4.7 Article

Studies of magnetic properties and HFEPR of octanuclear manganese single-molecule magnets

Journal

DALTON TRANSACTIONS
Volume 39, Issue 42, Pages 10160-10168

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c0dt00405g

Keywords

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Funding

  1. National Science Council of Taiwan [NSC-96-2113-M-030-010-MY2, NSC98-2113-M-030-003-MY2]
  2. US National Science Foundation [DMR0924374]
  3. National Science Foundation [DMR-0654118]
  4. State of Florida
  5. U.S. Department of Energy

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A new octanuclear manganese cluster [Mn(8)(Hpmide)(4)O(4)(EtCOO)(6)](ClO(4))(2) (1) is achieved by employing Hpmide as the ligand, and this paper examines the synthesis, X-ray structure, high-field electron paramagnetic resonance (HFEPR), magnetization hysteresis loops and magnetic susceptibilities. Complex 1 was prepared by two different methods, and hence, was crystallized in two space groups: P3(2)21 for 1a and P3(1)21 for 1b. Each molecule possesses four Mn(II) and four Mn(III) ions. The metal-oxo framework of complex 1 consists of three face-sharing cubes with manganese ions on alternate corners. The four Mn(III) cations have their Jahn-Teller elongation axes roughly parallel to the c axis of the crystal lattice. The dc magnetic susceptibility measurements reveal a spin-frustration effect in this compound. The ac magnetic susceptibilities, as well as the magnetization hysteresis measurements, clearly establish that complex 1a is a single-molecule-magnet (SMM) with a kinetic energy barrier (10.4 cm(-1)) for spin reversal. HFEPR further confirms that complex 1a is a new SMM with a magnetoanisotropy and quantized energy levels. However, interpretation of the complete set of measurements in terms of a well defined spin ground state is not possible due to the spin frustration.

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