Structurally modulated single-ion magnets of mononuclear β-diketone dysprosium(iii) complexes

Article abstract of DOI:10.1039/d0dt02864a

Five β-diketone based Dy(iii) single-ion magnets (SIMs), [DyIII(TTA)3(AIP)]·0.5CH3CH2OH·0.5H2O (1), [DyIII(TTA)3(APIP)]·2CH3OH·H2O (2), [DyIII(TTA)3(DPP)] (3), [DyIII(TTA)3(BPP)]·0.5CH3CH2OH (4) and [DyIII(TTA)3(AIP)]·1.5H2O (5), were fully synthesized through alteration of their phenanthroline derivates (AIP = 2-(anthracen-9-yl)-1H-imidazo[4,5-f][1,10]phenanthroline, APIP = 2-(4-(anthracen-9-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, DPP = 2,3-diphenylpyrazino[2,3-f][1,10]phenanthroline and BPP = 2,3-bis(2,5-dimethylthiophen-3-yl)pyrazino[2,3-f][1,10]phenanthroline). Magnetic investigations reveal that all the complexes perform as SIMs, with notably different effective barriers of 69.4 K (1), 147.3 K (2), 122.1 K (3) and 234.2 K (4) in zero direct current (dc) field. Complexes of 2 and 4 possess almost twofold higher effective barriers compared to 1 and 3. By analyzing the crystal structures, the distinct magnetic dynamics was found to stem from the variation in intermolecular hydrogen bond interactions and charge delocalization of auxiliary ligands. With the help of ab initio calculations, a change of auxiliary ligand brings about varying intensities of quantum tunnelling magnetization (QTM), which account for the distinguishable magnetic dynamics. With a combination of experimental and theoretical analyses, this work provides a visual and instructive perspective to the understanding of fine tuning auxiliary ligands to design structurally modulated SIMs of mononuclear β-diketone dysprosium(iii) complexes. This journal is

Full text of DOI:10.1039/d0dt02864a

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DOI: 10.1039/D0DT02864A
ARTICLE
Structurally modulated single-ion magnets of mononuclear β-
diketone dysprosium(III) complexes†
Ming Kong,a Xin Feng, a Jing Li, a Zhao-Bo Hu, a Jia Wang, a Xiao-Jiao Song, a Zhao-Yang Jing, a Yi-Quan
Received 00th January 20xx,
Accepted 00th January 20xx
Zhang,*b and You Song*a
DOI: 10.1039/x0xx00000x
Five β-diketone based Dy(III) single-ion magnets (SIMs) of [DyIII(TTA)3(AIP)]·0.5CH3CH2OH·0.5H2O (1),
[DyIII(TTA)3(APIP)]·2CH3OH·H2O (2), [DyIII(TTA)3(DPP)] (3), [DyIII(TTA)3(BPP)]·0.5CH3CH2OH (4) and [DyIII(TTA)3(AIP)]·1.5H2O (5),
have been fully synthesized through alteration of the phenanthroline derivates (AIP = 2-(anthracen-9-yl)-1H-imidazo[4,5-
f][1,10]phenanthroline, APIP
=
2-(4-(anthracen-9-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, DPP
=
2,3-
diphenylpyrazino[2,3-f][1,10]phenanthroline
and BPP 2,3-bis(2,5-dimethylthiophen-3-yl)pyrazino[2,3-
=
f][1,10]phenanthroline). Magnetic investigations reveal that all complexes perform as SIMs with notably different effective
barriers of 69.4 K (1), 147.3 K (2), 122.1 K (3) and 234.2 K (4) in zero direct current (dc) field. Complexes of 2 and 4 possess
almost twofold higher effective barriers than the comparative 1 and 3. By the analyzing the crystal structures, the distinction
of magnetic dynamic stems from the variation of intermolecular hydrogen bonds interaction and charge delocalization of
auxiliary ligands. With the help of ab initio calculation, the conspicuous variation of auxiliary ligand brings about varying
intensity of quantum tunnelling magnetization (QTM), which accounts for the distinguishable magnetic dynamic. With the
combination of experimental and theoretical analyses, this work provides a visual and instructive perspective to the
understanding of the authenticity of fine tuning of auxiliary ligand for designing such structurally modulated SIMs of
mononuclear -diketone Dysprosium(III) complexes.
