Tetranuclear dysprosium single-molecule magnets: Tunable magnetic interactions and magnetization dynamics through modifying coordination number

Article abstract of DOI:10.1039/c8dt05004j

The study of mononuclear lanthanide-based systems, where the observed Single Molecule Magnets (SMMs) properties originate from the local magnetic anisotropy of the single lanthanide ion, has been extensively investigated in the literature. The case for po

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Tetranuclear Dysprosium Single-Molecule Magnets: Tunable
Magnetic Interactions and Magnetization Dynamics through
Modifying Coordination Number
Received 00th January 20xx,
Accepted 00th January 20xx
Kun Zhang,*,ab Gao-Peng Li,b Vincent Montigaud,d Olivier Cador,d Boris Le Guennic,*,d Jinkui
DOI: 10.1039/x0xx00000x
Tang*,c and Yao-Yu Wang*,b
www.rsc.org/
The study of mononuclear lanthanide-based systems, where the observed Single Molecule Magnets (SMMs) properties
originate from the local magnetic anisotropy of the single lanthanide ion, has been extensively investigated in the
literature. The case for polynuclear lanthanide SMMs becomes more challenging both experimentally and theoretically
due to the complexity of such architectures involving interactions between the magnetic centers. Much interest was
devoted to the study of the structural effect on the magnetic interactions and relaxation dynamics. However, the
understanding of the structural influence on those two factors remains a difficult task. To address this issue, a system
containing two structurally related tetranuclear Dy(III) SMMs, namely Dy4(L)4(OH)2(DMF)4(NO3)2]∙2(DMF)∙(H2O) (1) and
[Dy4(L)4(OH)2(DMF)2(NO3)2] (2) (H2L = 2-(2-hydroxy-3-methoxybenzylideneamino)phenol), is introduced and investigated.
Through modifying the ligands on the changeable coordination sites, the intramolecular magnetic interactions and
relaxation dynamics in these two Dy(III)4 SMMs can be tuned. Both complexes exhibit slow relaxation of their
magnetization with a relaxation barrier of 114K for complex 2 while a blocking temperature below 2K is observed for
complex 1. Ab initio calculations reveal that changes in coordination numbers and geometries on the Dy(III) sites can
significantly affect the magnetic interactions as well as single-ion anisotropy. The combination of experimental work and
ab initio calculations offers insight into the relationship between structures and magnetic properties and sheds light on the
rational design of future polynuclear lanthanide SMMs with enhanced magnetic properties.
performance, which has been demonstrated by the
dysprosium metallocene cation [(CpiPr5)Dy(Cp*)]+ (CpiPr5 = penta
-iso-propylcyclopentadienyl, Cp* = pentamethylcyclopentadien
Introduction
Considerable attention has been bestowed on single molecule
magnets (SMMs) due to their great potential applications in
molecular spintronics, quantum computing and high-density
information storage.1-5 These molecular systems are
characterized by an intrinsic magnetic anisotropy and slow
relaxation of their magnetization.6 The lanthanide Dy(III) ion,
by virtue of its intrinsic large magnetic anisotropy and Kramers
yl) with record magnetic hysteresis at temperatures of up to
80K and relaxation barrier of 1541 cm-1.7 Therefore, interest
towards developing Dy(III) SMMs has been continuously
growing. In this research activity, subsequent endeavors are
increasingly devoted to the understanding of magneto-
structural relationships, which could in turn offers guidelines
for the structural optimization of magnetic properties.8-12 In
fact, achievements have been made to illustrate how the
structural and electrostatic perturbation affects the relaxation
dynamics in mononuclear Dy(III) SMMs through modulating
the coordination environment around metal centers combined
with ab initio calculation analysis.13-16 According to those
explorations, outstanding mononuclear Dy(III) SMMs can be
reached by synthesizing the architectures with high-symmetry
geometry and/or strong axial crystal field.17-24 However, for
systems containing two or more metal ions, the case becomes
more challenging both experimentally and theoretically due to
the complexity of such architectures involving interactions
between the magnetic centers,25-28 for which the magnetic
phenomena become hardly predictable.29-34 Even so,
understanding the relationship between structure and
magnetic anisotropy involving single metal ion as well as
6
doublet ground state of H15/2, has shown to be the most
appealing constituent for the construction of SMMs with high
a. School of Textile Science and Engineering, Xi’an Polytechnic University, Xi’an,
710048, P.R. China. E-mail: zhangkun625@foxmail.com.
b. Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the
Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry,
College of Chemistry & Materials Science, Northwest University, Xi'an, 710127,
P.R. China. E-mail: wyaoyu@nwu.edu.cn.
c. State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of
Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P.R. China.
E-mail: tang@ciac.ac.cn.
d. Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) - UMR 6226,
F-35000 Rennes, France. E-mail: boris.leguennic@univ-rennes1.fr.
K. Zhang and G.-P. Li contributed equally to this work.
Electronic Supplementary Information (ESI) available: Additional magnetic data,
additional figures. CCDC 1884388 for 2. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/x0xx00000x
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magnetic interactions between two ions becomes more T magnet. Variable-temperature magnetization was measured with
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DOI: 10.1039/C8DT05004J
important when such properties have been shown to an external magnetic field of 500 Oe in the temperature range of
synergically improve the magnetic relaxation properties in 1.8–300 K and the frequency dependent ac susceptibility was
polynuclear Dy(III) molecules.35-37
measured with an oscillating field of 2.0 Oe. Finely ground
Recently, it has been demonstrated that even subtle microcrystalline powder of 2 was immobilized in eicosane matrix
variations of the coordination environment around Dy(III) ion inside a polycarbonate capsule. Both the contributions of the
might drastically change the single-ion magnetic anisotropy eicosan and the capsule have been subtracted from the data
and magnetic interactions involved in polynuclear Dy(III) SMMs. obtained. Phase purity was checked by powder X-ray diffraction
33,34
Therefore, an approach based on minute changes to the (PXRD) using a Bruker AXS D8 Advance diffractometer with Cu-Kα (λ
structure and/or electronic properties becomes an effective =1.54056 Å) radiation.
strategy to explore the factors influencing the magnetic
Synthesis of Complex [Dy4(L)4(OH)2(DMF)2(NO3)2] (2) The
interactions and relaxation dynamics, which would led to mixture of Schiff-base H2L ligand (0.2 mmol, 48.6 mg) and
advances in the design of higher performance polynuclear triethylamine (0.4 mmol, 0.06 ml) in acetonitrile (CH3CN) (5 ml) was
Dy(III) SMMs.37,38 However, due to the variable and high stirred for 10 min. Then, solid Dy(NO3)3•6H2O (0.3 mmol, 131.6 mg)
coordination numbers as well as poor directionality of the was added and further stirred for 30 min. Next, after stirring for 30
rare-earth metal, modulating the coordination environment min, the dimethylformamide (DMF) (5 ml) solution of
(coordination numbers and geometries) around metal centers in hexafluoroacetylacetone (0.2mmol, 0.03 ml) and triethylamine (0.2
polynuclear Dy(III) architectures is very difficult.39 Thus, a mmol, 0.03 ml) was added to the above mixture and further stirred
current challenge is to assemble targeted polynuclear for 1 h. The resulting solution was filtered and the filtrate was
dysprosium(III) SMMs, thereby providing a means of tuning allowed to stand at room temperature for two days. Yellow block-
the relaxation dynamics and magnetic interactions through the shaped crystals suitable for single crystal analysis were formed by
influence of different coordination environments around the slow evaporation of solvent and were collected by careful filtration
metal site.
