Structures, magnetic refrigeration and single molecule-magnet behavior of five rhombus-shaped tetranuclear Ln(iii)-based clusters

Article abstract of DOI:10.1039/d0nj01969k

A series of coplanar tetranuclear Ln(iii)-based clusters, namely [Ln4(acac)4(L)6(μ3-OH)2]·[solvent] (Ln = Eu (1), Gd (2), Tb (3), Dy (4) and Er (5)), have been synthesized by using an 8-hydroxyquinoline Schiff base ligand (HL = 5-(2-thenylidene)-8-hydroxylquinoline) and acetylacetone. Their structures and magnetic properties have been completely characterized. The structure determination shows that clusters 1-5 are isostructural with a rhombus-shaped Ln4 core. The magnetic studies reveal that the Gd4 cluster (2) displays cryogenic magnetocaloric effects with a maximum-ΔSm value of 22.09 J kg-1 K-1 at 2.5 K and ΔH = 7.0 T; while ac susceptibility measurements show that single molecule-magnet behavior is exhibited by the Dy4 cluster (4) with the anisotropic barrier (ΔE/kB) of 75.01 K. Interestingly, more than one maximal out-of-phase ac signals (χ′′) were observed in 4, suggesting the operation of multiple magnetic relaxation processes in 4. In addition, the solid state luminescence properties reveal that clusters 1, 3, and 4 display the characteristic lanthanum luminescence at room temperature. This journal is

Full text of DOI:10.1039/d0nj01969k

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DOI: 10.1039/D0NJ01969K
Structures, magnetic refrigeration and single molecule-
magnet behavior of five rhombus-shaped tetranuclear
Ln(III)-based clusters
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Wen-Min Wang,a,b Lei Huai,a Xi-Wen Wang,a Kai-Jun Jiang,b Hai-Yun Shen,b Hong-
Ling Gao,b Ming Fang, c Jian-Zhong Cuib
Abstract
A serie of coplanar tetranuclear Ln(III)-based clusters, namely [Ln4(acac)4(L)6(μ3-
OH)2]·[solvent] (Ln = Eu (1), Gd (2), Tb (3), Dy (4) and Er (5)), have been synthesized
by using an 8-hydroxyquinoline Schiff base ligand (HL = 5-(2-thenylidene)-8-
hydroxylquinoline) and acetylacetone. The structures and magnetic properties of them
have been completely characterized. The structures determinations show that clusters
1-5 are isostructural with a rhombus-shaped Ln4 core. The magnetic studies reveal that
Gd4 cluster (2) displays cryogenic magnetocaloric effects with maximum −ΔSm value
of 22.09 J kg−1 K−1 at 2.5 K and ΔH = 7.0 T; while ac susceptibility measurements
show that single molecule-magnet behavior occurs for Dy4 cluster (4) with the
anisotropic barrier (ΔE/kB) of 75.01 K. Interestingly, more than one maxima out-of-
phase ac signals (χ″) were observed in 4, suggesting the operation of multiple magnetic
relaxation processes in 4. In addition, the solid state luminescence properties reveal that
clusters 1, 3, and 4 display the characteristic lanthanum luminescence at room
temperature.
a Department of Chemistry, Taiyuan NormalUniversity, Jinzhong 030619, China
b
Department of Chemistry, Tianjin University, Tianjin, 300072, China
c Department of Chemistry, Hebei Normal University of Science & Technology, Qinhuangdao 066004, China
*Corresponding Authors E-mail：cuijianzhong@tju.edu.cn, fangmingchem@163.com.
