Jump to main content
Jump to site search

Issue 30, 2018
Previous Article Next Article

Reversible ON–OFF switching of single-molecule-magnetism associated with single-crystal-to-single-crystal structural transformation of a decanuclear dysprosium phosphonate

Author affiliations

Abstract

{Dy5(EDDC)23-AcO)25-C15H11PO3)(μ4-C15H11PO3)(μ2-AcO)2(AcO)2(H2O)(CH3OH)2}24-C2O4xH2O (I), where H2EDDC is N′,N′′,E,N′,N′′,E-N′,N′′-(ethane-1,2-diylidene)dipyrazine-2-carbohydrazide and C15H11PO3H2 is 9-anthrylmethylphosphonic acid, is found to undergo two consecutive single-crystal-to-single-crystal transformations. The first is under UV irradiation (λ = 365 nm for 3 d in air) to {Dy5(EDDC)23-AcO)25-C15H11PO3)22-AcO)2(AcO)2(H2O)3}24-C2O4xH2O (I-UV) where the two CH3OH are replaced by two H2O and the second by annealing under N2 at 100 °C on a diffractometer or under Ar in a glovebox to {Dy5(EDDC)23-AcO)25-C15H11PO3)22-AcO)4(H2O)}24-C2O4) (I-A-N2 or I-A-Ar) where it has lost two H2O molecules. The second transformation is reversible by exposure to air at room temperature (I-A-N2-cool). While the overall structures are the same (retaining the space group P21/c), there is a considerable expansion of the unit cell from I (8171 Å3) to I-UV (8609 Å3) and I-A-N2 (8610 Å3) and the coordinations of the Dy atoms undergo major reconstructions. This is associated with switching the single-molecule-magnetism (SMM) from OFF for I to ON for I-UV and to OFF again for I-A-Ar in air. Such a switching mechanism associated with the retention of crystallinity is unique in the chemistry of dysprosium. The structure of the molecule is formed from two symmetry related pentamers joined by an oxalate. A related compound containing two isolated neutral pentamers {Dy5(EDDC)23-AcO)25-C15H11PO3)22-AcO)3(AcO)2(H2O)2}{Dy5(EDDC)23-AcO)25-C15H11PO3)(μ4-C15H11PO3)(μ2-AcO)3(AcO)2(CH3OH)2}·2CHCl3 (II) has also been isolated with closely related Dy coordination and it exhibits similar SMM behaviour in zero field.

Graphical abstract: Reversible ON–OFF switching of single-molecule-magnetism associated with single-crystal-to-single-crystal structural transformation of a decanuclear dysprosium phosphonate

Back to tab navigation

Supplementary files

Publication details

The article was received on 15 Mar 2018, accepted on 30 Jun 2018 and first published on 02 Jul 2018


Article type: Edge Article
DOI: 10.1039/C8SC01228H
Chem. Sci., 2018,9, 6424-6433
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    Reversible ON–OFF switching of single-molecule-magnetism associated with single-crystal-to-single-crystal structural transformation of a decanuclear dysprosium phosphonate

    H. Tian, J. Su, S. Bao, M. Kurmoo, X. Huang, Y. Zhang and L. Zheng, Chem. Sci., 2018, 9, 6424
    DOI: 10.1039/C8SC01228H

    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