Synthesis, Structures, and Single-Molecule Magnetic Properties of Three Dy2 Complexes

Article abstract of DOI:10.1002/asia.201801643

To explore the influences of the subtle structural variations in the ligand backbones on the single-molecule magnetic properties of dinuclear dysprosium(III) complexes, three ligands—H₂L₁ (H₂L₁=N₁,N

Full text of DOI:10.1002/asia.201801643

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Synthesis, Structures and Single Molecule Magnet Properties of
Three Dy2Complexes
Authors: Yu Ge, Yuan Huang, Jessenia Lisseth Becerra Montenegro,
Yanfeng Cui, wei Liu, Yahong Li, and BaoLin Wang
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To be cited as: Chem. Asian J. 10.1002/asia.201801643
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10.1002/asia.201801643
Chemistry - An Asian Journal
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Synthesis, Structures and Single Molecule Magnet Properties of
Three Dy2 Complexes
Yu Ge,[a] Yuan Huang,[a] Jessenia Lisseth Becerra Montenegro,[c] Yanfeng Cui,[a] Wei Liu,[a] Yahong
Li,*[a] and Bao-Lin Wang*[b]
Abstract: To explore the influences of the subtle structural
variations of the ligand backbones on the single molecule magnet
properties of dinuclear dysprosium(III) complexes, three ligands H2L1
(H2L1 = N1,N3-bis(salicylaldehyde)diethylenetriamine), H2L2 (H2L2 =
N1,N3-bis(3-methoxysalicylidene)diethylenetriamine) and H2L3 (H2L3
relationships between single-ion relaxation and the relaxation of
a molecular entity.[10]
Recent advances in this area reveal that Dy2 SMMs can be
achieved by employing a variety of ligands e.g. carboxylates,[11]
diketones,[12] Schiff-bases,[13-14] etc. Whereas, there are few
reports about the preparation of Dy2 SMMs by the combination
of salicylaldehyde Schiff-bases with carboxylic acids as the
ligands.[15-17]
=
N1,N3−bis(5−chlorosalicyladehyde)diethylenetriamine)
were
synthesized and employed to prepare the expected dinuclear
dysprosium(III) complexes. The three ligands differ in the
substituents at the benzene rings of the salicylaldehyde moieties.
The reactions of Dy(NO3)3·6H2O, pivalic acid and the ligands H2L1,
H2L2, and H2L3, respectively, generated complexes of formulae
[Dy2(L1)2(piv)2] (1), [Dy2(L2)2(piv)2] (2) and [Dy2(L3)2(piv)2]·2MeCN (3).
The purposeful attachment of the functional groups with varied sizes
at the benzene rings of the salicylaldehyde backbones resulted in
the slight differences of Dy−O−Dy bond angles and Dy···Dy bond
lengths in 1−3; consequently, three complexes exhibited distinct
magnetic properties. They all show slow magnetization relaxation
with energy barriers of 40.32 K (1), 31.67 K (2), and 33.53 K (3). The
CASSCF calculations were performed on 1−3 to rationalize the
observed slight discrepancy in the magnetic behavior. The
calculated results well explained the experimental outcomes.
In this work, we have used salicylaldehyde Schiff-bases H2L1
(H2L1
(H2L2 = N1,N3-bis(3-methoxysalicylidene)diethylenetriamine) and
H2L3 (H2L3 N1,N3-bis(5-chlorosalicyladehyde)diethylene-
= N1,N3-bis (salicylaldehyde)diethylenetriamine), H2L2
=
triamine) in combination with pivalic acid for the synthesis of Dy2
SMMs. The three ligands differ in the substituents at the
benzene rings of the salicylaldehyde backbones. Three
complexes of compositions [Dy2(L1)2(piv)2] (1), [Dy2(L2)2(piv)2] (2)
and [Dy2(L3)2(piv)2]·2MeCN (3) were generated. They all
exhibited SMM behavior. In this paper, the synthesis, structures
and magnetic properties of 1−3 are reported.
Introduction
Experimental
The study of single molecule magnets (SMMs) has received
sustainable interest over the past decades due to their potential
applications in the fields of memory storage, quantum
computation, spintronic devices, and molecular refrigeration,[1-2]
and so forth. Currently, the lanthanide-based SMMs are the
focus of this research topic. The high anisotropic nature of 4f
ions has certainly been advantageous for producing magnetic
materials on a molecular level.[3-4] Particularly DyIII ion is one of
the best candidates for magnetic centers, because it possesses
large magnetic moment and remarkable anisotropy, and may
