Slow Magnetic Relaxation Observed in Dysprosium Compounds Containing Unsupported Near-Linear Hydroxo- and Fluoro-Bridges

Article abstract of DOI:10.1021/acs.inorgchem.5b00343

The encapsulating N1,N3-bis(3-methoxysalicylidene)diethylenetriamine (H₂valdien) ligand was employed to isolate two novel Dy^III compounds which contain rare bridging pathways for lanthanide systems. Compound 1, [Na₂Dy

Full text of DOI:10.1021/acs.inorgchem.5b00343

Article
pubs.acs.org/IC
Slow Magnetic Relaxation Observed in Dysprosium Compounds
Containing Unsupported Near-Linear Hydroxo- and Fluoro-Bridges
Gabriel Brunet, Fatemah Habib, Ilia Korobkov, and Muralee Murugesu*
Department of Chemistry, University of Ottawa, 10 Marie-Curie, Ottawa, Ontario K1N 6N5, Canada
S
* Supporting Information
A B S T R A C T : T h e e n c a p s u l a t i n g N 1 , N 3 - b i s ( 3 -
methoxysalicylidene)diethylenetriamine (H2valdien) ligand was
employed to isolate two novel DyIII compounds which contain
rare bridging pathways for lanthanide systems. Compound 1,
[Na2DyIII2(valdien)2(μ-OH)(dbm)2(H2O)2][Na2DyIII2(valdien)2(μ-
OH)(NO3)2(dbm)2], where dbm− is dibenzoylmethanido, and
compound 2, [Na3DyIII2(valdien)2(μ-F)(μ3-F)2(Cl)2(MeOH)2]n·
0.5(MeOH)·(H2O), both exhibit linear lone hydroxo- and fluoro-
bridges, respectively, between the metal centers. The unit cell of 1
comprises two discrete dinuclear molecules, which differ slightly,
forming a cation−anion pair, while 2 forms a coordination polymer.
The magnetic investigations indicate that both compounds display
ferromagnetic coupling between the DyIII ions. Magnetic suscept-
ibility measurements in the temperature range 1.8−300 K reveal that
the DyIII ions in 1 are weakly coupled, resulting in a mononuclear single-molecule magnet-like behavior under an applied field. In
the case of 2, the stronger coupling arising from the fluoride-bridge, leads to zero-field single-molecule magnet (SMM) behavior
with a non-negligible anisotropy barrier (Ueff) of 42 K.
drastic impact on the magnetic relaxation.5b Similarly, the
bridging ligands, which act as potential superexchange path-
INTRODUCTION
■
Recent research into nanoscale magnetic materials has led to
ways, are also a key component in controlling the resulting
lanthanide ions becoming prime candidates in the synthesis of
magnetic behavior where the nonmagnetic ligands mediate the
coordination complexes. This can be partly attributed to their
inherently large spin−orbit coupling, thus leading to significant
magnetic coupling between metal ions. In fact, even the
magnetic anisotropy.1 Such anisotropy is known to lead to a
weakest coupling between two lanthanide ions can give way to
unique magnetic behavior such as intramolecular entangle-
magnet-like behavior of slow relaxation of the magnetization in
ment.5c Investigations on the type of magnetic interactions, or
these systems. Metal complexes which display these exciting
physical properties belong to a class of new magnetic materials,
lack thereof, which can be obtained from a specific type of
bridging moiety can provide further insight into understanding
termed single-molecule magnets (SMMs), that can potentially
magnetic behaviors leading toward higher energy barriers.
be employed in various high-tech devices such as memory
storage and quantum computers.2 The magnetic orbitals in
Consequently, we report the synthesis, structure, and magnetic
properties of two new lanthanide complexes featuring rare
lanthanide ions are located in the core 4f orbitals; thus,
bridging pathways for coordination complexes. The structural
superexchange pathways generally play a minimal role in the
magnetic interactions.3 Recent research, however, determined
element of a single hydroxide- or fluoride-bridge, in a near-
linear or linear fashion, between two metal centers proves to be
that the large anisotropy and non-negligible magnetic moments
quite uncommon for lanthanide coordination complexes, with
of lanthanide ions compensate for the weak exchange coupling
only three examples in the literature to date. Two dinuclear
and have yielded SMMs with the highest spin reversal barriers
EuIII-based systems have been reported by R. Tripier and co-
workers containing a linear Eu−F−Eu entity,6 while the
compound by Z. Shi et al. exhibits a 1D zigzag chain with
Dy2 cores bridged by unsupported fluoride anions, resulting in
slow relaxation of the magnetization under zero field.7 Also
notable is the work of J. Bendix and co-workers for their
magnetic studies carried out on 3d−4f systems which effectively
to date.4 Some of our recent studies involving a series of
lanthanide complexes containing {Dy2} cores have resulted in
high energy barriers for the reversal of the magnetization when
coordinated to the Schiff-base H2valdien ligand.5 It was also
discovered that the nature and strength of the magnetic
interaction between metal ions can be strongly influenced by
changes in the coordination environment of the metal center.