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Introduction
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Polynuclear lanthanide-based clusters have attracted much attention and got a rapid
development due to the unabated interest in magnetocaloric effects, single-molecule
magnets (SMMs), luminescence properties and catalytic properties of them during the
past two decades.1-4 Among these applications, the investigation of Ln(III)-based
SMMs have been of much more interest, not only because of their interesting magnetic
properties but also owing to the rapid development of molecular magnetism materials.5
Since the first Ln(III)-based SMM, namely [Pc2Tb], has been synthesized by Ishikawa
group in 2003,6 the Ln(III)-based SMMs have experienced fast development and many
of them with intriguing magnetism have been reported.7 Tong, Zheng and Layfield
groups did original and excellent works in design and synthesis of Ln(III)-based
SMMs.8 In 2016, Tong group reported a Dy(III)-based SMM displaying excellent
magnetic property with the effective energy barrier Ueff as large as 1025 K;9 shortly
afterwards, the group of Zheng reported a nearly perfect pentagonal bipyramidal Dy
compound with the larger Ueff of 1815 K.10 In 2018, the record of effective energy
barrier (Ueff ) has been broken by the group of Layfield, a dysprosium metallocene
cation [(Cpi/Pr5)Dy(Cp*)] + with the largest Ueff of 2219 K was reported, setting a the
record in this field of Ln(III)-based SMMs.11 For polynuclear lanthanide-based SMMs,
lots of interesting and well works were reported by the group of Tang.12 Among these
studies of polynuclear Ln(III)-based clusters, Dy3, Dy4 and Dy6 clusters with
outstanding SMMs behaviors were reported widely.13 These studies attracted and
promoted a rapid development of polynuclear Ln(III)-based SMMs.
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For another research field of polynuclear lanthanide-based clusters, the research of
magnetic refrigerant was one of frontier hot. Magnetic refrigeration depends on the
magnetocaloric effect (MCE), which represents isothermal magnetic entropy change
(ΔSm) and adiabatic temperature (ΔTad) in change of applied magnetic field.14
Researches show that the Gd(III) ion is the best and unique candidate for
constructing magnetic refrigeration materials.15 In view of this, lots of Gd(III)-based
clusters showing well and excellent magnetic refrigeration properties have been
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reported in these years.16 In 2014, Long’s group reported an unprecedented Gd104
DOI: 10.1039/D0NJ01969K
5
6
−1
cluster with a large magnetic entropy change (-ΔSm) of 46.9 J kg −1
K
(T = 2.0 K and
7
8
ΔH = 7 T).17 In 2015, a Gd60 nanocage with larger magnetic entropy change of -ΔS =
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−1
66.5 J kg −1
K
(T = 3K, ΔH =7 T) was reported by Zhao group. 18 It seems that the
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high nuclear Gd(III)-based clusters can get larger -ΔS values and excellent
magnetic refrigeration properties.
According to the above, although many exciting works based on the Ln(III)-based
mononuclear compounds or polynuclear clusters have been reported, there is still a
challenge for designing and constructing Ln(III)-based polynuclear clusters with
outstanding magnetic properties.19 In these years, our work mainly focus on the study
of magnetic refrigeration and single molecule magnets of Ln(III)-based polynuclear
clusters, and some Ln4 or Ln6 (LnIII = Gd and Dy) clusters show well magnetic
properties.20 Continue the previous work, in this paper, we have designed and
synthesized a series of rhombus-shaped tetranuclear lanthanide [Ln4] clusters
constructed by 8-hydroxyquinoline Schiff base and acetylacetone ligands (Scheme 1).
The structures and magnetic properties of them have been systematically studied in this
work.
Scheme 1 Thestructures of HL(left) and acac (right).
Experimental Section
Materials and Methods
All chemicals, rare earth salts and solvents used for the syntheses were reagent grade
without further purification. The β-diketionate salts Ln(acac)3·2H2O (Ln (III) = Eu, Gd,
Tb, Dy and Er) were synthesized according to the method in the literature.21 The 8-
hydroxyquinoline Schiff base ligand HL were synthesized according to the already
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reported methods.22
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Elemental analyses (EA) for C, H and N were performed on a Perkin-Elmer 240
CHN elemental analyzer. IR spectra were recorded in the range of 400−4000 cm-1 with
a Bruker TENOR 27 spectrophotometer using a KBr pellet. PXRD data were examined
on a Rigaku Ultima IV instrument with Cu Kα radiation (λ = 1.54056 Å), with a scan
speed of 10° min−1 in the range of 2θ = 5 − 50°. Luminescence properties were recorded
on an F-4500 FL spectrophotometer with a xenon arc lamp as the light source.
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Synthesis section
Synthesis of clusters 1-5. Ln(acac)3·2H2O (0.03 mmol) (Ln = Eu (1), Gd (2), Tb (3),
Dy (4) and Er (5)) and HL (0.03 mmol) were dissolved in acetonitrile / CH2Cl2 solution
(15 mL /5 mL). Then the mixture solution was stirred for about 4 h at 70 ℃. Finally, the
solution was filtered and kept in the dark and concentrated slowly by evaporation at
4 ℃. After about 5 days, light-colored yellow block crystals suitable for single crystal
X-ray diffraction analysis were isolated.
[Eu4(acac)4(L)6(μ3-OH)2]·CH3CN (1). Yield: 32% (based on Eu). Elemental
analysis (%) calcd for C106H87Eu4N13O16S6 (Fw = 2599.08): C, 48.94; H, 3.35; N, 7.00.
Found: C, 49.08; H, 3.29; N, 6.91. IR (KBr, cm−1): 3683 (m), 1560 (s), 1511 (s), 1464
(s), 1395 (m), 1312 (s), 1251 (w), 1093 (m), 1016 (w), 837 (m), 786 (m), 705 (m).
[Gd4(acac)4(L)6(μ3-OH)2]·CH3CN (2). Yield: 35% (based on Gd). Elemental
analysis (%) calcd for C106H87Gd4N13O16S6 (Fw = 2620.24): C, 48.55; H, 3.32; N, 6.95.
Found: C, 48.48; H, 3.46; N, 7.09. IR (KBr, cm−1): 3681 (m), 1558 (s), 1510 (s), 1465
(s), 1395 (m), 1310 (s), 1250 (w), 1093 (m), 1016 (w), 836 (m), 785 (m), 705 (m).
[Tb4(acac)4(L)6(μ3-OH)2]·CH3CN (3). Yield: 31% (based on Tb). Elemental analysis
(%) calcd for C106H87N13O16S6Tb4 (Fw = 2626.92): C, 48.42; H, 3.31; N, 6.93. Found:
C, 48.56; H, 3.48; N, 7.05. IR (KBr, cm−1): 3684 (m), 1560 (s), 1510 (s), 1464 (s), 1397
(m), 1313 (s), 1250 (w), 1095 (m), 1013 (w), 835 (m), 788 (m), 706 (m).
[Dy4(acac)4(L)6(μ3-OH)2]·CH3CN (4). Yield: 45% (based on Dy). Elemental
analysis (%) calcd for C106H87Dy4N13O16S6 (Fw = 2641.24): C, 48.16; H, 3.29; N, 6.89.
Found: C, 48.27; H, 3.15; N, 6.80. IR (KBr, cm−1): 3628 (m), 1598 (s), 1512 (s), 1463
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(s), 1397(s), 1313 (s), 1252 (w), 1093 (s), 1016 (w), 921 (w), 838 (m), 786 (s), 707 (s).
[Er4(acac)4(L)6(μ3-OH)2]·2CH3CN (5). Yield: 31% (based on Er). Elemental
analysis (%) calcd for C108H90Er4N13O17S6 (Fw = 2701.33): C, 47.98; H, 3.33; N, 6.74.
Found: C, 47.68; H, 3.45; N, 6.98. IR (KBr, cm−1): 3630 (m), 1598 (s), 1514 (s), 1465
(s), 1397(s), 1315 (s), 1250 (w), 1095 (s), 1015 (w), 920 (w), 837 (m), 786 (s), 705 (s).
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Magnetic measurements
Magnetic measurements were performed with a Quantum Design MPMS-XL7 and a
PPMS-9 ACMS magnetometer in temperature ranges 2.0–300 K. The polycrystalline
samples were grounded and placed in a gel capsule. A small amount of eicosane was
used to avoid movement of the sample during the measurement. Diamagnetic
corrections for the compounds were estimated using Pascal’s constants, and magnetic
data were corrected for diamagnetic contributions of the sample holder.23 Magnetic data
were fitted using the 0rigin 8.0 software.
Crystal Structure Determinations
Single crystal X-ray diffraction data of 1−5 were collected on a computer-
controlled Bruker P4 CCD area detector diffractometer, equipped with confocal
monochromatized Mo K radiation with a radiation wavelength of 0.71073 Å using the
- scan technique. The structures were solved by direct methods and refined with a
full-matrix least-squares technique based on F2 using the SHELXS-2016 and SHELXL-
2016 programs.24 Anisotropic thermal parameters were assigned to all non-hydrogen
atoms. The crystals of 1-5 were measured as soon as they were isolated from the
reaction solvents, hence, some disordered free solvent molecules were still existed in
the crystal structures. Some free solvent molecules were removed via “SQUEEZE” due
to their extreme disorder which can not be solved. Crystallographic data and structural
refinement parameters are listed in Table 1. The important bond lengths (Å) and angles
(°) for 1–5 are given in Tables S1−S5 (in ESI). CCDC (1; 1585585, 2; 1585587, 3;
1585588, 4; 1585589, 5; 1585590) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre.
