Communication
ChemComm
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zero dc field at various frequencies from 1 to 1500 Hz (ESI,† Fig. S7).
Clusters I to III displayed frequency-dependent in-phase (w0) and
out-of-phase (w00) signals at temperatures less than 5.0 K, indicating
the presence of slow relaxation of the magnetization that is char-
acteristic of SMMs.33 However, the out-of-phase (w00) signal for I
exhibited peaks at temperatures less than 2.8 K. In contrast, no such
peaks were observed for II and III in the same temperature range,
indicating that I exhibits a slightly stronger frequency dependence
than II and III. Considering that tunneling would make all the
maxima to fall at the same temperature but not to disappear, the
difference in the frequency-dependent out-of-phase (w00) signals
between I and II or III is probably related to the disorder of the
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22 Due to the poor-quality diffraction data of the enantiomer that
crystallizes in P3121, its structure was determined using the iso-
structural Gd compound.
+
NH4 in the crystal lattice. Although the energy barriers for I, II,
and III could not be obtained by fitting the Arrhenius expression,
if only one characteristic relaxation process is assumed to occur, the
energy barrier and t0 values can be approximated from fits of the ac
susceptibility data by adopting the Debye model and the equation
ln(w00/w0) = ln(ot0) + Ea/kBT, which has been applied for cluster
compounds.34 This analysis gave t0 E 7 ꢂ 10ꢀ5 s and Ea E 23 K
for I, t0 E 7 ꢂ 10ꢀ5 s and Ea E 9 K for II, and t0 E 7 ꢂ 10ꢀ5 s
and Ea E 10 K for III (ESI,† Fig. S8).
In conclusion, we have reported three polynuclear lanthanide
clusters, I, II, and III. Cluster I has S4 symmetry and crystallizes
in a centrosymmetric space group, whereas clusters II and III
have C2 symmetry and crystallize in a chiral space group. Cluster
I can reversibly transform into II and III if the NH4+ cation in I is
replaced with Et3NH+ and Me4N+, respectively. These results
indicate that symmetry breaking can be achieved through the
symmetric operation of achiral clusters with S4 symmetry. Magnetic
studies revealed existence of ferromagnetic interactions within the
clusters and anti-ferromagnetic interactions between the chiral
clusters in the lower-temperature range.
´
´
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We acknowledge the 973 Project from MSTC (grant no.
2012CB821704 and 2014CB845601) and the NNSFC (grant no.
21390391) and the Doctoral Fund of Ministry of Education of
China (20120121110012) for the financial support.
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