As an example, we have demonstrated that the use of stronger
electron withdrawing groups on capping ligands, while
maintaining a structurally comparable core, can indeed have a
Received: February 12, 2015
© XXXX American Chemical Society
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Scheme 1. Synthesis of the H2valdien Ligand
(w), 2890 (w), 1624 (s), 1596 (s), 1557 (m), 1519 (s), 1470 (s), 1401
(s), 1324 (s), 1215 (s), 1167 (m), 1108 (w), 1077 (m), 1040 (w),
1029 (w), 973 (m), 943 (w), 921 (m), 858 (m), 831 (m), 782 (w),
733 (s), 722 (s), 690 (m), 623 (m), 610 (m). Elemental analysis
expected: C 50.60%, H 4.49%, N 5.82%. Found: C 50.53%, H 4.28%,
N 5.66%.
display the potential of unsupported fluoride-bridges for
exhibiting slow magnetic relaxation.8 The high demand for
molecular magnetic systems with unsupported fluoride-bridged
linkages, due to their relative scarcity, is well-discussed in a
recent review by the aforementioned authors.9 Furthermore, it
is interesting to note that a few lanthanide organometallic
complexes do contain linear lone oxo-bridges; however, the
oxide products were often not intended as the reactions were
performed in inert atmosphere.10 Alternatively, to our knowl-
edge, there is only one example of a magnetic study carried out
on pure lanthanide coordination complexes with single near-
linear or linear hydroxo- or fluoro-bridges.7 Therefore, we set
out to investigate the resulting magnetic interactions from these
unusual bridging pathways for lanthanide coordination
complexes. The simplicity of dinuclear cores with centrosym-
metry allows for a better understanding of the magnetic
interaction between two spin carriers. The static and dynamic
susceptibility measurements reveal that both complexes exhibit
ferromagnetic coupling between the two DyIII centers as well as
slow relaxation of the magnetization.
Preparation of [Na3DyIII2(valdien)2(μ-F)(μ3-F)2(Cl)2(MeOH)2]n·0.5-
(MeOH)·(H2O) (2). Complex 2 was produced by the reaction of DyCl3·
6H2O (0.094 g, 0.25 mmol) in 5 mL of MeOH with H2valdien (0.092
g, 0.25 mmol) and Et3N (70 μL, 0.50 mmol) in 5 mL of MeOH and 5
mL of MeCN. The reagents were refluxed for 1 h at 80 °C. When
cooled to room temperature, NaF (0.031 g, 0.75 mmol) was added to
the reaction mixture giving a yellow solution. The resulting solution
was placed in a diethyl ether bath to facilitate crystallization. Colorless
rectangular crystals suitable for X-ray crystallography were obtained
over a period of 5 days with a yield of 35%. Selected IR (cm−1): 3568
(w), 3371 (br), 3211 (w), 2901 (w), 2834 (w), 2162 (w), 1979 (w),
1629 (s), 1598 (m), 1552 (w), 1470 (s), 1454 (s), 1406 (m), 1320
(m), 1233 (m), 1216 (s), 1169 (w), 1110 (m), 1079 (m), 1042 (w),
1044 (w), 973 (m), 933 (w), 914 (w), 857 (m), 834 (w), 784 (w), 726
(s), 623 (m). Elemental analysis expected: C 37.57%, H 4.30%, N
6.19%; %, F 4.19%. Found: C 37.76%, H 4.11%, N 6.44%, F 4.02%.
Preparation of [Na2GdIII2(valdien)2(μ-OH)(dbm)2(H2O)2]-
[Na2GdIII2(valdien)2(μ-OH)(dbm)2(NO3)2] (3). Compound 3 was
prepared following the same procedure as complex 1, using
Gd(NO3)3·6H2O (0.11 g, 0.25 mmol). X-ray quality colorless
rectangular crystals were recovered after 2 days. Yield: 66%. Selected
IR data (cm−1): 3281 (w), 2888 (w), 1623 (m), 1596 (m), 1518 (m),
1470 (s), 1452 (s), 1400 (s), 1324 (s), 1233 (m), 1214 (s), 1167 (w),
1108 (w), 1077 (m), 1039 (w), 972 (m), 942 (w), 917 (m), 857 (m),
828 (m), 733 (s), 722 (s), 691 (m), 622 (m), 610 (m). Elemental
analysis expected: C 51.04%, H 4.38%, N 5.95%. Found: C 50.78%, H
4.21%, N 5.90%.
