Inorganic Chemistry
Communication
with J/kB = −0.24(5) K and g = 2.02(5). This J value represents
the first estimation of an exchange coupling constant for a
cyanido-bridged RuIII/GdIII system.
ACKNOWLEDGMENTS
We are grateful to the UEFISCDI (Project PN-II-ID-JRP-RO-
FR-2011-2-0034), the Conseil Regional d’Aquitaine, the CNRS,
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In the absence of the magnetic data for other cyanide-based
RuIII/GdIII complexes, no comparison or magnetostructural
correlations can be made at this stage. Nevertheless, a
comparison with the exchange interaction of related systems
based on GdIII and another low-spin d5 ion, like FeIII, is possible.
For example, in the binuclear complex [(H2O)8Gd-NC-Fe-
(CN)5],11 the coupling is slightly larger, J/kB = −0.36 K (with H
= −2JSGd·SFe), but of the same order of magnitude. Obviously,
new cyanide-based MIII(d5)/GdIII complexes are necessary in
order to emphasize the role of the bridging angle, Gd−N−C, and
the role of the d metal ion (3d and 4d) on the magnitude of the
MIII−GdIII interaction. The field dependence of the magnet-
ization for 2 (Figures S1 and S2 in the SI) has been measured
below 8 K. The magnetization reaches 9.1 μB at 1.85 K and 7 T.
Thus, at this applied field, the weak antiferromagnetic
interactions (as it is also highlighted by the nonsuperposition
of the M versus H/T data; Figure S2 in the SI) are easily
compensated by the Zeeman effect. The discussion of the
magnetic properties for compounds 3 and 4 is less straightfor-
ward. The observed decrease of the χT product is due to the
superposition of two effects: depopulation of the Stark levels for
both TbIII and DyIII ions and likely weak intramolecular RuIII−
LnIII antiferromagnetic interactions. Nevertheless, weak ferro-
magnetic RuIII−LnIII interactions cannot be ruled out
completely, but in these two cases, if they are present, they are
overwhelmed by the intrinsic magnetic behavior of the LnIII ions.
The 1.8 K M versus H data for 3 and 4 (Figure S1 in the SI) show
that the saturation of the magnetization is not reached at 7 T
likely because of the strong magnetic anisotropy present in these
two systems, as it is also confirmed by the nonsuperposition of
the M versus H/T curves (Figure S2 in the SI). The alternating-
current measurements for all of the reported compounds did not
show any sign of slow relaxation of the magnetization above 1.8 K
and up to 1.5 kHz.
the University of Bordeaux, and the ANR (Grant ANR-12-IS07-
0004, CREMM project) for financial support.
DEDICATION
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Dedicated to Professor Herbert W. Roesky on the occasion of his
80th birthday.
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ASSOCIATED CONTENT
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S
* Supporting Information
Crystallographic data in CIF format [CCDC 1057815 (1) and
1057816 (3)], full experimental details, Figures S1 and S2, and
crystallographic Tables S1 and S2. The Supporting Information
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AUTHOR INFORMATION
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Corresponding Authors
Notes
The authors declare no competing financial interest.
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Inorg. Chem. XXXX, XXX, XXX−XXX