Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior
Abstract
Magnetic molecules that present a slow decay of their magnetization (molecular magnets) are very interesting both from a fundamental and applied points of view. While many approaches focus strongly on finding systems with strong magnetic anisotropy giving rise to large spin-reversal barriers, less is known on the behavior of magnetic tunnelling, which is also a fundamental component of molecular magnet behavior. In this work, we propose a model to describe both the spin-reversal barrier and magnetic tunnelling in Ni(II) trigonal bipyramidal complexes, which could be easily extended to other transitionmetal systems. Based on this model, we show the criteria that lead to the optimal complexes to find molecular magnet behavior. We test our proposal with multi-reference configuration-interaction (MRCI) and ligand-field-density-functional-theory (LF-DFT) first-principles calculations applied over several families of mononuclear Ni(II) complexes. As a salient result, we find that the complex... [NiCl3(Hdabco)(2)](+) (dabco is 1,4-diazabicyclo[2.2.2]-octane) displays both a very large magnetic anisotropy energy, 524 cm(-1), and a small tunnelling splitting, 0.2 cm(-1), when compared to other systems containing the same metal. We expect molecular magnet behaviour to be observed when small magnetic fields are employed to disrupt tunnelling. These values are reached due to the choice of ligands that favor a complete destruction of the Jahn-Teller distortions through spin-orbit coupling and an unquenched orbital momentum.
Source:
Chemical Science, 2014, 5, 4, 1453-1462Publisher:
- Royal Soc Chemistry, Cambridge
Funding / projects:
- Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-172035)
- Spanish Ministerio de Industria e Innovacion [FIS2009-07083]
- Serbian-Spanish collaboration project [PRI-AIBSE-2011-1230, 451-03-02635/2011-14/5]
Note:
- Peer-reviewed version: http://cer.ihtm.bg.ac.rs/handle/123456789/2912
DOI: 10.1039/c3sc52984c
ISSN: 2041-6520
WoS: 000332467400025
Scopus: 2-s2.0-84897744249
Collections
Institution/Community
IHTMTY - JOUR AU - Gruden-Pavlović, Maja AU - Perić, Marko AU - Zlatar, Matija AU - Garcia-Fernandez, Pablo PY - 2014 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1501 AB - Magnetic molecules that present a slow decay of their magnetization (molecular magnets) are very interesting both from a fundamental and applied points of view. While many approaches focus strongly on finding systems with strong magnetic anisotropy giving rise to large spin-reversal barriers, less is known on the behavior of magnetic tunnelling, which is also a fundamental component of molecular magnet behavior. In this work, we propose a model to describe both the spin-reversal barrier and magnetic tunnelling in Ni(II) trigonal bipyramidal complexes, which could be easily extended to other transitionmetal systems. Based on this model, we show the criteria that lead to the optimal complexes to find molecular magnet behavior. We test our proposal with multi-reference configuration-interaction (MRCI) and ligand-field-density-functional-theory (LF-DFT) first-principles calculations applied over several families of mononuclear Ni(II) complexes. As a salient result, we find that the complex [NiCl3(Hdabco)(2)](+) (dabco is 1,4-diazabicyclo[2.2.2]-octane) displays both a very large magnetic anisotropy energy, 524 cm(-1), and a small tunnelling splitting, 0.2 cm(-1), when compared to other systems containing the same metal. We expect molecular magnet behaviour to be observed when small magnetic fields are employed to disrupt tunnelling. These values are reached due to the choice of ligands that favor a complete destruction of the Jahn-Teller distortions through spin-orbit coupling and an unquenched orbital momentum. PB - Royal Soc Chemistry, Cambridge T2 - Chemical Science T1 - Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior VL - 5 IS - 4 SP - 1453 EP - 1462 DO - 10.1039/c3sc52984c ER -
@article{ author = "Gruden-Pavlović, Maja and Perić, Marko and Zlatar, Matija and Garcia-Fernandez, Pablo", year = "2014", abstract = "Magnetic molecules that present a slow decay of their magnetization (molecular magnets) are very interesting both from a fundamental and applied points of view. While many approaches focus strongly on finding systems with strong magnetic anisotropy giving rise to large spin-reversal barriers, less is known on the behavior of magnetic tunnelling, which is also a fundamental component of molecular magnet behavior. In this work, we propose a model to describe both the spin-reversal barrier and magnetic tunnelling in Ni(II) trigonal bipyramidal complexes, which could be easily extended to other transitionmetal systems. Based on this model, we show the criteria that lead to the optimal complexes to find molecular magnet behavior. We test our proposal with multi-reference configuration-interaction (MRCI) and ligand-field-density-functional-theory (LF-DFT) first-principles calculations applied over several families of mononuclear Ni(II) complexes. As a salient result, we find that the complex [NiCl3(Hdabco)(2)](+) (dabco is 1,4-diazabicyclo[2.2.2]-octane) displays both a very large magnetic anisotropy energy, 524 cm(-1), and a small tunnelling splitting, 0.2 cm(-1), when compared to other systems containing the same metal. We expect molecular magnet behaviour to be observed when small magnetic fields are employed to disrupt tunnelling. These values are reached due to the choice of ligands that favor a complete destruction of the Jahn-Teller distortions through spin-orbit coupling and an unquenched orbital momentum.", publisher = "Royal Soc Chemistry, Cambridge", journal = "Chemical Science", title = "Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior", volume = "5", number = "4", pages = "1453-1462", doi = "10.1039/c3sc52984c" }
Gruden-Pavlović, M., Perić, M., Zlatar, M.,& Garcia-Fernandez, P.. (2014). Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior. in Chemical Science Royal Soc Chemistry, Cambridge., 5(4), 1453-1462. https://doi.org/10.1039/c3sc52984c
Gruden-Pavlović M, Perić M, Zlatar M, Garcia-Fernandez P. Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior. in Chemical Science. 2014;5(4):1453-1462. doi:10.1039/c3sc52984c .
Gruden-Pavlović, Maja, Perić, Marko, Zlatar, Matija, Garcia-Fernandez, Pablo, "Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior" in Chemical Science, 5, no. 4 (2014):1453-1462, https://doi.org/10.1039/c3sc52984c . .