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

doi:10.1021/ic500885r

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 journal › Article › peer-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 language	English
Pages (from-to)	8970-8978
Number of pages	8
Journal	Inorganic Chemistry: including bioinorganic chemistry
Volume	53
Issue number	17
DOIs	https://doi.org/10.1021/ic500885r
Publication status	Published - 2 Sept 2014

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10.1021/ic500885r

http://pubs.acs.org/journal/inocaj

CCDC 1031794: Experimental Crystal Structure Determination
Kettles, F. J. (Contributor), Milway, V. A. (Contributor), Tuna, F. (Contributor), Valiente, R. (Contributor), Thomas, L. H. (Contributor), Wernsdorfer, W. (Contributor), Ochsenbein, S. (Contributor) & Murrie, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2014
DOI: 10.5517/cc13mnp2, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13mnp2&sid=DataCite
Dataset
CCDC 1031793: Experimental Crystal Structure Determination
Kettles, F. J. (Contributor), Milway, V. A. (Contributor), Tuna, F. (Contributor), Valiente, R. (Contributor), Thomas, L. H. (Contributor), Wernsdorfer, W. (Contributor), Ochsenbein, S. (Contributor) & Murrie, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2014
DOI: 10.5517/cc13mnn1, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13mnn1&sid=DataCite
Dataset
CCDC 1031792: Experimental Crystal Structure Determination
Kettles, F. J. (Contributor), Milway, V. A. (Contributor), Tuna, F. (Contributor), Valiente, R. (Contributor), Thomas, L. H. (Contributor), Wernsdorfer, W. (Contributor), Ochsenbein, S. (Contributor) & Murrie, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2014
DOI: 10.5517/cc13mnm0, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13mnm0&sid=DataCite
Dataset

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@article{01dbf71a2c044ae590e4c7b96e1916d3,

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

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. {\textcopyright} 2014 American Chemical Society.",

author = "Kettles, {Fraser J.} and Milway, {Victoria A.} and Floriana Tuna and Rafael Valiente and Thomas, {Lynne H.} and Wolfgang Wernsdorfer and Ochsenbein, {Stefan T.} and Mark Murrie",

year = "2014",

month = sep,

day = "2",

doi = "10.1021/ic500885r",

language = "English",

volume = "53",

pages = "8970--8978",

journal = "Inorganic Chemistry: including bioinorganic chemistry ",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "17",

}

TY - JOUR

T1 - Exchange interactions at the origin of slow relaxation of the magnetization in {TbCu3} and {DyCu3} single-molecule magnets

AU - Kettles, Fraser J.

AU - Milway, Victoria A.

AU - Tuna, Floriana

AU - Valiente, Rafael

AU - Thomas, Lynne H.

AU - Wernsdorfer, Wolfgang

AU - Ochsenbein, Stefan T.

AU - Murrie, Mark

PY - 2014/9/2

Y1 - 2014/9/2

N2 - 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.

AB - 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.

U2 - 10.1021/ic500885r

DO - 10.1021/ic500885r

M3 - Article

SN - 0020-1669

VL - 53

SP - 8970

EP - 8978

JO - Inorganic Chemistry: including bioinorganic chemistry

JF - Inorganic Chemistry: including bioinorganic chemistry

IS - 17

ER -

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

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Datasets

CCDC 1031794: Experimental Crystal Structure Determination

CCDC 1031793: Experimental Crystal Structure Determination

CCDC 1031792: Experimental Crystal Structure Determination

Cite this