afford SMMs with higher energy barriers.[5-6] Among the
dysprosium-based SMMs, Dy2 SMMs have attracted intense
attention of the chemists and physicists around the world.[7-8]
There are many reasons for this, but the preliminary impetuses
include the elucidation of the effects of the magnetic interactions
on relaxation of magnetization, the interpretation of the possible
orientation of anisotropy,[9] as well as the illustration of the
Materials and Physical Measurements
All solvents and reagents were obtained from commercial
sources and used without further purification. Fourier Infrared
(FTIR) spectra were acquired in the 4000−600 cm−1 range with a
Bruker Tensor 27 FTIR spectrophotometer. The elemental
analyses for C, H and N were performed on Perkin-Elmer 2400
analyzer. 1H NMR spectra were recorded at ambient
temperature on Bruker Avance-III 600 MHz NMR spectrometer,
and 1H NMR chemical shifts were referenced to the solvent
signal in CDCl3. Powder XRD patterns were obtained through a
Rigaku D/Max-2500 diffractometer at 40 kV and 100 Ma with a
Mo-target tube and
a graphite monochromator. Magnetic
susceptibility measurements were performed in the temperature
range of 2−300 K, using a Quantum Design MPMS XL-7 SQUID
magnetometer.
Synthesis of the Ligands
N1,N3-bis(salicylaldehyde)diethylenetriamine (H2L1)
[a] Yu Ge, Yuan Huang, Yanfeng Cui, Wei Liu, Prof. Dr. Yahong Li
College of Chemistry, Chemical Engineering and Materials Science
Soochow University, Suzhou 215123, China
E-mail: liyahong@suda.edu.cn.
[b] Prof. Dr. Bao-Lin Wang
Jiangsu Key Laboratory for NSLSCS
School of Physical Science and Technology
Nanjing Normal University, Nanjing 210023, China
E-mail: blwang@njnu.edu.cn
[c] Jessenia Lisseth Becerra Montenegro
College of Environmental Engineering, University of Waterloo,
Waterloo N2L3G1, Canada
The ligand H2L1 was synthesized by mixing salicylaldehyde
(0.025 mol) with diethylenetriamine (0.0125 mol) in EtOH (40
mL). After the reaction mixture was stirred at room temperature
for 5 hours, yellow precipitates were formed. The yellow
precipitates were filtered, washed with n-hexane (3×10 mL)
and collected as a yellow powder. Yield: 2.46 g (79%). Anal.
calcd for C17H19N3O2: C 69.24, H 6.86, N 13.55; found: C 69.43,
H 6.80, N 13.49. IR (KBr, cm-1): 2842 (w), 1629 (s), 1580 (w),
1496 (m), 1460 (w), 1416 (w), 1337 (w), 1277 (s), 1210 (w),
1150 (m), 1116 (w), 1040 (w), 1021 (w), 973 (w), 894 (w), 852
Supporting information for this article is given via a link at the end of
the document.
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10.1002/asia.201801643
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(w), 751 (s), 736 (s), 657 (w), 640 (w). 1H NMR (600 MHz,
Chloroform-d) δ 8.29 (s, 2H), 7.18 (d, J = 7.4 Hz, 2H), 6.92 (d, J
= 8.2 Hz, 2H), 6.82 (t, J = 7.4 Hz, 2H), 3.65 (t, J = 5.4 Hz, 4H),
3.06 – 2.83 (m, 4H).
[Dy2(L3)2(piv)2]·2MeCN (3)
Yellow block crystals of 3 were collected and washed with
MeOH. Yield: 102 mg (75% yield based on Dy). Anal. calcd for
C50H58Cl4Dy2N8O8: C 43.34, H 4.05, N 8.63; found: C 43.97, H
4.28, N 8.20. IR (KBr, cm-1): 2914 (w), 2193 (s), 1540 (s), 1525
(w), 1484 (s), 1467 (s), 1431 (m), 1386 (w), 1225 (w), 1190 (m),
1175 (m), 1088 (w), 1069 (w), 983 (w), 932 (w), 877 (w), 867 (m),
835 (m), 800 (m), 745 (w), 700 (s), 647 (m), 608 (w).
N1,N3-bis(3-methoxysalicylidene)diethylenetriamine (H2L2)
and N1,N3-bis(5-chlorosalicyladehyde)diethylenetriamine
(H2L3)
The ligands H2L2 and H2L3 were obtained in the same way as
that of H2L1 except replacing salicylaldehyde with o-vanillin and
5-chlorosalicyladehyde, respectively.
X-Ray Data Collection and Structure Determination
Single-crystal X-ray diffraction data for 1−3 were collected on
Bruker SMART APEX II CCD diffractometer equipped with
graphite-monochromated Mo-K ( = 0.71073 Å) by using the
Φ/ω scan technique. Absorption correction was based on
symmetry equivalent reflections using the SADABS program.
The crystal structures of 1−3 were solved by direct methods and
refined on F2 by full-matrix least-squares methods with the
SHELXL program.[18] Crystal data parameters for 1−3 are
summarized in Table 1. Selected bond lengths and angles for
1−3 were listed in Table S1. CCDC 1843525 (1), 1843524 (2),
1843523 (3) contain all supplementary crystallographic data of
the three complexes for this paper.
The yield of H2L2 is 3.69 g (82%). Anal. calcd for C20H25N3O4: C
64.58, H 6.94, N 11.34; found: C 63.67, H 6.78, N 11.31. IR (KBr,
cm-1): 2827 (w), 1627 (s), 1466 (w), 1440 (s), 1412 (w), 1376 (m),
1333 (w), 1300 (w), 1253 (w), 1167 (m), 1148 (s), 1127 (w),
1080 (w), 1024 (w), 991 (s), 980 (m), 964 (w), 903 (m), 863 (w),
838 (w), 776 (m), 759 (m), 733 (s), 641 (w), 633 (w), 615 (w),
608 (w). 1H NMR (600 MHz, Chloroform-d) δ 8.30 (s, 2H), 6.95 –
6.66 (m, 6H), 3.85 (s, 2H), 3.67 (s, 4H), 2.95 (s, 4H).
The yield of H2L3 is 3.80
g (81%). Anal. calcd for
C18H21N3O2Cl2: C 54.80, H 5.24, N 9.68; found: C 54.55, H 5.26,
N 9.54. IR (KBr, cm-1): 2802 (w), 1632 (s), 1574 (w), 1481 (m),
1393 (s), 1362 (w), 1301 (w), 1275 (s), 1208 (m), 1187 (m),
1137 (w), 1116 (w), 1086 (w), 1068 (w), 1045 (m), 1032 (w),
1007 (w), 965 (w), 954 (w), 920 (w), 904 (w), 890 (s), 878 (s),
827 (m), 777 (w), 718 (w), 685 (w), 645 (s). 1H NMR (600 MHz,
Chloroform-d) δ 8.23 (d, 2H), 7.25 – 7.09 (m, 4H), 6.84 (d, J =
8.6 Hz, 2H), 3.68 (s, 4H), 2.96 (s, 4H).
N
N
N
N
N
H
H2L1
OH
OH
O
N
H
O
H2L2
Synthesis of 1−3
OH
Cl
OH
Cl
[Dy2(L1)2(piv)2] (1)
A 10 mL Pyrex glass tube was loaded Dy(NO3)3·6H2O (46 mg,
0.1 mmol), H2L1 (45 mg, 0.1 mmol), pivalic acid (10 mg, 0.1
mmol), MeCN (1 mL), MeOH (1 mL) and triethylamine (14 mg,
0.1 mmol). The glass tube was sealed and heated in an oven to
70°C for 2 d, and then cooled to ambient temperature. Yellow
block crystals of 1 were collected and washed with MeOH. Yield:
74 mg (65% yield based on Dy). Anal. calcd for C46H56Dy2N6O8:
C 48.22, H 5.22, N 7.33; found: C 48.21, H 4.93, N 7.33. IR (KBr,
cm-1): 2968 (w), 1626 (s), 1594 (w), 1531 (s), 1472 (s), 1443 (w),
1425 (w), 1352 (m), 1311 (w), 1276 (m), 1241 (w), 1226 (w),
1196 (m), 1160 (m), 1147 (w), 1124 (w), 1088 (w), 1043 (w), 991
(w), 931 (m), 910 (s), 895 (w), 856 (w), 792 (m), 759 (s), 745 (m),
637 (w), 608 (m).
N
N
H2L3
N
H
OH
OH
Scheme 1. The structures of three ligands.
Results and Discussion
Synthetic and Spectral Aspects
To generate the dinuclear complexes with SMM properties and
to evaluate the influences of the subtle structural variations on
the magnetic properties, three salicylaldehyde Schiff-bases with
rich coordination atoms were selected as flexible ligands and
pivalic acid which possesses both steric hindrance and terminal
coordination sites was chosen as an ancillary ligand.
Compounds 2 and 3 were prepared in the same method as
that of 1 except that H2L1 was replaced by H2L2 and H2L3,
respectively.
The solvothermal reactions of Dy(NO3)3·6H2O with the
salicylaldehyde Schiff-bases (Scheme 1) and pivalic acid at
1:1:1 molar ratio in acetonitrile and methanol at 70 ℃ afforded
complexes 1−3. They are air and moisture stable compounds.
They were characterized by elemental analyses. The structures
of these complexes were further confirmed by single crystal X-
ray diffraction analysis.
[Dy2(L2)2(piv)2] (2)
Yield: 86 mg (68% yield based on Dy). Anal. calcd for
C50H64Dy2N6O12: C 46.95, H 5.44, N 6.55; found: C 47.43, H
5.10, N 6.64. IR (KBr, cm-1): 3218 (w), 2911 (w), 2190 (w), 1640
(s), 1621 (w), 1594 (s), 1537 (w), 1506 (m), 1484 (s), 1468 (m),
1445 (w), 1428 (w), 1418 (m), 1340 (m), 1388 (s), 1350 (s),
1332 (w), 1262 (w), 1241 (w), 1218 (w), 1166 (s), 1143 (s), 1120
(m), 1110 (w), 1093 (w), 1079 (w), 1039 (w), 1000 (w), 986 (w),
971 (m), 938 (m), 897 (w), 852 (w), 829 (m), 808 (w), 792 (w),
744 (m), 734 (s), 716 (m), 640 (w), 626 (w), 609 (w).
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10.1002/asia.201801643
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chelates with two DyIII ions in a μ2:η2:η1:η1:η1:η1 mode. The
Dy1···Dy1A distance is 3.789(3) Å and the Dy1−O1−Dy1A angle
is 110.19(7)°. The Dy1−O1, Dy1−O1A, Dy1−O2, Dy1−O3 and
Dy1−O4 bond lengths are 2.328(3), 2.368(3), 2.185(16),
2.411(3), and 2.429(3) Å, and the bonds lengths of Dy1−N are
2.542(4), 2.543(4) and 2.368(3) Å, respectively.
The coordination environments of DyIII ions in 2 and 3 are
identical with those of 1; whereas the bond lengths and bond
angles around DyIII ions in 2 and 3 are slightly different,