anisotropy barrier for SIMs, the anisotropic Kramers ion Dy(III)
is a good candidate for its large mJ (15/2) and degenerate
ground states. In the past, numerous studies on high-
performance SIMs have manifested that the highly symmetrical
Dy(III)-based SIMs, such as D4d, D5h and D6h, can minimize the
electron repulsion around the lanthanide ion and stabilize the
mJ = ±15/2 state to avoid quantum tunnelling magnetization
(QTM).12-20
The structures with approximate square-antiprismatic or
dodecahedron coordination polyhedron are of great interest
owing to the promising application in constructing SIMs and
facile synthesis.13 Such SIMs have demonstrated that subtle
modification by lattice solvents, auxiliary ligand and
intermolecular interaction usually result in the distortion of
coordination-sphere and thus bring out distinct magnetic
relaxation behavior.16,21,23b Thus, the series of eight-coordinate
Dy-β-diketones complexes of [Ln(β-diketone)3L] have been
extensively used to construct high-performance Dy(III) SIMs
through regulation of the auxiliary ligands.22,23 As building block
for linking phenanthroline ligand, the protonated five-
membered imidazole ring and non-protonated six-membered
pyrazine ring has been confirmed as effective groups to regulate
intermolecular hydrogen bond and transmit charge conjugation
effects.12,23d Therefore, these types of complexes containing
bridged imidazole or pyrazine moiety can efficiently modulate
the magnetic structure of lanthanide-based SIMs.
Introduction
The lanthanide single-ion magnets (Ln(III)-SIMs), displaying slow
relaxation of magnetization as an important member of single
molecule magnets (SMMs), have raised worldwide attention for
their significant single-ion magnetic anisotropy. Such property
is rooted in large unquenched orbital angular momentum and
intrinsic strong spin orbit coupling of lanthanide ions, especially
Dy(III), Tb(III) and Er(III) ions.1-3 In addition, further
understanding of magneto-structural correlations contributes
to the explanation between macroscopic magnetic properties
and the quantum effects in SMMs. Recently, the development
of Dy(III)-based SIMs with high anisotropy barrier that aiming at
maximum relaxation energy barrier and the highest blocking
temperature is of great interest for their potential applications
of high density data storage, quantum computation and
spintronics.4-10 The top trend towards the goal now is to control
the symmetry of lanthanide ions.11 Considering a large magnetic
a
State Key Laboratory of Coordination Chemistry, School of Chemistry and
Chemical Engineering, Collaborative Innovation Center of Advanced
Microstructure, Nanjing University, Nanjing 210023, People’s Republic of China.
b Jiangsu Key Lab For NSLSCS, School of Physical Science and Technology, Nanjing
Normal University, Nanjing 210023, People’s Republic of China.
† Electronic Supplementary Information (ESI) available: Synthetic procedure,
crystallographic relative data, SHAPE analysis, PXRD and magnetic relative data,
calculated results. CCDC 1994048 and 1994050-1994052, 2033641. For ESI and
crystallographic data in CIF or other electronic format see
DOI: 10.1039/x0xx00000x
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Scheme 1. Schematic chemical structure of complexes 1-4.
package and by subsequent difference Fourier syntheses. The
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all hydrogens were determined theoretiDcOalIl:y10a.1n0d39r/eDfi0nDeTd02w86i4thA
isotropic thermal parameters riding on their parents. All non-
hydrogen atoms were refined by a full-matrix least-squares
technique based on F2. All calculations were performed by
SHELXTL-97.27-29
Magnetic Measurements
There has been evidence that the local symmetry of Dy(III)
ions plays a key role in modulating the single-ion anisotropy.11
Meanwhile, the electron-donating or -withdrawing effect of
auxiliary ligands that indirectly influences the electrostatic
potential (ESP) around the central Dy(III) ions, is also the
decisive factor to regulate the magnetic dynamic, especially in
facilitating the suppression of fast relaxation. According to
previous report, it has been proven that the notional electron-
withdrawing effect of β-diketone results in the reduction of
magnetic relaxation barriers.24 Therefore, how electron effect
of auxiliary ligand influences the magnetic dynamic are indeed
necessary to completely explore.
The alternating current (ac) magnetic susceptibility data were
collected using a PPMS (1 and 2) or MPMS (3, 4 and 5)
magnetometer with an ac field of 5 Oe or 2 Oe in the
frequencies ranging from 1 to 10000 or 1-999 Hz respectively.
The direct current (dc) magnetic susceptibility data of 1-5 were
measured in the temperature range from 1.8 to 300 K using
MPMS magnetometer. Experimental susceptibilities were
corrected for the diamagnetism of the samples as estimated
from Pascal’s tables and of the sample holder by a previous
calibration.30
Ab initio Calculations
Herein, we present four Dy-β-diketones complexes based on
phenanthroline ligand with different electron-donating groups
linked by imidazole or pyrazine moiety, that is, [Dy(TTA)3AIP]
(1), [Dy(TTA)3APIP] (2), [Dy(TTA)3DPP] (3), and [Dy(TTA)3BPP] (4)
(Scheme 1). The Dy(III) centre with eight-coordination
environment of N2O6 bear the distorted square-antiprismatic or
triangular dodecahedron geometry. The magnetic relaxation
studies and CASSCF/SI-SO calculations indicated that these
properties can be modified by the slightly modulated auxiliary
phenanthroline ligands.
Complete-active-space
self-consistent-field
(CASSCF)
calculations based on the experimental single crystal X-ray data
were performed with the MOLCAS 8.4 program package on
individual Dy(III) fragment for each complex. For CASSCF
calculations, the basis sets used are atomic natural orbitals from
the MOLCAS ANO-RCC library: ANO-RCC-VTZP for Dy(III) ion;
VTZ for close O and N; VDZ for distant atoms. The calculations
employed the second order Douglas-Kroll-Hess Hamiltonian,
where scar relativistic contractions were taken into account in
the basis set and the spin-orbit coupling were handled
separately in the restricted active space state (RASSI-SO)
procedure. The active electrons in seven active spaces contain
all f electrons CAS (9 in 7) for each Dy(III) fragment. The
maximum number of spin-free states that are possible with our
hardware include all 21 sextets, 128 from 224 quadruplets, and
130 from 490 doublets for Dy(III) fragment.31
Experimental
Materials and methods
All chemicals and solvents are commercially available and used
without further purification. The ligands of DPP and BPP are
synthesized by the cyclization combining 1,10-phenanthroline-
5,6-diamine with corresponding 1,2-dione.25,26 The other two
ligands, AIP and APIP, are synthesized by a similar ring closing
reaction using corresponding aromatic carbaldehyde and
phenanthroline-5,6-dione (Scheme S1†). Elemental analyses of
C, H and N were recorded on a PerkinElmer 240C elemental
Synthesis of AIP and APIP. The synthesis route of AIP and APIP
is similar and here AIP as an example showed below. In a 100
mL round bottom flask, 1.03 g (5 mmol) of anthracene-9-
carbaldehyde and 1.05 g (5 mmol) of 1,10-phenanthroline-5,6-
dione are mixed and then 5.00 g of ammonium acetate is added
meanwhile together with 40 mL of glacial acetic acid. The
solvent was removed after refluxing overnight and poured in
water accompanied with yellow precipitate. After the filtration
and evaporation, the target product was further purified by
recrystallization in ethanol, yielding a yellow power (1.79 g,
86%). APIP: The target product was further purified by
recrystallization in ethanol, yielding a yellow power (1.81 g,
75%). AIP: MALDI-TOF-MS (m/z) Calcd. for C27H16N4: 396.14,
1
analyzer. H-NMR and MALDI-TOF-MS data were obtained on
Bruker Advance III 500 MHz nuclear resonance spectrometers
and Bruker ultraflex treme TOF/TOF.
X-ray Crystallography
The single-crystal X-ray measurements of 1-4 were carried out
on a Bruker D8 venture diffractometer fitted with a PHOTON-
100 COMS detector with Mo Kα radiation (λ = 0.71073 Å) by
using an ω scan mode at 153 K. The diffraction data were
treated using SAINT, and all absorption corrections were carried
out by using SADABS. All non-hydrogen atoms were labelled by
Patterson’s method using the SHELXS programs of the SHELXTL
1
found 397.320. H-NMR (500 MHz, DMSO-d6) δ 14.22 (s, 1H),
9.10 (dd, J = 4.3, 1.8 Hz, 2H), 8.97 (dd, J = 8.0, 1.8 Hz, 1H), 8.93
(s, 1H), 8.79 (dd, J = 8.2, 1.7 Hz, 1H), 8.28 (d, J = 8.4 Hz, 2H), 7.89
–7.78 (m, 4H), 7.63 (ddd, J = 8.4, 6.5, 1.2 Hz, 2H), 7.56 (ddd, J =
8.8, 6.5, 1.3 Hz, 2H). APIP: MALDI-TOF-MS (m/z) Calcd. for
C33H20N4: 472.17, found 473.344. 1H-NMR (500 MHz, DMSO-d6)
2 | J. Name., 2012, 00, 1-3
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δ 13.97 (s, 1H), 9.09 (dd, J = 7.6, 1.8 Hz, 1H), 9.09 (s, 1H), 9.01 product was further purified by flash chromatography, yielding
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DOI: 10.1039/D0DT02864A
(ddd, J = 8.2, 3.9, 1.7 Hz, 2H), 8.75 (s, 1H), 8.60 – 8.54 (m, 2H), a white power (1.90 g, 77.5%). DPP: The target product was
8.21 (d, J = 8.5 Hz, 2H), 7.90 (ddd, J = 25.0, 8.2, 4.3 Hz, 2H), 7.74 further purified by recrystallization in ethanol, yielding a yellow
– 7.64 (m, 4H), 7.58 (ddd, J = 8.3, 6.5, 1.1 Hz, 2H), 7.50 (ddd, J = power (77%). DPP: MALDI-TOF-MS (m/z) Calcd. for C26H16N4:
1
8.0, 6.5, 1.3 Hz, 2H).
384.14, found 385.326. H-NMR (500 MHz, DMSO-d6) δ 9.52
Synthesis of DPP and BPP. The synthesis routes of DPP and BPP (dd, J = 8.1, 1.8 Hz, 2H), 9.26 (dd, J = 4.3, 1.8 Hz, 2H), 7.98 (dd, J
are similar and here BPP as an example showed below. In a 100 = 8.1, 4.3 Hz, 2H), 7.73 – 7.67 (m, 4H), 7.52 – 7.40 (m, 6H). BPP:
mL round bottom flask, 1.05 g (5 mmol) of 1,10-phenanthroline- MALDI-TOF-MS (m/z) Calcd. For C26H20N4S2: 452.11, found
1
5,6-diamine and 1.50
g
(5.4 mmol) of 1,2-bis(2,5- 453.286. H-NMR (500 MHz, DMSO-d6) δ 9.43 (dd, J = 8.2, 1.8
dimethylthiophen-3-yl) ethane-1,2-dione are mixed, and then Hz, 1H), 9.24 (dd, J = 4.3, 1.8 Hz, 1H), 8.82 (dd, J = 5.0, 1.6 Hz,
25 mL methanol is subsequently added together with 25 mL of 1H), 8.11 (dd, J = 7.6, 1.6 Hz, 1H), 7.96 (dd, J = 8.1, 4.4 Hz, 1H),
glacial acetic acid. The solvents are removed after refluxing for 7.53 (dd, J = 7.5, 5.0 Hz, 1H), 6.92 (d, J = 1.3 Hz, 1H), 6.71 (d, J =
10 hours and poured in water accompanied with white 1.3 Hz, 1H), 2.72 – 2.56 (m, 3H), 2.40 (s, 3H), 2.37 (d, J = 3.5 Hz,
precipitate. After the filtration and evaporation, the target 3H), 2.32 (s, 3H).
Fig. 1 Crystal structures, polyhedrons around the Dy(III) ions, packing model and hydrogen bonds interaction for 1 (a), (b), (c) and 2 (d), (e), (f). The hydrogen atoms and lattice
solvents are omitted for clarity. Colour code: Dy, light-blue; O, red; N, blue; C, grey; F, green; S, yellow. The bottom pictures: along the a axis.
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Fig. 2 Crystal structures, polyhedrons around the Dy(III) ions and packing model for 3 (a), (b), (c) and 4 (d), (e), (f). The hydrogen atoms and lattice solvents are omitted
for clarity. Color code: Dy, light-blue; O, red; N, blue; C, gray; F, green; S, yellow. The bottom pictures: along the a axis
Synthesis of [DyIII(TTA)3(AIP)]·0.5CH3CH2OH·0.5H2O (1), calculated C, 47.06; H, 2.71; N, 4.30. found C, 46.55; H, 2.66; N,
[DyIII(TTA)3(DPP)] (3) and [DyIII(TTA)3(BPP)]·0.5CH3CH2OH (4). 4.21.
In a 100 mL round bottom flask, HTTA (0.066 g, 0.3 mmol) and Synthesis of [DyIII(TTA)3(APIP)]·2CH3OH·H2O (2). Complex 2
triethylamine (0.067g, 0.6 mmol) were added to 30 mL of was synthesized similarly to that of 1 as described above and
ethanol. After 30 minutes of stirring, Dy(NO)3·5H2O (0.044 g, 0.1 the distinction was just the solvent of ethanol replaced by
mmol) was added and 5 minutes later, the corresponding ligand methanol with yields of 56%. C59H42DyF9N4O9S3 (2): calculated
dissolved in dichloromethane and ethanol was added (AIP: 0.04 C, 51.33; H, 3.07; N, 4.06. found C, 50.99; H, 2.91; N, 4.01.
g (1 mmol) for 1), DPP: 0.038 g (1 mmol) for 3 and BPP: 0.045 g Synthesis of [DyIII(TTA)3(AIP)]·1.5H2O (5). Complex 5 was
(1 mmol) for 4. The yellow precipitate was collected after synthesized by dissolving crystal sample of complex 1 in ethanol
stirring overnight. The yellow crystals were obtained by slow solvent along with addition of two drops of trifluoroacetic acid
evaporation of dissolved precipitate in a mixed solvent of (TFA) and then slowly evaporated for three days.
dichloromethane and ethanol with yields of 72%, 81% and 66%
respectively. Elemental analysis for C52H32DyF9N4O7S3 (1):
calculated C, 49.79; H, 2.57; N, 4.47. found C, 49.61; H, 2.65; N,
Results and discussion
4.50.C50H28DyF9N4O6S3 (3): calculated C, 49.61; H, 2.33; N, 4.63.
found C, 49.21; H, 2.12; N, 4.56. C51H35DyF9N4O6.5S5 (4):
Synthesis and General Characterizations
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The title complex was synthesized with the molar ratio of 1:1 by The variable-temperature magnetic susceptibilities of four
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DOI: 10.1039/D0DT02864A
a substitution reaction of intermediate forerunner Dy(TTA)3 complexes were measured on microcrystalline samples over the
with the auxiliary phenanthroline ligand, which was generated temperature range 1.8-300 K under an applied field of 1 kOe. As
by a ring closing reaction with a high yield. The bulk crystal shown in Fig. 3 and Fig. S2†, at room temperature, the
samples of four complexes are all stable in air at room experimentally observed mT values of 13.91 (1), 13.83 (2),
temperature. Furthermore, the purity of the powder samples 13.92 (3) and 13.94 (4) cm3Kmol-1 are consistent with the
was characterized by powder X-ray diffraction pattern and the expected value of 14.17 cm3Kmol-1 for one independent ground
experimental data agree well with the simulated results based state of Dy(III) ion (6H15/2, S = 5/2, L = 5, J = 15/2, g = 4/3).33 As
on the single-crystal diffraction data (Fig. S1, ESI†).
the temperature decrease, the mT values decrease gradually
until about 50 K and then drops sharply to reach corresponding
minimum values of 12.02, 10.17, 11.10 and 9.58 cm3Kmol-1,
which is mainly responsible for the progressive depopulation of
Crystallography
Single crystals of 1-4 can be easily obtained by a method of excited Stark sublevels and/or weak intermolecular interaction
evaporation of mother solutions. Crystal structures of these of typical behaviour for Dy(III) ion.12 As the solid line shown, the
four complexes are depicted in Fig. 1 and Fig. 2, respectively. fitted results by MOLCAS software are in good accordance with
The details of crystallographic refinement parameters are the experimental values. The calculations give the
summarized in Table S1†. Those selected bond lengths and intermolecular interaction zJ′ values of −0.001 (1), −0.04 (2),
bond angles are listed in Table S2† and Table S3†. Four −0.03 (3) and −0.07 (4). Furthermore, the variation of
complexes crystallize in monoclinic space group of C2/c (1), magnetization of 1-4 are tested at 1.8, 2.5, 5.0 and 10.0 K,
monoclinic space group of P21/c (2), monoclinic space group of respectively. The magnetization M versus H plots of four
P21/c (3) and orthorhombic space group of P212121 (4), complexes at 1.8 K rapidly increases at low field and then reach
respectively. The centre eight-coordinated Dy(III) ion is in the corresponding maximum values of 5.16, 5.18, 5.14 and 5.16,
coordination environment of [DyN2O6], of which six oxygen NB at 7.0 T, which are far less than the theoretical saturated
atoms come from three β-diketones and two nitrogen atoms value of 10 NB (gJ  J) and indicates well-separated excited
come from auxiliary ligand. The evaluated local coordination Kramers doublets as a result of strong crystal-field splitting.21,34
geometry of 2 and 4 is in close proximity to triangular The non-superposition of M versus H plots at different
dodecahedron while 1 and 3 is closed to square antiprism with temperatures implies a sign of significant magnetic anisotropy
distortion values of 0.506, 1.126, 0.596 and 1.026 by SHAPE and/or the suggested low-lying excited states. In addition, the
software.32 The Dy-O/N bond lengths are in the range of 2.288- magnetization hysteresis as an important characteristic of
2.345/2.550-2.584 Å (1), 2.302-2.337/2.555-2.571 Å (2), 2.314- magnetic bistability was also measured at 1.8 K to verify the
2.347/2.541-2.544 Å (3) and 2.288-2.353/2.569-2.590 Å (4). The slow relaxation of magnetization. As shown in Fig. 3, the M
shortest intermolecular Dy···Dy distances are 9.197 (1), 10.536 versus H plots shows clearly visible butterfly-sharped hysteresis
(2), 11.019 (3) and 11.765 (4) Å which are not necessary to loop for 1 and 4. All of the above discussions suggest the
preclude any intermolecular interactions between adjacent possibility of SMM property of four complexes.
molecules. For complexes 3 and 4, adjacent molecules are
stacked side by side along a axis while for 1 and 2, the
intermolecular ··· stacking interaction between anthracene
group and phenanthroline part form the head-to-tail dimers
and abreast array with the centroid-to-centroid distances of
3.590 (3) and 3.729 (4) Å (Fig. 1 and Fig. 2). The imidazole rings
as donor and acceptor of hydrogen bonds are linked by lattice
solvents between adjacent molecules in complexes 1 and 2.