EXPERIMENTAL SECTION
■
General Considerations. All manipulations were performed
under aerobic/ambient conditions. All materials were used as received
from Aldrich, TCI America, and Strem Chemicals without further
purification.
Synthesis of N1,N3-Bis(3-methoxysalicylidene)diethylenetriamine
(H2valdien). The H2valdien ligand was synthesized according to a
previously reported method,5a with a slight modification (Scheme 1).
The change of solvent from EtOH to i-PrOH has shown to facilitate
the precipitation process.
Physical Measurements. X-ray crystallographic data were
collected on single colorless crystals mounted on a glass fiber for
complexes 1−3. Unit cell measurements and intensity data collections
were performed on a Bruker-AXS SMART 1 k CCD diffractometer
using graphite monochromated Mo Kα radiation (λ = 0.710 73 Å).
The data reduction included a correction for Lorentz and polarization
effect, with an applied multiscan absorption correction (SADABS).11
The crystal structures were solved and refined using the SHELXTL
program suite.12 Direct methods yielded all non-hydrogen atoms
which were refined with anisotropic thermal parameters. All hydrogen
atom positions were calculated geometrically and were riding on their
respective atoms. Crystallographic data for the structures reported in
this paper have been deposited with the Cambridge Crystallographic
Center as supplementary publication no. CCDC 990947−990949.
Crystallographic data is presented in Table S1 of the Supporting
Information.
To a solution of o-vanillin (3.80 g, 0.025 mol) in 30 mL of isopropyl
alcohol, dried through molecular sieves, was added a solution of
diethylenetriamine (1.23 mL, 0.0125 mol) in 10 mL of isopropyl
alcohol. The resulting orange solution was refluxed for 2 h, and after
cooling to room temperature, the solvent was removed under reduced
pressure to give an orange oil. The latter oil was left to stand overnight
in a refrigerator at a temperature of 5 °C from which a yellow
precipitate was collected by suction filtration and washed with diethyl
1
ether. Yield = 96%. NMR H (CDCl3, 400 MHz): δ 2.97 (t, 2H,
CH2N), 3.69 (t, 2H, CH2N), 3.88 (s, 3H, OCH3), 6.90 (t, 1H,
Ar), 6.99 (d, 2H, Ar), 8.32 (s, 1H, NCH). Selected IR (cm−1): 3419
(w), 3056 (w), 2995 (w), 2935 (w), 2900 (w), 2835 (w), 1629 (m),
1468 (s), 1416 (m), 1376 (w), 1335 (w), 1269 (s), 1146 (w), 1128
(w), 1080 (m), 1024 (w), 964 (m), 875 (m), 838 (m), 778 (m), 734
(s), 665 (w).
Preparation of [Na2DyIII2(valdien)2(μ-OH)(dbm)2(H2O)2]-
[Na2DyIII2(valdien)2(μ−OH)(dbm)2(NO3)2] (1). The reaction of
dibenzoylmethane (Hdbm) (0.17 g, 0.75 mmol), H2valdien (0.090
g, 0.25 mmol), and NaOH (0.060 g, 1.50 mmol) in 8 mL of MeOH
and 5 mL of MeCN with Dy(NO3)3·6H2O (0.11 g, 0.25 mmol) in 2
mL of MeOH resulted in a clear yellow solution. The resulting filtrate
was placed in a diethyl ether bath to assist the crystallization process.
After 2 days, X-ray quality colorless rectangular-shaped crystals of 1
were isolated with a yield of 68%. Selected IR (cm−1): 3287 (w), 3152
Infrared spectroscopy was performed on a Nicolet 6700 FT-IR
spectrometer in the 400−4000 cm−1 range.
NMR analyses were conducted using the Bruker Avance 400 MHz
spectrometer equipped with an automatic sample charger and a 5 mm
autotuning broadband probe with Z gradient.
The magnetic susceptibility measurements were obtained using a
Quantum Design Superconducting Quantum Interference Device
(SQUID) magnetometer MPMS-XL7 that works between 1.8 and 300
K for direct current (dc) applied fields ranging from −7 to 7 T.