indicating that the attachment of the functional groups at the
benzene rings of salicylaldehyde backbones results in the subtle
structural variations. Considering the effects of the bond angles
and the bond lengths of 1−3 on their magnetic properties, they
are summarized in Table 2.
For lanthanides, the geometries of metal centers are strongly
correlated to the local anisotropy of the paramagnetic ions. Thus,
a systematic analysis of coordination geometry was carried out.
The program SHAPE 2.0 was used to analyze the exact
geometry of the eight-coordinated dysprosium.[19] The calculated
results indicate triangular dodecahedron (D2h) geometry for 1−2,
3_a, 3_b with minimum CShM values of 1.736, 2.293, 1.913,
and 2.262, respectively. The minimum CShM values reveal that
the configurations of 1−3 are slightly different.
Table 1. Crystallographic data for 1−3
1
2
3
Empirical formula
Formula weight
Crystal system
Space group
a/Å
C46H56Dy2N6O8 C50H64Dy2N6O12 C50H58Cl4Dy2N8O8
1145.96
triclinic
P1¯
1266.07
triclinic
P1¯
1365.84
monoclinic
P21/n
9.850(2)
10.935(2)
10.966(2)
74.522(6)
85.808(6)
84.963(6)
1132.5(4)
1
10.922(2)
11.530(3)
12.385(3)
68.405(7)
76.038(7)
62.728(6)
1283.9(5)
1
19.8837(16)
13.0974(11)
21.7140(18)
90
b/Å
c/Å
α/°
β/°
100.217(3)
90
γ/°
Volume/Å3
Z
5565.2(8)
4
ρcalcg/cm3
μ/mm-1
1.680
1.637
1.630
3.333
2.954
2.914
(a)
F(000)
570.0
634.0
2712.0
Crystal size/mm3
Θ range
Index ranges
0.4 × 0.18 × 0.15 0.6× 0.5 × 04 0.6 × 0.5 × 0.4
3.38 to 55.016 4.552 to 55.326 4.92 to 55.108
-12 ≤ h ≤ 12
-14 ≤ k ≤ 14
-14 ≤ l ≤ 14
-14 ≤ h ≤ 14
-15 ≤ k ≤ 14
-16 ≤ l ≤ 16
-24 ≤ h ≤ 25,
-17 ≤ k ≤ 17,
-28 ≤ l ≤ 27
Reflections collected 27822
50932
108132
Independent reflections5256
5923
12759
Rint = 0.0645
Rint = 0.0588
Rint = 0.0801
Data/restraints/
parameters
5256/0/283
5923/0/321
12759/0/657
(b)
Goodness-of-
1.172
1.110
1.020
fit on F2
Final R indexes
[I≥2σ (I)]
R1 = 0.0389,
wR2 = 0.0975
R1 = 0.0332,
R1 = 0.0401,
wR2 = 0.0945 wR2 = 0.0878
R1 = 0.0353, R1 = 0.0556,
wR2 = 0.0956 wR2 = 0.0945
1.73/-2.00 1.21/-1.75
Final R indexes
[all data]
Largest diff.
peak/hole
/ e Å-3
R1 = 0.0389,
wR2 = 0.0975
1.88/-2.10
Crystal Structure Description
Crystal Structures of 1−3
(c)
The single-crystal X-ray diffraction studies showed that
complexes 1−2 crystalize in the triclinic space group P1¯ and
compound 3 crystalizes in the monoclinic space group P21/n.
Complexes 1−3 are isostructural, thus only the structure of 1
was described in detail. The molecule of 1 consists of two DyIII
2−
ions, two L1 ligands and two pivalate ions. The Dy1 atom is
coordinated by two phenolate oxygen atoms and three amino
nitrogen atoms from one L12− ligand, two oxygen atoms from one
2−
pivalate ion and one oxygen atom from the other L1 ligand.
Each DyIII ion exhibits triangular dodecahedron geometry. The
two symmetry-related DyIII ions are doubly bridged by the two
2−
2−
phenolate oxygen atoms from two L1 ligands. Each L1 ligand
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10.1002/asia.201801643
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(d)
decreasing gradually in the range of 300−25 K, reaching to a
minimum value of 3.94 cm3 mol-1 K at 2 K.
The room-temperature MT value of 26.70 cm3 mol-1 K for 2 is
close to the expected value of 28.34 cm3 mol-1 K for two
uncoupled DyIII (6H15/2, g = 4/3) ions. By increasing temperature,
MT value of 2 exhibits a very slow decrease which accelerates
upon lowering the temperature below 20 K, giving a minimum
value of 5.14 cm3 mol-1 K.
The MT value of 3 is 28.91 cm3 mol-1 K at 300 K, which is
approached to the theoretical value of 28.34 cm3 mol-1 K for two
magnetically isolated DyIII (6H15/2, g = 4/3) ions. With the
decreasing of temperature, MT value decreases gradually and
then sharply to a value of 7.84 cm3 mol-1 K.
Figure 1. (a) The molecular structure of [Dy2(L1)2(piv)2] (1); (b) The molecular
structure of [Dy2(L2)2(piv)2] (2); (c) The molecular structure of
[Dy2(L3)2(piv)2]·2MeCN (3); (d) Coordination polyhedron of the DyIII ions in 1−3.
Color code: purple (Dy), red (O), blue (N), gray (C).
30
25
1
2
20
Table 2. Selected bond distances [Å] and angles [°] for 1, 2, 3_a, 3_b.
3
15
1
2
3_a
3_b

Dy1-Dy1A
Dy1-O1
3.798 (4)
2.328(3)
3.810(4)
3.8350(5)
2.355(3)
3.8226(4)
2.361(3)
10
5
2.391(3)
Dy1-O2
2.202(3)
2.213(3)
2.202(3)
2.196(3)
Dy1-O3
2.415(3)
2.420(3)
2.415(3)
2.409(3)
0
50
100
150
200
250
300
T / K
Dy1-O4
2.388(3)
2.406(3)
2.388(3)
2.413(3)
Dy1-N1
2.559(3)
2.564(3)
2.559(3)
2.535(3)
Figure 2. Temperature dependence of magnetic susceptibilities in the form of
T vs. T for 1−3 at 2-300 K with a dc applied field of 1000 Oe.
Dy1-N2
2.551(3)
2.553(3)
2.551(3)
2.564(3)
Dy1-N3
2.557(3)
2.536(3)
2.557(3)
2.524(3)
O1-Dy1-O3
O1-Dy1-O4
O1-Dy1-N1
O1-Dy1-N2
O1-Dy1-N3
O2-Dy1-O1
O2-Dy1-O3
O2-Dy1-O4
O2-Dy1-N1
O2-Dy1-N2
O2-Dy1-N3
O3-Dy1-N1
O3-Dy1-N2
O3-Dy1-N3
O4-Dy1-O3
O4-Dy1-N1
O4-Dy1-N2
O4-Dy1-N3
N2-Dy1-N1
N2-Dy1-N3
N3-Dy1-N1
Dy1A-O1-Dy1
78.38(10)
130.71(10)
69.07(10)
129.30(10)
148.33(10)
88.37(10)
102.62(11)
82.95(11)
155.94(11)
138.15(10)
72.48(10)
84.60(11)
72.76(11)
84.85(11)
53.85(10)
83.08(11)
120.30(11)
125.58(11)
65.88(11)
65.70(11)
131.43(11)
110.19(7)
78.38(10)
130.71(10)
69.07(10)
129.30(10)
148.33(10)
88.37(10)
102.62(11)
82.95(11)
155.94(11)
138.15(10)
72.48(10)
84.60(11)
72.76(11)
84.85(11)
53.85(10)
83.08(11)
120.30(11)
125.58(11)
65.88(11)
65.70(11)
131.43(11)
106.74(1)
77.96(10)
127.38(10)
69.90(10)
129.13(10)
146.01(10)
86.91(10)
104.31(12)
82.17(11)
155.29(11)
138.53(11)
72.12(11)
84.68(11)
71.99(11)
84.52(11)
53.95(10)
84.32(11)
120.67(10)
123.37(11)
66.05(11)
66.41(11)
132.33(11)
109.07(10)
77.68(9)
As the purpose of our research is to explore the effects of the
structural variations on the magnetic properties, we studied the
magnetization dynamics of 1−3. The temperature dependence of
alternating current (ac) magnetic susceptibilities for 1−3 were
determined at the indicated frequencies of 1, 10, 32, 100, 320,
660, 780 and 1000 Hz under zero dc field (Figure 3). The ac
magnetic susceptibilities of 1−3 all presented frequency
dependent character in the in-of-phase (') and out-of-phase
signal ('') at zero direct current (dc) field, indicating that they are
128.39(10)
70.29(10)
130.03(10)
145.65(10)
85.64(10)
102.62(11)
82.25(10)
153.48(11)
139.71(11)
73.29(11)
84.81(11)
71.65(11)
84.81(11)
53.94(10)
83.41(11)
119.05(11)
124.24(11)
66.47(11)
66.81(11)
133.19(11)
108.38(10)
SMMs.
(a)
1Hz
10Hz
4.0
32Hz
100Hz
320Hz
666Hz
780Hz
1000Hz
3.2
2.4
1.6
0.8
0.0

0
5
10
15
20
25
T / K
1.6
1.2
0.8
0.4
0.0
1Hz
10Hz
32Hz
100Hz
320Hz
666Hz
780Hz
1000Hz
Magnetic Studies
The direct-current (dc) magnetic susceptibility measurements of
1−3 were performed on polycrystalline samples at a temperature
range of 2−300 K under an applied magnetic field of 1000 Oe.
The data are plotted as MT versus T in Figure 2.

For complex 1, the MT value is 29.67 cm3 mol-1 K at room
temperature, which is approached to the two uncoupled DyIII
(6H15/2, g = 4/3) ions of 28.34 cm3 mol-1 K. The MT value of 1 is
0
5
10
15
20
25
T / K
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(b)
(a)
1Hz
10Hz
3.0
32Hz
1.6
1.2
0.8
0.4
0.0
2.5
2.0
1.5
1.0
100Hz
320Hz
666Hz
780Hz
1000Hz


0.5
0.0
0
5
10
15
20
25
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
T / K
' / cm3 mol-1
1Hz
10Hz
32Hz
(b)
1.2
0.8
0.4
0.0
100Hz
320Hz
666Hz
780Hz
1000Hz
1.2
0.8
0.4
0.0


0
5
10
15
20
25
T / K
(c)
0.0
0.5
1.0
1.5
2.0
2.5
 '/cm3mol-1
1Hz
10Hz
32Hz
100Hz
320Hz
667Hz
780Hz
999Hz
2.0
1.6
1.2
0.8
0.4
(c)
0.6
0.4
0.2
0.0


0
5
10
15
20
25
T / K
0.0
0.4
0.8
1.2
1.6
1Hz
10Hz
 '/cm3mol-1
0.6
0.4
0.2
0.0
32Hz
Figure 4. Cole-Cole plots of 1−3 measured from 2.5 to 8 K for 1(a), 3 to 10 K
for 2(b), 3 to 9 K for 3(c) under zero dc field. The solid lines are best fits to the
experimental data.
100Hz
320Hz
667Hz
780Hz
999Hz
The Cole-Cole plots (Figure 4) have been fitted using a
generalized Debye model. It implied that the thermally activated
relaxation processes of 1−3 have wide distribution of relaxation
times. The curvatures of lnτ versus 1/T plots at low temperature
indicate other relaxation pathways may exist. For an Orbach-
type relaxation, the relaxation time (τ0) and barrier will follow the
Arrhenius equation ln τ = ln τ0 + Ueff/kBT (Equation 1), where Ueff
is the effective spin-reversal barrier and kB is the Boltzmann

0
5
10
15
20
25
T / K
Figure 3. Temperature dependence of the in-phase (χ') and out-of-phase (χ'')
susceptibilities for 1(a), 2(b) and 3(c) in the range to 22 K. The
constant. The fit of the above-mentioned equation affords Ueff
=
2
40.32 K, 31.67 K, 33.53 K and τ0 = 3.06 × 10-6 s, 9.19 × 10-6 s,
2.17 × 10-6 s for 1−3, respectively.
susceptibilities are determined at 1 Hz, 10 Hz, 32 Hz, 100 Hz, 20 Hz, 666 Hz,
780 Hz, 900 Hz, 1000 Hz frequencies under zero dc field.
Other relaxation processes may exist at low temperature, thus
the magnetic data of 1−3 are fitted by the equation (2): 1/τ = CTn
+τ0-1 exp(-Ueff/kBT), in which the spin-lattice relaxation of both the
Orbach and Raman processes are considered (Figure 5).[20] The
best fit of the equation (2) on the whole temperature range
provides Ueff = 39.99 K, τ0 = 1.9 × 10-6 s, C = 86.11 s-1 K-0.27, n =
0.55 for 1, Ueff = 36.78 K, τ0 = 5.62 × 10-6 s, C = 63.36 s-1 K-0.57, n
= 0.57 for 2, and Ueff = 41.68 K, τ0 = 2.6 × 10-6 s, C = 118.36 s-1
K-0.58, n = 0.58 for complex 3.
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Complexes 1−3 join a small family of DyIII SMMs with pivalic acid
as ancillary ligands (Table 3).[21] Pivalic acid is a particular
compound, which could fulfill both the chelating and steric
hindrance requirements, giving clusters with smaller nuclearities.
Among the reported DyIII SMMs utilizing pivalic acid as co-
ligand, the energy barriers of 1−3 are relatively higher.
(b)
-3
-4
-5

-6
A comparison of the energy barriers among 1−3 indicates a
correlation of energy barriers with their structures. The CShM
values of 1, 2, 3_a and 3_b are 1.736, 2.293, 1.913 and 2.262,
respectively, thus, the configuration of 1 is more close to a
standard triangular dodecahedron (D2h), leading to the higher
energy barrier of 1 consequently. This result reveals that the
attachment of functional groups at the benzene rings of
salicylaldehyde motifs causes the subtle variations of the
configurations of complexes, leading to the alteration of the
2
-7
Orbach
Orbach+Raman
-8
-9
-10
0.05 0.10
0.15 0.20 0.25 0.30
T -1 / K-1
0.35 0.40
(c)
-4.5
-5.0
-5.5
-6.0
-6.5
-7.0
-7.5
-8.0
-8.5
magnetic properties.
(a)
-4
-5

