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Dalton Transactions
Page 4 of 5
DOI: 10.1039/C6DT04490E
COMMUNICATION
Journal Name
where Jdip and Jexch are parameters of the dipolar and exchange (FWO) and the University of Leuven through the INPAC and
interactions respectively, while ꢏ
on the Dy(III) sites.
̃
= ±1/2 are the ground pseudospin Methusalem programs. V. V. is a post-doc of the Fonds
Wetenschappelijk Onderzoek-Vlaanderen.
Table 2 The Ising parameters for the magnetic interactions in
complexes 1 and 2
Notes and references
J
exch (cm-1)
Complex Jdip (cm-1)
1
R. D. Willett, D. Gatteschi and O. Kahn, Magneto-Structural
Correlations in Exchange Coupled Systems, Dordrecht, The
Netherlands, 1985.
Fitted (POLY_ANISO)
1
2
+6.03
+5.86
-7.33
-3.40
2
3
O. Kahn, Molecular Magnetism, VCH, New York, 1993.
W. H. Crawford, H. W. Richardson, J. R. Wasson, D. J.
Hodgson and W. E. Hatfield, Inorg. Chem., 1976, 15, 2107-
2110.
The dipolar interaction was calculated directly, while the
exchange-coupling parameters were determined by the fitting of
the magnetic susceptibility data (Fig. 2). The best fit is given by the
parameters shown in Table 2. This data shows that in both
complexes, the dipolar interaction (Jdip) is ferromagnetic, whereas
the exchange interaction (Jexch) is antiferromagnetic. In complex 1,
the exchange interaction is stronger than the dipolar interaction, so
the total magnetic interaction is antiferromagnetic. In contrast, the
dipolar interaction in complex 2 is stronger than the exchange
interaction and the total interaction is ferromagnetic. This agrees
4
(a) S. M. Gorun and S. J. Lippard, Inorg. Chem., 1991, 30,
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5446; (c) K. Zhang, M. Kurmoo, L. Q.
, 3516.
3
with the experimental data, in which complex
1 shows
6
7
L.E. Roy and T. Hughbank, J. Am. Chem. Soc., 2006, 128, 568-
575.
antiferromagnetic and complex 2 shows ferromagnetic behaviour
(Fig. 2). Thus, it can be concluded that the different magnetic
behaviours of complexes 1 and 2, despite their very similar
structures, result from the different sensitivities of the dipolar
interaction and the exchange interaction to the structural variations,
more specifically, from the different magnitudes of the exchange
interaction. Although the subtle structural variations cannot change
the sign of the exchange interaction, they significantly change its
magnitude, which is enough to make the dipolar interaction
stronger and, as a result, changes the sign of the total magnetic
interaction. This confirms that in lanthanide complexes, the
magnetic interactions can be tuned through even minor structural
variations. In addition, Table S10 shows the calculated low-lying
exchange levels. The exchange splitting is only 0.3 cm-1 in complex 1
and 1.4 cm-1 in complex 2. This explains why these two complexes
do not show a clear peak in the out-of-phase AC susceptibility at 2 K
(Fig. 3b, d). However, complex 2 has a more axial ground state
(Table S5-S9), which shows that the observed SMM behaviour in
complex 2 originates from a single Dy(III) ion, since at 4 K, the
exchange interaction does not play any role due to the small
exchange splitting of only 1.4 cm-1.
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In summary, slight structural variations within two structurally
similar dinuclear Dy(III) single molecule magnets has been
demonstrated to impart major changes in the magnetic interactions
states. The combination of our experimental observations with Ab
initio calculations improves our understanding about how the
transition between the two magnetic interaction states
(antiferromagnetic or ferromagnetic) could be triggered by
structural variations, which offers an illuminating insight into the
magneto-structural correlation for lanthanide complexes.
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This work was supported by the NSFC (Grants 21371142,
21531007, 21471124 and 21501142), the NSF of Shaanxi
Province (Grant 2016JQ2003) and China Postdoctoral Science
Foundation (Grant 2015M572590). D. L. is a PhD student
funded by the China Scholarship Council. V. V and L. F. C.
acknowledge the support of the Flemish Science Foundation
14 W.-B. Sun, P.-F. Yan, S.-D. Jiang, B.-W. Wang, Y.-Q. Zhang, H.-
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,
4 | J. Name., 2012, 00, 1-3
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