B
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Measurements were performed on restrained crushed polycrystalline
samples of 14.2, 18.8, and 15.0 mg of complexes 1−3, respectively,
wrapped in a polyethylene membrane. Alternating current (ac)
susceptibility measurements were performed under an oscillating ac
field of 3 Oe and ac frequencies that ranged from 0.1 to 1500 Hz. The
magnetization data was collected at 100 K to check for ferromagnetic
impurities that were absent in all samples. All magnetic data were
corrected for the sample holder as well as other diamagnetic
contributions.
of the H2valdien ligands to the metal ions is promoted by the
full deprotonation of the molecules through the addition of a
base, such as Et3N or NaOH, which enables the phenoxides to
act as bridging groups in both coordination pockets. Complex 1
also incorporates an additional chelating ligand, the dbm−
(dibenzoylmethanido) anion, which can exist in two possible
tautomeric forms. Under the basic conditions of the synthesis,
the negatively charged enol form of dbm− is favored. These
dbm− molecules serve as capping agents forming six-membered
coordination rings with the Dy atoms resulting in isolated
molecular entities. For compound 2, the addition of NaF was
initially used to introduce fluoride anions as secondary ligands;
however, single-crystal X-ray crystallography revealed that the
sodium cations had linked the {Dy2} units forming a stable
one-dimensional coordination polymer.
́ ́
Elemental analysis was performed at the Universite de Montreal.
RESULTS AND DISCUSSION
■
Syntheses. The H2valdien ligand has been synthesized
following a known procedure with slight modifications:5a
a
Schiff-base reaction between the primary amine groups of
diethylenetriamine and the aldehyde group of o-vanillin. The
increasingly well-known H2valdien ligand is an ideal candidate
to encapsulate the larger lanthanide ions due to its flexibility as
well as presenting two possible coordination pockets which can
encapsulate the metal center.5,13 The presence of multiple
coordination pockets, such as the N3O2 and O4 donor sets of
H2valdien, encourages the formation of multinuclear 4f
complexes while also allowing a certain degree of control
over the interaction between metal centers. In the cases of 1
and 2, the DyIII ions occupy the N3O2 pocket while the sodium
cations take up the O4 donor sets (Figure 1). The coordination
Structural Analysis. The molecular structures of 1 and 2,
obtained through single-crystal X-ray data are shown in Figures
2 and 3, respectively. The structural analysis of compound 1
Figure 3. Molecular structure of the dinuclear unit in compound 2.
Selected symmetry equivalent atoms are denoted by an additional “a”
in the label. The lone linear fluoro-bridge is shown in black bonds.
Color code: green (F), yellow (DyIII), red (O), blue (N), purple (Na),
light blue (Cl), and gray (C). Hydrogen atoms and solvent of
crystallization have been omitted for clarity.
Figure 1. Coordination pockets of the valdien2− ligand observed in 1
and 2. Color code: orange bonds (N3O2 pocket) and blue bonds (O4
pocket).
Figure 2. Molecular structures of compound 1A (left) and 1B (right). Symmetry equivalent labels are denoted by an additional “a” in the label
(Dy1a and Dy2a). The lone hydroxo-bridges are shown in black bonds. Color code: yellow (DyIII), red (O), blue (N), purple (Na), gray (C), black
(H). Selected hydrogen atoms are omitted for clarity.
C
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Figure 4. Coordination polyhedra of the DyIII ions showing the distorted dodecahedral geometry in 1A (left) and 1B (right).
shows a dinuclear core in which the DyIII atoms are eight-
coordinate and adopt a distorted dodecahedral geometry
(Figure 4). In comparison, compound 2 presents a polymeric
chain of {Dy2} units, where the metal centers are seven-
coordinate and are in a distorted pentagonal bipyramidal
geometry (Figure 5). Complex 1 crystallizes in the monoclinic
by an additional two oxygen atoms (O15 and O16 for 1A and
O5 and O6 for 1B) from dbm− and another oxygen atom
originating from a hydroxide ion (O17 in 1A and O10 in 1B),
while in 2, two fluorides take up the axial positions of the
pentagonal bipyramid. For 2, the Dy1−F1−Dy1a and Dy2−
F2−Dy2a angles have been determined to be ∼180°. In both
compounds, Na+ ions occupy the O4 coordination pocket of
the valdien2− ligand. In complex 1, the distance separating
Dy1−Dy1a and Dy2−Dy2a is 4.55 and 4.52 Å, respectively,
longer than typical DyIII dimers bridged by two hydroxides,14
while 2 has a separation of 4.40 and 4.42 Å between Dy1−Dy1a
and Dy2−Dy2a, respectively. Selected bond distances and
angles for 1 and 2 are presented in Table 1.
