Exchange interactions at the origin of slow relaxation of the magnetization in {TbCu3} and {DyCu3} single-molecule magnets

Fraser J. Kettles, Victoria A. Milway, Floriana Tuna, Rafael Valiente, Lynne H. Thomas, Wolfgang Wernsdorfer, Stefan T. Ochsenbein, Mark Murrie

    Research output: Contribution to journalArticlepeer-review

    Abstract

    New {TbCu3} and {DyCu3} single-molecule magnets (SMMs) containing a low-symmetry LnIII center (shape measurements relative to a trigonal dodecahedron and biaugmented trigonal prism are 2.2-2.3) surrounded by three CuII metalloligands are reported. SMM behavior is confirmed by frequency-dependent out-of-phase ac susceptibility signals and single-crystal temperature and sweep rate dependent hysteresis loops. The ferromagnetic exchange interactions between the central LnIII ion and the three CuII ions could be accurately measured by inelastic neutron scattering (INS) spectroscopy and modeled effectively. The excitations observed by INS correspond to flipping of CuII spins and appear at energies similar to the thermodynamic barrier for relaxation of the magnetization, ∼15-20 K, and are thus at the origin of the SMM behavior. The magnetic quantum number Mtot of the cluster ground state of {DyCu3} is an integer, whereas it is a half-integer for {TbCu 3}, which explains their vastly different quantum tunneling of the magnetization behavior despite similar energy barriers. © 2014 American Chemical Society.
    Original languageEnglish
    Pages (from-to)8970-8978
    Number of pages8
    JournalInorganic Chemistry: including bioinorganic chemistry
    Volume53
    Issue number17
    DOIs
    Publication statusPublished - 2 Sep 2014

    Fingerprint

    Dive into the research topics of 'Exchange interactions at the origin of slow relaxation of the magnetization in {TbCu3} and {DyCu3} single-molecule magnets'. Together they form a unique fingerprint.

    Cite this