3
Orbach
Orbach+Raman
-6

1
Orbach
Orbach+Raman
-7
-8
-9
0.10
0.15
0.20
0.25
0.30
0.35
0.40
T -1 / K-1
Figure 5. Temperature dependence of magnetic relaxation times under zero
dc fields for 1 (a), 2 (b) and 3 (c). The blue solid lines represent data fits to the
Equation (1) and the red solid lines represent data fits to Equation (2).
0.10
0.15
0.20
0.25
0.30
0.35
T -1 / K-1
Table 3 Examples of Ueff in Dy2 SMMs coordinated with pivalate ligand
Complexes
Magnetic behavior
Magnetic Field/ Oe
Energy barrier/
K
τ0/ s
[Dy4(L1H)2(μ3-OH)2(η2-piv)2(μ2-η1: η1Piv)2][21a]
[Dy2(L2H)2(μ2-piv-κ2O,O′)2(NO3-κ2O,O′)2][21b]
AF
AF
AF
F
zero
zero
zero
500
40.92
40
1.5×10−7
6.5×10−5
8.81×10-5/ 1.48×10-6
2.5×10-5
1.1×10-5
2.6×10-2
1.2×10−7
/
[21c]
[Dy2(H2L3)2 (µ-piv)2(piv)2]·2CHCl3
8.96/ 35.5
18.07
5.4
[Dy4(µ3-OH)4(L4)4(µ2-piv)4(MeOH)4] [21d]
[Ln4(µ3-OH)2(ampdH4)2(piv)10]·4CH3CN[21e]
[Dy5(LH)4(η1-piv)(η2-piv)3(μ2-η2η1piv)2(H2O)]·Cl·9.5H2O·5MeOH [21f]
[Dy12Na3(μ3-OH)2(hmmp)6(piv)12(CO3)6(MeOH)6]OH·5MeOH [21g]
[[Dy2(L6H2)2(μ2-η1:η1-piv)]Cl·2MeOH·H2O
[Dy4(L6H)2(μ3-OH)2(piv)4(MeOH)2]·4MeOH·2H2O [21h]
[Dy8(L7H2)4(μ-piv)4(η2-piv)4(μ-OMe)4]·8CH3OH[21i]
[Dy2(L8)2(piv)2] (1)[this work]
AF
AF
AF
F/AF
F/AF
AF
AF
AF
AF
zero
3000
zero
zero
zero
zero
zero
zero
zero
5.2
3.5
no peak
no peak
not SMMs
40.32
31.67
33.53
/
/
3.06×10-6,
9.19×10-6,
2.17×10-6
[Dy2(L9)2(piv)2] (2)[this work]
[Dy2(L10)2(piv)2]·2MeCN (3) [this work]
piv = pivalate; L1H2 = 2-{[6-(hydroxymethyl)pyridin-2-yl]methyleneamino}phenol); L2H2 = N′-(2-hydroxy-3-methoxybenzylidene)acetohydrazide; H3L3 = 2,2’-(2-
hydroxy-3-methoxy-5-methylbenzylazanediyl)diethanol; L4H = [1,3-bis(o-methoxyphenyl)-propane-1,3-dione]; ampdH4 = 3-amino-3-methylpentane-1,5-diol; L5H3
N’-(2-hydroxy-3-(hydroxymethyl)-5-methylbenzylidene)acetohydrazide; hmmpH2 2-[(2-hydroxyethylimino)methyl]-6-methoxyphenl; L6H4 6-((bis(2-
hydroxyethyl)amino)methyl)-N’-((8-hydroxyquinolin-2-yl)methylene)picolinohydrazide; L7H5 (2E,N′E)-N′-(3-((bis(2-hydroxyethyl)amino)methyl)-2-hydroxy-5-
methylbenzylidene)-2-(hydroxyimino)propanehydrazide; H2L8 N1,N3-bis(salicyladehyde)diethylenetriamine; H2L9 N1,N3-bis(3-methoxysalicylidene)
diethylenetriamine; H2L10=N1,N3−bis(5−chlorosalicyladehyde)diethylenetriamine (this work). F = ferromagnetic, AF = antiferromagnetic.
=
=
=
=
=
=
MOLCAS 8.2[22] and Single_Aniso[23] programs (see Supporting
Information for details). The lowest eight Kramers doublets
(KDs) and the corresponding g tensors of complexes 1−3 are
shown in Table S6, where the energy gaps between the lowest
two KDs are similar for three complexes. The mJ components for
the lowest two doublets of individual DyIII fragments for 1−3 are
Theoretical Calculation
Complete-active-space
self-consistent
field
(CASSCF)
calculations on individual DyIII fragments for 1−3 on the basis of
X-ray determined geometries have been carried out with
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10.1002/asia.201801643
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shown in Table S7, where the ground states of three complexes
are all mostly composed by mJ = 15/2 state. However, the first
excited state of complex 3 is composed by several mJ states (mJ
= 13/2, 1/2 and 3/2 have the similar weights). For the first
excited state of 1 and 2, the mJ = 13/2 state is predominant. The
corresponding quantum tunneling gaps of individual DyIII
fragments for 1−3 are shown in Figure S18 where the gaps in
the ground state of 1 and 3 are both about 10−2 µB, and therefore
the QTM is suppressed at low temperature. But, that of 2 is
about 10−1 µB, therefore allowing a fast QTM in its ground state.
Although their magnetic anisotropies of 1−3 mainly come from
individual DyIII fragments, the DyIII-DyIII interactions have some
influence on their slow magnetic relaxation processes.
differences in the bond lengths of Dy−O1, and the bond angles
of Dy−O−Dy in compounds 1−3, which are caused by the
alteration of the substituents at the benzene rings of the
salicylaldehyde moieties. Complexes 1−3 exhibit SMM
behaviors with slight difference in energy barriers. Theoretical
calculations are consistent with the experiment results.
Acknowledgements
The authors appreciate the financial support from Natural
Science Foundation of China (21272167 and 21772140),
Natural Science Foundation of Jiangsu Province of China
(BK20171213), a Project Funded by the Priority Academic
Program Development of Jiangsu Higher Education Institution,
and the project of scientific and technologic infrastructure of
Suzhou (SZS201708).
From Table S6, the calculated ground gz values of individual
DyIII fragments for 1−3 are all close to 20, and thus the DyIII−DyIII
exchange interactions for complexes 1−3 were approximately
regarded as the Ising type during the fitting. The program
Poly_Aniso[23] (see Figure S18) was used to fit the magnetic
susceptibilities of complexes 1−3 using the exchange
parameters from Table 4. This indicated that the magnetic
properties of 1−3 may have slight difference.
Keywords: single molecule magnets •dysprosium ion • pivalate•
Schiff−base • energy barrier
CCDC: 1843525 (1), 1843524 (2), 1843523 (3) respectively.
Table 4. Fitted exchange coupling constant Jexch, the calculated dipole-dipole
interaction Jdip and the total J between DyIII ions in complexes 1−3 (cm−1). The
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intermolecular interactions zJ´ of complexes 1−3 were fitted to −0.02 cm−1
−0.11 cm−1 and −0.12 cm−1, respectively.
,
1
2
3
Jexch
Jdip
Jtotal
−1.50
−2.91
−4.41
−1.75
−2.98
−4.73
−1.50
−2.91
−4.41
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All parameters from Table 4 were calculated with respect to the