Table 1. Selected Bond Distances (Å) and Angles (deg) for 1
and 2
Figure 5. Coordination polyhedron of the DyIII ions showing the
slightly distorted pentagonal bipyramid in 2.
Compound 1
Dy1−N1
Dy1−N2
Dy1−N3
Dy1−O1
Dy1−O3
Dy1−O5
Dy1−O6
Dy1−O10
O5−Dy1−O6
Dy1−O10−Dy1a
2.515(3)
2.545(3)
2.563(3)
2.294(2)
2.253(2)
2.405(2)
2.447(3)
2.272(1)
69.26(8)
180.00
Dy2−N5
Dy2−N6
Dy2−N7
Dy2−O11
Dy2−O13
Dy2−O15
Dy2−O16
Dy2−O17
O15−Dy2−O16
Dy2−O17−Dy2a
2.549(4)
2.554(3)
2.569(4)
2.268(3)
2.270(3)
2.362(2)
2.451(3)
2.299(8)
68.39(9)
160.48
P21/n space group and exhibits centrosymmetric geometry
where the central oxygen atoms (O10 and O17) lie on an
inversion center. The element of centrosymmetry is strongly
supported by the fact that refinement in a different space group
resulted in a visible increase of the final Rf values. On the other
hand, compound 2 crystallizes in the triclinic P1 space group
̅
forming a chain consisting of a repeating unit of four DyIII ions
through the connection of two {Dy2} dimers. Each of the
{Dy2} cores displays centrosymmetric geometry through the
inversion centers which lie on F1 and F2. In both complexes,
the potential magnetic superexchange pathway between DyIII
ions is composed of a single bridging group, a hydroxide for 1
and a fluoride ion for 2. It is important to note that, in the case
of 2, the assignment of the central atom is not trivial due to the
isoelectronic nature of fluoride and hydroxide anions. The
higher stability of the fluoride anion, due to electronegativity
effects, as well as the striking similarities between the DyIII−F
distances for 2 (2.20 and 2.21 Å for Dy1−F1 and Dy2−F2,
respectively) and the only other reported single fluoride-bridge
between two DyIII ions (2.22 Å), strongly suggests the
assignment of fluoride;7 however, the nature of the bridging
ligand cannot be unambiguously determined. The coordination
spheres of all DyIII metal centers in 1 and 2 both include three
nitrogen atoms and two oxygen atoms belonging to the
pentadentate valdien2− ligand and therefore take up the N3O2
coordination pocket. It is noteworthy that the single-crystal X-
ray crystallography study for 1 revealed two dinuclear complex
in the same unit cell. The [Na2DyIII2(valdien)2(μ-OH)-
(dbm)2(H2O)2]+ cation will hereafter be referred to as 1A,
while the [Na2DyIII2(valdien)2(μ-OH)(dbm)2(NO3)2]− anion
will be 1B. In complex 1, the coordination sphere is completed
Compound 2
Dy1−F1
Dy1−F4
2.202(3)
2.137(4)
2.518(6)
2.505(6)
2.530(6)
2.239(4)
2.278(5)
4.403(4)
5.050(4)
180.00
Dy2−F2
Dy2−F3
2.209(2)
2.141(4)
2.502(6)
2.509(6)
2.516(6)
2.238(4)
2.273(5)
4.418(4)
180.00
Dy1−N1
Dy1−N2
Dy1−N3
Dy1−O2
Dy1−O3
Dy1−Dy1a
Dy1a-Dy2
Dy2−F2−Dy2a
Dy2−N4
Dy2−N5
Dy2−N6
Dy2−O6
Dy2−O7
Dy2−Dy2a
Dy1−F1−Dy1a
Furthermore, in both compounds the valdien2− ligand
molecules form a plane which is perpendicular to the lone
bridge. In compound 1, however, the dbm− groups are
positioned toward the extremities of the molecule and form
bite angles of 69.26° and 68.39° for Dy1 and Dy2, respectively.
These dbm− molecules act as capping agents and lead to the
formation of well-isolated compounds (Figure 2), whereas in 2,
the Na+ ions play a key role in the formation of a stable one-
dimensional coordination polymer (Figure 3). The repeating
unit of the chain is shown in Figure S1 in the Supporting
Information.
D
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In molecule 1A, terminal H2O groups are coordinated to
Na2 (Figure 2, left), while in 1B, terminal NO3 are
distance of 10.14 Å between the neighboring units. Close
inspection also reveals the presence of hydrogen bonding
between O18 of the terminal water molecule and O8 of an
adjacent nitrate group, which occurs through a distance of 2.77
Å. For 2, it can be seen from the packing arrangement along the
b axis in Figure 7 that the dinuclear units are linked via Na+ ions
−
coordinated to the corresponding Na1 ions (Figure 2, right).
Due to the different bridging modes observed between nitrate,
which is bidentate, and the water molecules, which are
monodentate, the resulting geometry of the Na+ ions is
affected. More precisely, in the structure of 1A, the Na2 ions
adopt a trigonal prismatic geometry whereas, in 1B, the Na1
ions are in a square face monocapped trigonal prism
arrangement. An additional difference in the molecular
structures of 1A and 1B to consider is the bridging of the μ-
OH groups. Compound 1B would represent the first example,
to our knowledge, of a linear hydroxo-bridge forming a Dy1−
O10−Dy1a angle as close as possible to 180°. However, in the
case of 1A, there is a 50%−50% disorder on the μ-OH oxygen
atom forming a Dy2−O17−Dy2a angle of 160.5°. This
variation of the bridging angle in the μ-OH moiety may be
caused by the structural differences between the two molecules,
which were previously mentioned. With the purpose of
verifying that the central oxygen atoms (O10 and O17) are
in fact hydroxo-bridges, bond valence sum (BVS) calculations
were carried out on these O atoms. The BVS values for both
corresponded to 1, indicating that the oxygen atoms are
monoprotonated (Supporting Information, Table S2). In order
to ascertain the accuracy of our calculations, we applied the
same equation on compounds consisting of two DyIII ions
bridged by an oxo center, as well as a Dy4 aggregate bridged by
a μ4-OH moiety, where in both cases the calculations correctly
predicted BVS values of 2 and 1, respectively, for the oxygen
atoms.10f,15
Figure 7. Packing arrangement of 2 along the b axis showing chains
aligned in a parallel fashion highlighting the lone linear bridges in
black. Color code: yellow (Dy), red (O), blue (N), light blue (Cl),
purple (Na), green (F), and gray (C). Methanol and water solvent
molecules are omitted for clarity.
into chains (this can also be seen in the packing diagrams along
the a and c axes in the Supporting Information, Figures S4 and
S5, respectively). The chains are arranged in a parallel fashion
with the closest interchain metal−metal distance of 11.80 Å.
The structural element of a near-linear lone hydroxo-bridge
proves to be a rare feature among metal complexes, where only
a handful have been reported to date.16 It is worth mentioning
that 1A and 1B are the first lanthanide-only compounds
containing this structural element. A few examples exist in the
literature for transition metal compounds containing single
hydroxo-bridges unsupported by ancillary ligands, notably a
dinuclear iron(III) compound with a Fe−O−Fe angle of
173.60° by C. A. Reed et al.,16b as well as another dinuclear
iron(III) compound synthesized by C. A. Grapperhaus and co-
workers giving a corresponding Fe−O−Fe angle of 166.70°.16d
It is interesting to point out that both compounds are cationic
species as in the case of 1A. In similar fashion to the hydroxo-
bridge, a linear or near-linear lone fluoro-bridge proves to be
just as uncommon, where, to our knowledge, there exists only
three reported pure lanthanide coordination compounds
exhibiting this feature.6,7 Consequently, we set out to
investigate the type of magnetic interaction that would arise
from such unique bridging pathways.
The packing diagram for 1 along the a axis, presented in
Figure 6, shows discrete dinuclear units with a zig-zag
arrangement of the molecules. This can also be illustrated
along the b and c axes from Supporting Information Figures S2
and S3, respectively. We can also observe an antiparallel
arrangement between the layers with the closest metal−metal
Magnetic Properties. It must be noted that while the
metal centers in both compounds are encapsulated in similar
fashion by the valdien2− ligand as well as display a similar type
of bridging, their inherent structural differences (i.e., seven vs
eight coordination numbers) will have a significant impact on
both the dc and ac magnetic susceptibilities due to the change
in crystal field splitting. Therefore, the following analysis of the
magnetic behaviors of 1 and 2 is of two very distinct systems.
The dc magnetic susceptibility measurements for both 1 and 2
were performed between 1.8 and 300 K under an applied dc
field of 1000 Oe. The χT versus T plots of 1 and 2 are
presented in Figure 8, where the χT product at room
Figure 6. Packing arrangement of 1 along the a axis showing the
antiparallel ordering of the molecules, as well as the intermolecular
hydrogen bonding as shown by the orange dotted lines. Color code:
yellow (Dy), red (O), blue (N), purple (Na), and gray (C).