Driven by ··· stacking interaction, the two neighbour
interacted imidazole rings form two hydrogen bonds by means
of one bridged water molecule in 1, while multiple hydrogen
bonds by water and methanol molecules make up a circle
hydrogen bonds interaction as a result of elongate distance
between the two imidazole rings, which is due to the
introduction of benzene ring of auxiliary ligand in 2 (Fig. 1). For
the six-membered pyrazine ring in complexes 3 and 4, the
hydrogen bond interaction associated with pyrazine ring is
absent. However, the obvious hydrogen bonds interaction
Fig. 3 The variable-temperature magnetic susceptibilities of 1 and 4 under an external
field of 1 kOe in the temperature range of 1.8-300 K (top view, insert: field-dependent
among ethanol molecules filled in the holes along the a axis in
complex 4, makes the shortest intermolecular Dy···Dy distance
magnetization at 1.8, 2.5, 5.0 and 10 K. The solid line represents the best fitted results.)
(11.765 Å) to be longer than it in 3 (11.019 Å) (Fig. 2).
and magnetic hysteresis loops for 1 and 4 at 1.8 K under the sweep rate of 200 Oe/s.
Static Magnetic Properties
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Dynamic Magnetic Properties
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The dynamic magnetic susceptibility for microcrystalline were
measured under zero dc external field to investigate the SMM
properties of four complexes. As shown in Fig. 4 and Fig. S3 and
S4†, both the frequency- and temperature-dependent in-phase
(') and out-of-phase ('') signals of ac magnetic susceptibilities
make the clear attitude of slow relaxation of magnetization. The
frequency-dependent out-of-phase ('') peaks that
demonstrate the “freezing” of the spins by anisotropy barriers
move to higher frequency as the increase of temperature at
high frequencies region. However, the immobility of out-of-
phase ('') peaks (Fig. 4) and tails of in-phase (') and out-of-
phase ('') versus T plots among complexes 1-4 at low
temperature are attributed to the intervention of QTM which
rooted in the incomplete blocking of anisotropy barriers and is
in response to the mixing of two ground states of degenerate
Kramers Dy(III) ions under zero field. In this case, the thermally
activated spin reversal is inhabited by a fast temperature-
independent quantum relaxation. In the meantime, there is
indeed evidence that the relaxation time may distribute in a
wide band as a result of the wide peaks of '' magnetic
susceptibilities. The quasi-semicircles of Cole-Cole plots are
fitted by generalized Debye model to give  factors in the range
of 0.23-0.18 (1.8-14 K) for 1, 0.26-0.11 (2.0-19 K) for 2, 0.13-0.05
(1.8-11 K) for 3 and 0.31-0.09 (1.8-18 K) for 4, which is
consistent with the above analysis of wide distribution of
relaxation time. In the high-temperature region, the
temperature dependence of relaxation time suggests it to be
thermally activated and the extracted magnetic relaxation time
 plotted as a function of 1/T that followed an Arrhenius law is
fitted the linear experimental data to give the effective energy
barriers (Δ/kB) and pre-exponential factors (0) of 69.4 K and
6.2410‒8 s (1), 147.3 K and 4.8210‒9 s (2), 122.1 K and
1.510‒9 s (3), 234.2 K and 7.310‒11 s (4), respectively. At low
temperature, the approximate linear dynamic shows the
expected pure quantum regime with  values of 0.0004 (1),
0.002 s (2), 0.0008 (3) 0.003 (4) which indicates a relatively
faster relaxation of 1 and 3 than 2 and 4, and consistent with
the experimentally determined effective energy barriers (see
ESI†).
Fig. 5 a) The Cole-Cole fitted data for 1, 2, 3 and 4 under the optimal field (800 (1),
1000 (2), 1500 (3) and 1000 (4) Oe) by generalized Debye model (the solid lines
represent the best results). b) The extracted magnetic relaxation time  plot as a
function of 1/T of four complexes under the optimal field. The straight lines
represent data fitting with Arrhenius law and the curves lines represent the best
fitting based on eq. 1.