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Table 1. Crystallographic Data and Structure Refinements for clusters 1-5.
Compounds
1
C106H87Eu4N13O16S6
2599.08
2
C106H87Gd4N13O16S6
2620.24
3
C106H87N13O16S6Tb4
2626.92
4
C106H87Dy4N13O16S6
2641.24
5
formula
C108H90Er4N13O17S6
2701.33
Mr (g mol−1
T (K)
)
113.15
113.15
113.15
113.15
113.15
cryst syst
Monoclinic
P21/n
Monoclinic
P21/n
Monoclinic
P21/n
Monoclinic
P21/n
Monoclinic
P21/n
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Space group
a (Å)
b (Å)
c (Å)
15.148(3)
12.762(2)
28.486(4)
90
15.115(5)
12.699(4)
28.477(9)
90
15.1763(9)
12.7802(7)
28.3434(16)
90
15.194(3)
12.779(2)
28.304(5)
90
15.189(2)
12.7422(19)
28.246(4)
90
 ()
 ()
101.850(9)
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102.116(8)
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102.5790(10)
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102.649(4)
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102.961(2)
90
γ ()
V (Å3)
5389.5(15)
2
5344(3)
2
5365.4(5)
2
5362.3(15)
2
5327.3(14)
2
Z
3
cryst size (mm )
0.20 x 0.18 x 0.12
1.602
0.20 x 0.18 x 0.12
1.628
0.20 x 0.18 x 0.12
1.626
0.20 x 0.18 x 0.12
1.635
0.20 x 0.16 x 0.12
1.684
−3
Dc (g cm )
−1
μ (mm )
2.480
2.636
2.790
2.941
3.307
Rint
0.0597
0.0932
0.0238
0.0356
0.1515
limiting indices
-17<=h<=17
-15<=k<=15
-33<=l<=33
42915
-17<=h<=17
-14<=k<=15
-32<=l<=33
43749
-18<=h<=15
-15<=k<=15
-31<=l<=33
44596
-19≤ h ≤19
-16<=k<=16
-23<=l<=36
53324
-18<=h<=18
-15<=k<=15
-33<=l<=33
38038
reflns collected
params
773
726
773
726
735
GOF on F2
1.090
1.084
1.084
1.073
1.013
R1, wR2 [I >2σ(I)]
R1, wR2 (all data)
0.0648, 0.2021
0.0755, 0.2106
0.0763, 0.1667
0.1232, 0.1871
0.0339, 0.0982
0.0385, 0.1010
0.0302, 0.0802
0.0370, 0.0835
0.0357, 0.0813
0.0463, 0.0832
Results and discussion
Crystal structures of clusters 1–5
Single-crystal X-ray diffraction analysis reveal that clusters 1–5 are isomorphous and
crystallize in the monoclinic system space group P21/n with Z = 2, so, the structure of
Dy(III)-based cluster 4 is selected and described in detail. As shown in Fig. 1, the
molecular structure of 4 is mainly composed of four Dy3+ ions, four acac-, six Schiff
base ligand L- and two μ3-OH. Each central Dy3+ is eight coordinated, and their
coordination polyhedrons can be described as a distorted square-antiprismatic geometry
(Table S6), which was identified by using Shape 2.0 software. The Dy1 atom connected
by two N atoms (N1 and N3) and six O atoms (O1, O2, O3, O4, O5, and O8), while the
central Dy2 atom is connected by one N atom (N5) and seven O atoms (O1a, O2a, O3,
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O6, O7, O8, and O8a) with a O7N coordination environment (Fig. S1). The Schiff base
ligand L- adopts a μ2-O coordination mode to connect two central Dy3+ ions, and the
acac- adopts a bidentate chelate coordination mode to connect each central Dy3+ ion
(Fig. 2). The core four Dy3+ ions are bridged by six μ2-O and two μ3-O atoms forming
a rhombus-shaped [Dy4] (Fig. S2). In the Dy4 core, the important bond lengths of Dy-
N are in the range of 2.513(3)–2.548(3) Å, and Dy–O bond lengths are in the range of
2.301(2)-2.416(2) Å; and the O–Dy–O bond angles are in the range of 67.81(8)–
144.61(9)°. These important bond lengths and bond angles are comparable to those of
already reported Dy4 clusters.25 Furthermore, the adjacent Dy···Dy distances of 4 are
3.5381(8) and 3.8616(6) Å, and the bidiagonal Dy···Dy distances are 3.8114(9) and
6.3508(10) Å. The Dy2−Dy1−Dy2a and Dy1−Dy2−Dy1a angles are 118.178°and
61.822°.
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Fig. 1 Molecular structure for 4 (solvent molecules and all hydrogen atoms are omitted for clarity).
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Fig. 2 Coordination modes of HL (left) and acac− (right) in 4.
Powder X-ray diffraction
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To confirm the phase purity of Ln4 clusters 1−5, the polycrystalline products of 1−5
have been characterized by X-ray powder diffraction (PXRD) at room temperature (Fig.
S3). The observed XRD patterns are in good agreement with the results simulated from
the single crystal data, indicating the high purity of the synthesized polycrystalline
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samples 1-5.
Luminescence properties
The solid-state luminescence properties of three Ln4 clusters 1, 3 and 4 were
measured at room temperature. As shown in Fig. S4, for cluster 1, with the excitation
of 295 nm, four characteristic peaks at 545, 592, 615 and 701 nm occur in the visible
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5
5
5
region, corresponding to the transitions of D1→7F1, D0→7F1, D0→7F2 and D0→7F4.
These characteristic peaks are commonly observed in EuIII-compounds.26 Under the
excitation of 296 nm, the emission spectra of cluster 3 exhibit the characteristic
emissions of TbIII ions, the emission band at 491, 546, 589 and 625 nm can be attributed
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5
5
5
to the D4→7F6, D4→7F5, D4→7F4 and D4→7F3 transitions, respectively.27 Among
5
them, the D4→7F5 transition is the strongest. Under the excitation of 290 nm, for cluster
4, two characteristic peaks of DyIII can be observed in the emission spectra, which
4
4
belong to the transitions of F9/2 → 6H15/2 (480 nm) and F9/2 → 6H13/2 (576 nm).28
Magnetic properties
Magnetic studies were performed on polycrystalline samples of compounds 2-5.
Direct-current (dc) magnetic susceptibility studies of these compounds have been
carried out in the in the temperature range 2.0–300 K with an applied magnetic field of
1000 Oe. The plots of χMT vs. T are shown in Fig. 3. At 300 K, the observed χMT
-1
products of 2-5 are 31.56 (2), 47.44 (3), 56.55 (4) and 45.95 (5) cm3 K mol ,
respectively; which are in good agreement with the theoretical values for four non-
interacting LnIII ions: four GdIII ions (8S7/2, g = 2) give 31.52 cm3 K mol−1 for 2, four
TbIII ions (7F6, g = 3/2) give 47.28 cm3 K mol−1 for 3; four DyIII ions (6H15/2, g = 4/3)
give 56.68 cm3 K mol−1 for 4 and four ErIII ions (4I15/2, g = 6/5) give 56.28 cm3 K mol−1
8

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for 5. For cluster 2, as the temperature is lowered, the χMT values stay almost constant
5
6
7
in the temperature range 300−25 K and then drops rapidly to a minimum value of 15.83
8
9
-1
cm3 K mol at 2.0 K, which indicate the presence of a weak antiferromagnetic
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interaction between the GdIII ions.29 For clusters 3−5, upon lowering the temperature,
the χMT values decrease slowly down to approximately 50 K then rapidly down to 2.0
K reaching values of 38.80 (3), 29.48 (4), and 25.60 cm3 K mol−1 (5). The downtrend
of χMT vs. T curves for 3-5 can be ascribed to the weak antiferromagnetic exchange
between the LnIII ions in the compounds system and/or the thermal depopulation of the
LnIII Stark sublevels.30
Fig. 3 Plots of χMT vs. T for compounds 2-5 under 1000 Oe dc field.
The field dependence of the magnetization for 2 was measured at 0−8.0 T between
2.0 and 10.0 K (Fig. 4). The M versus H curves display a gradual increase with the
increasing field, and the M versus reach saturation values of 28.09 Nβ for 2 at 2.0 K
and 8.0 T, which are extremely approximate with the theoretical value of 28.0 Nβ for
four individual Gd(III) (S = 7/2, g = 2) ions. Because of the relatively high magnetic
density and the isotropy of GdIII ion of the polynuclear gadolinium-based cluster, the
magnetocaloric effect of the Gd4 cluster 2 was studied. Magnetic entropy changes (-
ΔSm) of 2 are calculated from the M versus H data to evaluate the MCE, and the -ΔSm
values can be calculated by using the Maxwell equation: ΔSm(T) = ∫ [∂M (T, H) /∂T]H
dH.31 As shown in Fig. 5, the maximum value of magnetic entropy change (-ΔSm) of
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are 24.46 J kg−1 K−1 at 2.0 K and ΔH = 7.0 T for 2, which is smaller than the cDaOlcI:u1l0a.1t0e3d9/D0NJ01969K
values of 26.34 J kg−1 K−1 for four uncorrelated GdIII (S = 7/2) ions based on the
equation −ΔSm = nRln(2S + 1) (where R is the gas constant, and S is the spin state).
The difference of maximum −ΔSm between the experimental and theoretical values for
2 are mainly due to the antiferromagnetic interaction in 2.32 The observed−ΔSm value
4
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of 2 is smaller than the values of some Gd4 clusters, however, the −ΔSm value of 8 is
bigger than other Gd4 compounds (Table 2).33-35
Fig. 4 M versus H plots for 2 at T = 2.0−10.0 K and H = 0−8.0 T.
Fig. 5 Temperature dependence of magnetic entropy change (−ΔSm) as calculated from the
magnetization data of 2 at T = 2.0−10.0 K and 0−7.0 T.
Table 2 Comparison of −ΔSm values among cluster 2 and some reported Gd4 clusters.
Gd4 Clusters
Magneticinteraction −ΔSm (J kg−1 K−1) (ΔH)
ref
Cluster 2
AF 24.46 (7 T)
This work
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DOI: 103.130a39/D0NJ01969K
[Gd4(L)2(dbm)6(CH3OH)2]
[Gd4(L)2(dbm)6(C2H5OH)2]
AF
AF
21.39 (5 T)
20.26 (7 T)
17.77 (7 T)
22.11 (7 T)
25.08 (7 T)
16.35 (7 T)
20.8 (7 T)
33a
33b
33b
33c
33d
33e
33f
34a
34b
34c
34d
34e
34e
34f
34f
35a
35b
35c
35d
35e
[Gd4(dbm)4L6(μ3-OH)2]·5CH3CN·0.5CH2Cl2
[Gd4(acac)4L6(μ3-OH)2]·2CH3CN
[Gd4(acac)4L6(μ3-OH)2]·CH3CN·0.5CH2Cl2
[Gd4(dbm)4(L)6(μ3-OH)2]·5CH3CN
[Gd4(acac)4L6(μ3-OH)2]
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
AF
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[Gd4(acac)4(μ3-OH)2(L)6]·4CH3CN
[Gd4(μ3-OH)2L6(acac)4]·2CH3CN
{[Gd4(L)6(pbd)4(μ3-OH)2]·2CH3CN}
[Gd4(L)6(tmhd)4(μ3-OH)2]
23.37 (7 T)
18.85 (7 T)
21.42 (7 T)
20.85 (7 T)
17.94 (7 T)
19.39 (7 T)
16.21 (7 T)
31.23 (7 T)
27.06 (7 T)
34.46 (7 T)
27.96 (7 T)
29.0 (7 T)
[Gd4(μ3-OH)2(tmhd)4L6]·2CH3CN
[Gd4(μ3-OH)2L6(acac)4]·2.5CH3CN
[Gd4(μ3-OH)2L6(tmhd)4]·CH3CN·CH3CH2OH
[Gd4(CO3) (L)4(acac)2(H2O)4]·2CH3CN
[Gd4CO3L4(acac)2(MeOH)2(H2O)2]·MeOH·H2O
[Gd4(HL)4(μ2-CH3O)4]·4CH3OH
[Gd4(acac)6L2(CH3O)2(CH3OH)4]
[Gd4(HL)4(μ2-CH3O)4]·4CH3OH
[Gd4(μ3-OH)4(L)4(μ2-piv)4(MeOH)4]
[Gd4(μ3-OH)2(L)2L1L2(HOCH3)2]·11H2O
25.57 (7 T)
27.2 (7 T)
In order to probe the magnetic relaxation dynamics of the Dy4 cluster 4, the
alternating-current (ac) magnetic susceptibility measurements were performed as a
function of the temperature on polycrystalline samples under zero dc magnetic field
with an ac oscillating field of 3.0 Oe (Fig. 6). Both in-phase (χ′) and out-of-phase (χ″)
of 4 become frequency dependent and occurrence of two distinct peaks for the out-of-
phase ac signals (χ″) is evident during the frequency range 911 Hz to 2311 Hz,
indicating the possible occurrence of a multiple relaxation process. Such a behavior has
been described in recent reported Dy4 clusters and has been attributed to the occurrence
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of two different DyIII coordination environment in 4.36 During the low frequency region
111 and 511 Hz, only one peak for the out-of-phase ac signals (χ″) was observed, and a
rising tail was occurred during 8.0-2.0 K, indicate the presence of quantum tunneling
effect (QTM) in 4.37
DOI: 10.1039/D0NJ01969K
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Fig. 6 Temperature dependence of in-phase (χ′) and out-of-phase (χ″) components of the ac
magnetic susceptibility under zero dc field for 4.