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analogue of 2, it can be seen from the χT versus T plot that the
increase of the χT product at low temperature is more
pronounced in 2 at temperatures below 20 K. This behavior
may suggest a stronger interaction between metal centers
bridged by a single fluoride ion rather than a single hydroxide-
bridge; however, the difference in the χT product could also be
attributed to a change in the eigenvectors of the ground state.
Field dependence of the magnetization, M, measurements
show a rapid increase in the magnetization at low fields up to
10.1 μB (1) and 10.5 μB (2) at 1.8 K and 7 T (Figure 9).
Figure 8. Temperature dependence of the χT product at 1000 Oe for
compounds 1 (pink), 2 (blue), and 3 (green) with χ being the molar
magnetic susceptibility equal to M/H per mole of the compound. The
solid line corresponds to the best fit for 3.
Figure 9. Field dependence of the magnetization, M, at the indicated
temperatures for compounds 1 (left) and 2 (right) illustrating the
nonsaturation. Inset: M versus HT−1 plot showing nonsuperposition of
the magnetization curves at different temperatures.
temperature is 27.74 cm3 K mol−1 for 1 and 27.62 cm3 K mol−1
for 2, which is within reasonable agreement of the expected
value of 28.34 cm3 K mol−1 for two uncoupled DyIII ions
Additionally, the M versus HT−1 plots (Figure 9, insets), at
varying temperatures, show magnetization curves that are not
surperimposable on a single master curve. Consequently, these
plots suggest the presence of non-negligible magnetoanisotropy
and/or low-lying excited states for compounds 1 and 2. In the
case of the GdIII analogue, the observed saturation of 12.91 μB
at 7 T (Supporting Information Figure S6) is within reach of
the theoretical value of 14.00 μB (g = 2.00) for two GdIII ions.
Moreover, the magnetization curve can be fit using a Brillouin
function, which allows for a comparison of the g value derived
from the χT versus T fit. Using this method, a g value of 1.87
was obtained, which is comparable to the value calculated
through the χT versus T fit mentioned previously.
Alternating current (ac) magnetic measurements were
performed on 1 and 2 under zero dc field, in order to
investigate potential slow relaxation of the magnetization
originating from SMM behavior. For 1, the in-phase, χ′, plot
shows a frequency-dependent signal under zero applied dc field
(Figure 10, left). We can also observe a slight shoulder
structure around 5.5 K which can be more visible in the out-of-
phase component χ″. This shoulder in both the real (χ′) and
imaginary (χ″) components of the ac magnetic susceptibility
measurements indicates the presence of multiple relaxation
processes that can in part be attributed to the cocrystallization
5
4
(6H15/2, S = /2, L = 5, g = /3). For 1, the χT values remain
relatively constant before reaching a minimum value of 25.3
cm3 K mol−1 at 11 K and then increasing sharply to a maximum
value of 28.76 cm3 K mol−1 at 2 K. In compound 2, the χT
product continuously increases reaching a maximum of 55.4
cm3 K mol−1 at 1.8 K. For both compounds, the increase of χT
at low temperatures is indicative of intramolecular ferromag-
netic coupling between the metal centers. This weak interaction
is negligible at high temperature and is often masked at high
temperatures by the thermal population of the excited states of
DyIII ions, as is commonly observed in lanthanide com-
pounds.17 In order to probe the strength of the magnetic
interaction between lanthanide ions, the synthesis of GdIII
analogues is common practice due to its isotropic nature.18
While we successfully synthesized the GdIII analogue of 1,
identified as compound 3, we were unsuccessful in obtaining an
identical analogue of 2. At room temperature, the χT product of
3 was determined to be 14.60 cm3 K mol−1, which is in good
agreement with the expected value of 15.76 cm3 K mol−1 for
7
two uncoupled GdIII ions (8S7/2, S = /2; L = 0, g = 2).
Furthermore, it can be seen from Figure 8 that the magnetic
interaction between metal ions changes from ferromagnetic for
DyIII, to antiferromagnetic in GdIII, revealed by the decrease of
the χT value when lowering the temperature. A few examples of
this behavior have been previously reported and are explained
by the variation of the effective magnetic dipole moment at low
temperatures due to f−f interactions.19 The application of the
van Vleck equation to Kambe’s vector coupling scheme by
using the isotropic spin Hamiltonian H = −2JSa·Sb with Sa = Sb
7
= /2 allows us to reproduce the variation of χT versus T. The
best-fit parameters obtained are J = −0.051(3) cm−1 and g =
1.93(9). The exchange interaction for a pure lanthanide
dinuclear system through a single hydroxo-bridge is therefore
quite weak, due to the shielded f orbitals which prevent
adequate overlap with bridging ligand orbitals. It is interesting
to note, however, that while unsuccessful in obtaining the GdIII
Figure 10. Temperature dependence of the in-phase χ′ (left) and out-
of-phase χ″ (right) ac susceptibility signals under zero dc field for 1.
