a barrier of 1468 cm−1 and open magnetic hysteresis as high as 72 K at a sweep rate of 3.1 mT s−1. Magneto-structural correlations are discussed with the goal of guiding the synthesis of future high operating temperature DyIII metallocenium single-molecule magnets.

Graphical abstract: High-temperature magnetic blocking and magneto-structural correlations in a series of dysprosium(iii) metallocenium single-molecule magnets

Back to tab navigation

Supplementary files

Publication details

The article was received on 01 Sep 2018, accepted on 18 Oct 2018 and first published on 18 Oct 2018


Article type: Edge Article
DOI: 10.1039/C8SC03907K
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    High-temperature magnetic blocking and magneto-structural correlations in a series of dysprosium(III) metallocenium single-molecule magnets

    K. Randall McClain, C. A. Gould, K. Chakarawet, S. J. Teat, T. J. Groshens, J. R. Long and B. G. Harvey, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C8SC03907K

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements