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Inorganics 2018, 6(2), 58; https://doi.org/10.3390/inorganics6020058

Molecular Engineering of High Energy Barrier in Single-Molecule Magnets Based on [MoIII(CN)7]4− and V(II) Complexes

Shubnikov Institute of Crystallography of Federal Scientific Research Centre “Crystallography and Photonics” RAS, Leninsky Prospect 59, 119333 Moscow, Russia
Received: 1 May 2018 / Revised: 25 May 2018 / Accepted: 28 May 2018 / Published: 30 May 2018
(This article belongs to the Special Issue Single-Molecule Magnets)
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Abstract

Molecular engineering of high energy barrier Ueff in single-molecule magnets (SMMs) of general composition MoIIIkVIIm based on orbitally-degenerate pentagonal-bipyramidal [MoIII(CN)7]4− complexes with unquenched orbital momentum and high-spin V(II) complexes is discussed. In these SMMs, the barrier originates exclusively from anisotropic Ising-type exchange interactions −Jxy(SixSjx + SiySjy) − JzSizSjz in the apical cyano-bridged pairs MoIII–CN–VII, which produce a double-well energy profile with a doubly degenerate ground spin state ±MS. It is shown that the spin-reversal barrier Ueff is controlled by anisotropic exchange parameters Jz, Jxy, and the number n of apical MoIII–CN–VII groups in a SMM cluster, Ueff ~ 0.5|JzJxy|n; it can reach a value of many hundreds of wavenumbers (up to 741 cm−1). This finding provides a very efficient straightforward strategy for further scaling Ueff to high values (>1000 cm−1) by means of enhancing exchange parameters Jz, Jxy, and increasing the number of [MoIII(CN)7]4− complexes in a SMM molecule. View Full-Text
Keywords: single-molecule magnet; magnetic anisotropy; spin-reversal barrier; anisotropic exchange interactions; Molybdenum(III) heptacyanometallate single-molecule magnet; magnetic anisotropy; spin-reversal barrier; anisotropic exchange interactions; Molybdenum(III) heptacyanometallate
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).
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Mironov, V.S. Molecular Engineering of High Energy Barrier in Single-Molecule Magnets Based on [MoIII(CN)7]4− and V(II) Complexes. Inorganics 2018, 6, 58.

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