F
DOI: 10.1021/acs.inorgchem.5b00343
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
of the two structurally different {Dy2} units. Furthermore, a
frequency-dependent tail of a peak can be observed in the
variation of χ″, for measurements that lie at temperatures below
1.8 K (Figure 10, right), the operating limit of our SQUID.
Such χ″ signals are indicative of a slow magnetization relaxation
process and suggest possible SMM behavior.20 The presence of
merely tails of peaks rather than full peaks reveals that the slow
relaxation of the magnetization is highly influenced by the
quantum tunneling of the magnetization (QTM) through the
spin reversal barrier commonly found in dinuclear lanthanide
SMMs.21 Furthermore, without a clearly defined peak it is
difficult to quantify the energy barrier that prevents the reversal
of the spins. One method to shortcut the QTM involves the
application of a dc field during the ac measurements. With the
application of a 1000 Oe dc field on a polycrystalline sample of
1, the emergence of frequency-dependent ac peaks could be
clearly observed in the out-of-phase measurements (Figure S7
of the Supporting Information). This confirms the presence of
significant QTM, and thus, compound 1 can be considered as a
field-induced SMM.
higher temperatures, more symmetrical semicircles can be
obtained. The data can be fitted using a generalized Debye
model. The α values range from 0.03 up to 0.19 where the α
parameter has a tendency to be inversely proportional to the
temperature. In other words, with decreasing temperatures we
can expect an increase of the α values. This is in part due to the
QTM which occurs at low temperatures.
CONCLUSION
■
The use of H2valdien, an encapsulating Schiff-base ligand,
coupled with ancillary ligands, has allowed the synthesis of
three centrosymmetric lanthanide dimers which were fully
characterized. These compounds exhibit unique bridging
pathways for lanthanide coordination complexes. The lone
hydroxo-bridge, which effectively separates the DyIII ions in the
discrete molecules of 1, and similarly, the fluoride moieties of
the coordination polymer of 2, both induce ferromagnetic
interactions between metal centers. However, the GdIII
analogue of 1 revealed weak intramolecular antiferromagnetic
interactions giving a J = −0.05 cm−1. Furthermore, the DyIII
analogue of 1 exhibits slow relaxation of the magnetization, as
demonstrated under an applied field, while 2 displays SMM
behavior at zero-field with an anisotropic barrier of Ueff = 42 K.
To achieve our goal of isolating compounds with increasingly
higher energy barriers, an understanding of the magnetic
behaviors resulting from specific types of bridging pathways will
be essential. To this end, the present work reports three new
compounds containing rare near-linear unsupported hydroxide-
and fluoride-bridges as potential superexchange pathways in
lanthanide coordination compounds resulting in slow relaxation
of the magnetization.
For compound 2, ac measurements performed with zero dc
field resulted in a temperature and frequency-dependent signal
below 17 K. The χ″ component of the ac susceptibility clearly
exhibits a frequency-dependent full peak with one maximum
(Figure 11). This is indicative of superparamagnet-like behavior
ASSOCIATED CONTENT
■
S
* Supporting Information
Crystallographic data (including CIF files), additional structural
comparisons, and magnetic measurement plots for 1−3. The
Supporting Information is available free of charge on the ACS
Publications website at DOI: 10.1021/acs.inorgchem.5b00343.
Figure 11. Frequency dependence of the in-phase χ′ (left) and out-of-
phase χ″ (right) ac susceptibility signals under zero dc field for 2.
of slow magnetization relaxation of a SMM. The thermally
activated relaxation follows an Arrhenius-like behavior (τ = τ0
exp(Ueff/kT)), where the anisotropy energy barrier obtained
from the fitting is Ueff = 42 K (τ0 = 5.54 × 10−6 s) (Figure S8 of
the Supporting Information).
In order to further investigate the relaxation mechanism of 2,
the graphical representation of χ″ versus χ′ (Cole−Cole plot)
in the temperature range 1.8−14 K confirms the presence of a
single relaxation process (Figure 12). At temperatures below 2
K, QTM causes a slight distortion of the semicircles, while at
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: m.murugesu@uottawa.ca. Phone: 613-562-5800 ext.
2733. Fax: 613-562-5170.
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given the approval to the final version
of the manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the University of Ottawa, NSERC, and CIHR
(Discovery and RTI grants, Vanier Graduate Scholarship) as
well as CFI for their financial support.
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