(58% yield based on Dy). IR spectra (cm−1): 3612(m), 3421(m),
Herein, we demonstrate an intriguing and promising route 3057(m),2999(m), 2935(m), 1645(s), 1604(s), 1549(m), 1483(s),
to modulate the magnetic interactions and relaxation 1458(s), 1383(s), 1281(s), 1252(s), 1223(s), 1174(m), 1101(m),
dynamics in Dy(III)4 SMMs.40 Specifically, the template complex 1072(m), 1030(m), 970(m), 866(m), 820(m), 739(m), 700(m),
[Dy4(L)4(OH)2(DMF)4(NO3)2]·2(DMF)·(H2O) (1; H2L = 2-(2-hydroxy- 634(w), 567(m), 503(m). Elemental analysis found (calc.)% for
3-methoxybenzylideneamino)phenol), reported in our complex 2: C: 38.69(38.80); H: 3.09(3.15); N:5.88(5.84).
previous work, possesses two equivalent changeable Dy(III)
X-Ray Crystallography
sites with tunable coordination environment.34 In the present
Single-crystal X-ray diffraction measurements of the complexes
work, a Dy(III)4 SMM [Dy4(L)4(OH)2(DMF)2(NO3)2] is presented (2,
were carried out on a Bruker Apex II CCD diffractometer with
Figure 1), by removing two DMF ligands at the Dy1 site
graphite monochromated MoKα radiation (λ = 0.71073 Å) at 296 K
compared to complex 1, while the coordination environment
for 2. The structures were solved using the direct method (SHELXS)
and refined by means of the full-matrix least-squares method
(SHELXL) on F2.43 Anisotropic thermal parameters were used for the
around Dy2 center is not changed.41 Through this targeted
modification of coordination number and geometry on
determined metal sites, the intramolecular magnetic
non-hydrogen atoms and isotropic parameters for the hydrogen
interactions and relaxation dynamics in these two Dy(III)4
atoms. Hydrogen atoms were added geometrically and refined
SMMs can be modulated. Thus, the present [Dy4] system
using a riding model. Crystallographic data and refinement details
provides an elegant model to understand the factors that
are given in Table S1. CCDC 1884388 (2) contains the
supplementary crystallographic data for this paper. The structure of
2 has recently been reported by Li et al.41 for crystals obtained from
different sources and using different synthetic procedures, with
almost the same bond length and angle but very different magnetic
influence the magnetic interactions and relaxation dynamics
and a simple way to optimize the magnetic performance of the
polynuclear dysprosium SMMs.
properties (vide infra).
Experimental section
Chemicals and Physical Measurements
Results and discussion
Crystal structures
All reagents were purchased from commercial sources and used as
received. 2-(2-Hydroxy-3-methoxybenzylideneamino)phenol (H2L)
was prepared by condensation of 2-aminophenol and o-vanillin in a
1:1 molar ratio in hot ethanol according to a modified procedure re-
ported previously.42 All reactions were carried out under aerobic
conditions. Elemental analyses (C, H, N) were determined with an
Elementar vario EL III Analyzer. The FT-IR spectra were recorded
from KBr pellets in the range 4000-400 cm-1 on a Bruker Tensor 27
spectrometer. The magnetization data of complex 2 was recorded
on a Quantum Design VSM SQUID magnetometer equipped with a 7
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Fig. 1 Molecular structure of 1 and 2, hydrogen atoms and solvent
Direct current magnetic susceptibility measVuierwemArteicnletsOnlionef
molecules have been omitted for clarity. The {Dy4O8} core and the polycrystalline samples of complexes 1 andD2OaI:r1e0.p10e3rf9o/rCm8DeTd0u50n0d4eJr
modification of coordination environment around Dy1 and Dy1a an external field of 500 Oe in the temperature range of 1.8–300 K to
were highlighted.
probe their magnetic behavior (Fig. 2). The room-temperature χMT
values of 56.86 and 57.04 cm3 K mol−1 for 1 and 2 are in good
agreement with the expected value of 56.68 cm3 K mol-1 for four
uncoupled Dy(III) (6H15/2, g = 4/3) ions.45 When decreasing the
temperature, both complexes behave similarly with a decrease of
the χMT product. A sharp decrease below 50 K is observed upon
lowering temperature, reaching minimum values at 1.8 K of 36.26
cm3 K mol-1 for 1 and 28.69 for 2. The observed decrease of χMT can
be attributed to the gradually thermal depopulation of the Stark
sublevels of the Dy(III) ions and/or intramolecular
antiferromagnetic magnetic interaction between the Dy(III) ions, as
observed in other dysprosium complexes.46
The magnetization (M) plots as a function of field (H) for
complex 2 below 5 K (Fig. S2) reveals a relatively rapid increase of
the magnetization at low fields followed by a slow linear increase at
high fields without a clear complete saturation. The high-field linear
variation of the magnetization suggests the presence of excited
states relatively closed in energy to be mixed by the magnetic field.
This is also supported by the observation that, while plotting the M
vs HT-1 at different fields (Fig. S2), the curves are not all
superimposed on a single master-curve.47 As already showed for 1,
no hysteresis was observed for 2, in the range of [-30; 30] kOe at
1.8 K (Fig. S3).
Single-crystal X-ray structural analysis reveals that the two
complexes are centrosymmetric and crystallize in the monoclinic
P21/c space group. As seen in Fig. 1, the key feature of both
complexes is that four Dy(III) ions are nearly coplanar in a regular
parallelogram, forming a distorted defective dicubane {Dy4O8} core.
Specifically, in each of two symmetry-related Dy2(L)2 moieties of
both complexes, two Dy(III) ions (Dy1 and Dy2 or Dy1a and Dy2a)
are linked by two μ2-phenoxo oxygen atoms from two symmetry
equivalent L2- ligands, and the moieties are further linked by two μ3-
hydroxide ligands. Only small structural variations for the geometry
of {Dy4O8} core were found in the two complexes (Supporting
Information, Table S2). The coordination environment of Dy2 in
both complexes is completed by one N atom and four phenoxo O
atoms from L2- ligands and one μ3-hydroxide O, one methoxide O
and one DMF O, making it eight-coordinated with a distorted
square antiprism geometry. The very similar continuous shape
measures (5.413 and 6.206 for 1 and 2, respectively) of Dy2
determined by SHAPE software44 and bond lengths and angles
(Table S3) reveal almost identical coordination spheres of the Dy2
centers in 1 and 2. The Dy1 in 1 is nine-coordinated and builded
with one N atom and three phenoxo O atoms from L2- ligands and
two μ3- hydroxide O, two nitrate O and one DMF O, adopting a
distorted tricapped trigonal prism with a D3h point group. In
contrast, the Dy1 coordination sphere in complex 2 is obtained by
removing the DMF ligand from the Dy1 in complex 1 (Fig. 1).
Consequently, the Dy1 became eight-coordinated surrounded by
one N atom and three phenoxo O atoms from L2- ligands and two
μ3- hydroxide O, two nitrate O, adopting a distorted biaugmented
trigonal prism with a C2v point group. In addition, the intermolecular
Dy•••Dy distances are over 9 Å.
Magnetic properties
Fig. 3 Comparison of temperature dependent out-of-phase (M’’) ac
susceptibility for complexes 1 and 2 under zero dc field.
Compared to static magnetic properties, the dynamic properties
of lanthanide SMMs appear to be more sensitive to a subtle change
of the coordination environment surrounding the Dy(III) centers (in
our case, the coordination number and geometry), which can be
detected through ac magnetic susceptibility measurements at low
temperature.48 As shown in Fig. 3 and S4, both complexes display
temperature-dependent M’’ signal, which indicates slow relaxation
of the magnetization. However, no maximum value was observed
above 2 K for complex 1, suggesting a blocking temperature lower
than 2 K. In contrast, complex 2 shows different behaviour. The
maximum of M’ and M’’ value at 997 Hz are much higher than that
of complex 1 (Fig. 3). In order to extract relaxation times (τ), ac
susceptibility data can be fitted with a generalized Debye model, as
shown in Cole–Cole (M’’ vs. M’) diagrams (Fig. S5, S6, Table S4).49
Fig. 2 Plots of the T versus temperature for complexes 1 and 2 in
an applied magnetic field of 500 Oe. Inset: schematic
representation of the contributions of magnetic interactions
considered in the calculations.
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The plot of lnτ versus T-1 was obtained to gain insight into the Fig. 5 Schematic representation of the main g tensor VcioewmAprtoicnleeOnntlionef
dynamics of relaxation of the magnetization of 2. As seen in Fig. 4, each Dy center, green line for Dy1 and Dy1DaOaIn: d10b.1l0a3c9k/Clin8DeTf0o5r0D0y42J
an obvious curvature showed in the plot, indicating that a and Dy2a, for the model complexes 1’ 34 and 2’. Dy, O, N, F and C
combination of other relaxation mechanisms has to be taken into atoms are represented as orange, red, blue, yellow and grey
account. It is worth noting that other relaxation processes, such as spheres, respectively. H atoms are omitted for clarity.
Raman process, can coexist with Orbach relaxation. Therefore, the
The results revealed almost identical features at the Dy2/Dy2a
data over the entire temperature range were analyzed by the
sites between the two complexes with an almost pure (97%)
following equation (1):
|±15/2⟩ ground state and an Ising type, strongly axial anisotropy (gZ
lnτ = -ln[CT n + τ0-1exp(-Ueff/kB T)]
(1)
around 19.7), consistent with the above structural analysis (Table
S5-S12). For Dy1/Dy1a (the metal centers with varying coordination
numbers and geometries, vide supra), a different behavior was
found between model complexes 1’ and 2’. Indeed, a mixed ground
state with a major contribution of the |±15/2⟩ spin states was
obtained for Dy1 of 1’ (77% |±15/2> + 15% |±11/2>) corresponding
to a calculated ground state g tensor (gX = 0.49, gY = 1.22, gZ = 18.06).
In 2’, the variation of the coordination sphere around the Dy1/Dy1a
centers led to a decrease of the transversal components of the g
tensor (gX = 0.17, gY = 0.46 and gZ = 18.45) with a mixed ground
state (80% |±15/2> + 14% |±11/2>).
where the two terms represent the Raman and Orbach processes,
respectively (C is the coefficient of Raman process, Ueff is the energy
barrier to magnetization reversal, and kB is the Boltzmann constant).
The best fitting was found for C = 162.5 s-1 K-1.6, n = 1.6, τ0 = 1.58 ×
10-9 s, and Ueff/kB = 114 K. The obtained τ0 value falls into the
expected range of 10-5–10-12 s for the Dy(III)-based SMMs reported
previously.50
In order to get a global picture of the magnetic properties
observed in these complexes, intramolecular interactions (Fig. 2)
are taken into account in the calculations while intermolecular
magnetic interactions are not considered due to the large
intermolecular Dy•••Dy distances. The representation of the
calculated magnetic susceptibility for model 2’, χMT in the
temperature range of 2-300K are presented in Fig. S7. A first set of
calculations was performed considering only dipolar interactions
(Jdip, blue curve on Fig. S7). The resulting calculated χMT curve
reproduces the decrease upon cooling before reaching a minimum
value of 51.87 cm3 K mol-1 at 18 K. The χMT product then increases
upon further cooling to reach a value of 74.90 cm3 K mol-1 at 2 K.