S
pseudospin
= 1/2 of the DyIII ions. For complexes 1−3, the
total coupling parameters J (dipolar and exchange) was included
into fit the magnetic susceptibilities. The calculated and
experimental χMT versus T plots of complexes 1−3 are shown in
Figure S18 where the fit for 1 is close to the experimental
data.[24a] However, the fits for complexes 2 and 3 have some
deviation from the experiment. The DyIII-DyIII interactions in
complexes 1−3 within Lines model[24b] are all antiferromagnetic.
The main magnetic axes on DyIII ions for complexes 1−3 were
indicated in Figure S19, where the magnetic axes on DyIII for
complexes 1−3 are all antiparallel. Moreover, we gave the
exchange energies and the main values of the gz for the lowest
two exchange doublets of 1−3 in Table S8 where the gz value of
the ground exchange state for complexes 1−3 are all 0.000,
which confirms that the DyIII−DyIII couplings are all
antiferromagnetic. These calculation results are well consistent
with the experimental results.
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Conclusion
In summary, solvothermal reactions of Dy(NO3)3·6H2O with three
salicylaldehyde Schiff-base ligands H2L1 (H2L1
bis(salicylaldehyde)diethylenetriamine), H2L2 (H2L2
=
=
N1,N3-
N1,N3-
bis(3-methoxysalicylidene)diethylenetriamine) and H2L3 (H2L3 =
N1,N3−bis(5−chlorosalicyladehyde)diethylenetriamine), in the
presence of pivalic acid as ancillary ligand, yielded eight-
coordinated dinuclear complexes 1−3. They all contain μ2-
phenoxyl oxygen atom bridged Dy2O2 cores. There are slight
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Entry for the Table of Contents (Please choose one layout)
Yu Ge, Yuan Huang, Jessenia Lisseth
Becerra Montenegro, Yanfeng Cui, Wei
Liu, Yahong Li* and Bao-Lin Wang*
1.6
1.2
0.8
Page No. – Page No.

0.4
Synthesis, Structures and Single
Molecule Magnet Properties of Three
Dy2 Complexes
0.0
0
5
10
15
20
25
T / K
0.6
1.2
0.8
 0.4
0.0
0.4
0.2
0.0

T / K
0
5
10
15
20
25
0
5
10
15
20
25
T / K
Three
dinuclear
complexes
[Dy2(L1)2(piv)2]
(1),
[Dy2(L2)2(piv)2]
(2),
[Dy2(L3)2(piv)2]·2MeCN (3) are synthesized and characterized. The subtle structural
differences result in variations of the magnetic properties.
This article is protected by copyright. All rights reserved.