The frequency dependencies of the ac susceptibility were measured under the zero
dc fields to further explore the SMMs behaviors of cluster 4. As show in Fig. 7, both
the in-phase (χ′) and out-of-phase (χ″) signals of the ac susceptibility of 4 show
temperature dependencies, which further indicate the presence of slow relaxation of the
magnetization in cluster 4.38 Because of the strong overlap of peaks at low temperatures,
the evaluation of the effective energy barriers (ΔE/kB) for magnetization reversal and
relaxation times has been possible only for the high-temperature feature. The relaxation
time τ data of 4 derived from the out-of-phase (χ″) peaks in the form of lnτ plotted as a
function of 1/Tp (Fig. 8). The relaxation time τ data obey the Arrhenius law τ = τ0 exp
(ΔE/kBT) at high-temperature range.39 The best fitting results give the energy barriers
ΔE/kB = 75.0 K and the pre-exponential factor τ0 = 1.57×10−7 s. The ΔE/kB value of
cluster 4 obtained is higher than or comparable to these of other tetranuclear dysprosium
complexes based on 8-hydroxyquinoline Schiff base and β-diketionate ligands, smaller
than those of some Dy4 clusters reported in the literature.40 The τ0 of the cluster 4 is
consistent with the reported value of 10-6-10-12 s for Dy-based clusters SMMs.41
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Fig. 7 Frequency dependence of in-phase (χ′) and out-of-phase (χ″) components of the ac magnetic
susceptibility under zero dc field for 4.
Fig. 8 Plot of ln(τ) vs. T-1 for 4 obtained under zero dc field, and the red line represents the Arrhenius
fitted result.
As shown in Fig. 9, the Cole–Cole plots of χ'' vs. χ' for cluster 4 show nearly semi-
circle shapes and the generalized Debye model was employed to fit these data.42 The
best fitted parameter α = 0.16-0.58 for 4 was obtained. The relatively large distribution
coefficients α of cluster 4 indicate that there is a wide distribution of relaxation time in
cluster 4.
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Fig. 9 Cole−Cole plots for 4 at zero dc field at the indicated temperatures. The solid lines indicate
the best fits to the experiments with the generalized Debye model.
Conclusion
In conclusion, we have successfully synthesized five polynuclear lanthanide
compounds with {LnIII4} cores, which show rhombus-shaped arrangement. The
magnetic investigation reveal that Gd4 cluster 2 displays cryogenic magnetocaloric
effects with maximum −ΔSm value of 24.46 J kg−1 K−1 at 2.0 K and ΔH = 7.0 T. It is a
relatively larger magnetic entropy change (−ΔSm) value among the reported Gd4
clusters based on 8-hydroxyquinoline Schiff base ligand. Whereas the tetranuclear
Dy(III)-based cluster 4 shows single-molecule magnet (SMM) behavior with multiple
magnetic relaxation processes. The energy barriers (ΔE/kB) of 4 are 75.0 K and τ0 =
1.57×10−7 s.
Conflicts of interest
There are no conflicts to declare.
Acknowledgment
This work was supported financially by the National Natural Science Foundation of
China (21571138), the Scientific and Technological Innovation Programs of Higher
Education Institutions in Shanxi (No. 201802099), the Fund for Shanxi “1331 Project”
Key Innovative Research Team, Key Laboratory of Ecological Restoration of Water
Pollution (Taiyuan Normal University).
Notes and references
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Table of contents
Rhombus-shaped Gd4 cluster displays magnetic refrigeration property, and Dy4 cluster shows
remarkable SMMs behaviors .
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