This strong increase of the χMT values observed in the low
temperature range can be attributed to ferromagnetic dipolar
interactions between the Dy(III) centers. Clearly, contrary to
experimental results, the theoretical description of the low
temperature behavior of 2 misses some important components that
may be ascribed to exchange interactions. These exchange
interactions are considered in subsequent calculations (Jdip + Jex) in
order to balance the dipolar coupling contributions (Jdip). These
exchange parameters are fitted to obtain the best agreement with
the experimental dc magnetic data (Fig. S7). The exchange
interaction between the Dy2 and Dy2a centers (J22a) is not
considered in the calculations due to both the large Dy•••Dy
distance and the lack of bridging ligands. A scan over the three
different exchange values has been carried between -2.5 and 2.5
cm-1 (in the Ising model) and the set of J12, J11a and J21a values
corresponding to the best fit of the experimental χMT data obtained
for each compound are reported in Table 1.
Fig. 4 Plot of ln(τ) versus T-1 for 2 under zero dc-field, where τ is the
relaxation time, T is the temperature (K). The blue line represents
the fit to multiple relaxation processes using eqn 1.
Theoretical Calculations
To give more insights in the influence of the Dy(III) coordination
sphere modifications on the single-ion magnetic properties as well
as on the intramolecular magnetic interactions in these complexes,
ab-initio SA-CASSCF/SI-SO calculations were performed using the
Molcas 8.0 program package (computational details in Supporting
Information).51 Following the computational protocol employed in
our previous work on a model complex 1’,34 the principal
components of the g tensor and the wave function composition of
the ground state multiplet are calculated for each Dy centers of the
model complex 2′, in the effective spin ½ approximation. The
orientations of the main g-values (gZ components) of each Dy center
are represented in Fig. 5.
Table 1. Best fitted exchange values (cm-1, in the Ising model) for
model complexes 1’ and 2’ within the scan range [-2.5; 2.5] cm-1.
Complex J12 (cm-1) J21a(cm-1) J11a (cm-1)
1’
2’
-1.75
0
-2.5
-2
1
-2.25
From complexes 1 to 2, efforts have been focused on the
minute structural changes to explore the factors determining
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environment located on the Dy1/1a center. The results show that
the change of the coordination sphere around Dy1/1a, from nine-
coordinated in complex 1 to eight-coordinated in 2, leads to a slight
decrease of the antiferromagnetic contribution between the two
nonequivalent Dy(III) centers (J12) while the exchange contribution
between the two equivalent Dy(III) centers (J11a) evolve from ferro
to antiferromagnetic (Table 1). The low temperature χMT behavior
observed for 2 is explained by the overall antiferromagnetic
intramolecular Dy•••Dy exchange interactions that dominate the
ferromagnetic dipolar contributions.
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Conclusions
To summarize, the combination of experimental and
theoretical techniques allowed the study of a new Dy(III)4
complex. On one hand the expertise in the synthesis allowed
the selective change of coordination number and geometry on
one of the magnetic center. On the other hand, the theoretical
approach shed light on the effect of these structural
modifications on the magnetic properties both on the local
magnetic properties of the changeable site and on the
intramolecular magnetic framework existing between the four
magnetic Dy(III) ions. Indeed, the local change in the magnetic
properties, on the Dy1/1a sites, induced a modification of the
magnetic interactions within the polynuclear unit. These
modifications are reflected in the relaxation process occurring
in the system allowing an enhancement of the latter from less
than 2K for 1 to 114K for 2. This work offers hints in the
modulation and optimization of SMM properties in
dysprosium(III) polynuclear systems.
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Acknowledgements
This work was supported by National Natural Science
Foundation of China (Grants 21531007, 21525103 and 21521092),
Natural Science Basic Research Plan in Shaanxi Province of China
(Program No. 2018JQ2026), Scientific Research Program Funded by
Shaanxi Provincial Education Department (Program No. 18JK0355).
V.M. is thankful to ERC (project no. 725184) for fundings. B.L.G.
thanks the French GENCI/IDRIS-CINES center for high-performance
computing resources.
28 M. J. Giansiracusa, E. Moreno-Pineda, R. Hussain, R. Marx,
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DOI: 10.1039/C8DT05004J
The magnetic interactions and relaxation dynamics are modulated in two polynuclear
dysprosium(III) SMMs through a fine control of the coordination environment on the
changeable coordination sites.