In general, external magnetic field can be applied to
effectively suppress the QTM process.23 The ac magnetic
susceptibilities under different external fields were detected to
search an optimal field and the '' versus H were recorded with
varying applied fields. The significant signals of maximal value
at the magnetic fields of 1500 (1), 1000 (2), 1000 (3) and 800 Oe
(4) represent an instruction of field-induced magnetization and
the slowest relaxation, thus these external magnetic field were
selected as the optimal field to suppress the QTM process. As
the Fig. S5† shows, the rising tails of in-phase (') and out-of-
phase ('') versus T plots disappear apparently at low
temperatures by reference to that in zero field plot and show
obvious shift to high temperature as the increase of frequency.
These phenomena indicate that the QTM is indeed effectively
suppressed. The magnetic relaxation time  are extracted
according to the corresponding Cole-Cole fitting. The thermal
activated energy barriers of 102.0 K (1), 167.0 K (2), 141.1 K (3)
and 240.0 K (4) are achieved by fitting the high-temperature
experimental data using Arrhenius law. Furthermore, the
multiple relaxation processes of Direct, Raman and Orbach are
taken into account using eq. 1 to clarify the whole behaviours
in the ln() vs 1/T plots. The best fitted parameters were
obtained, that is, A = 1.1 s-1K-1, C = 0.0095 s-1K-5.45, n = 5.45, τ0 =
Fig. 4 Frequency dependence of the out-of-phase ('') ac susceptibility of 1, 2, 3
and 4 in zero dc field.
5.4710-9 s, Δ/kB = 102.0 K (1); A = 0.05 s-1K-1, C = 0.0001 s-1K-6.51
,
n = 6.51 τ0 = 1.0610-9 s, Δ/kB = 167.0 K (2) A = 0.001 s-1K-1, C =
0.025 s-1K-4.84, n = 4.84, τ0 = 7.0110-10 s, Δ/kB = 141.1 K (3); A =
1.11 s-1K-1, C = 0.12 s-1K-3.75, n = 3.75, τ0 = 1.7510-11 s, Δ/kB =
240.0 K (4).
휏−1 = 퐴푇 + 퐶푇푛 + 휏0-1exp(−/푘퐵푇)
(1)
6 | J. Name., 2012, 00, 1-3
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ARTICLE
The dynamic magnetic studies reveal the significant difference
among four complexes, which indicates the distinct influence of
the ligand field on various relaxation mechanisms. The analysis
of X-ray single crystal structure shows that the slight changes of
the ligand can lead to transformation of the local geometrical
configuration of the Dy(III) centre and thus regulate the slow
magnetic relaxation. What was known is that the different local
symmetry and coordination bond distance can bring an
effectively influence on the ligand fields, which frankly give rise
to diverse magnetic behaviours. Nevertheless, the novel
magnetic anisotropy is dominated not only by local symmetry,
but also by simultaneously complicated factors such as,
electrostatics, guest molecules and delocalization effect of
neutral ligand. Therefore, in-depth theoretical explorations of
magneto-structural correlations are full of worth.
View Article Online
DOI: 10.1039/D0DT02864A
Ab Initio Calculations
Fig. 7 The Magnetization blocking barriers in 1, 2, 3 and 4, respectively. The thick
black lines represent the KDs as a function of their magnetic moments along the
magnetic axis. The green lines correspond to diagonal QTM, and the blue lines
represent Orbach relaxation process. The red arrows represent the most possible
path for magnetic relaxation. The numbers at each arrow stand for the mean
absolute values of the transversal magnetic moments.
For a better theoretical elucidation of the prominent difference
of magnetic properties of four complexes, the CASSCF
calculations based on X-ray single crystal structures have been
performed on individual Dy(III) fragment for each complex
through MOLCAS 8.4 and SINGLE_ANISO programs. The
computational results are presented in the Supporting
Information in detail. The calculated lowest spin-orbit energies
and the correlative g tensors manifest the strong axial
anisotropy of the ground KD with g values: gx = 0.025, gy = 0.036,
gz = 19.517 (mJ = ±15/2, 1); gx = 0.009, gy = 0.010, gz = 19.458
(mJ = ±15/2, 2); gx = 0.017, gy = 0.024, gz = 19.561 (mJ = ±15/2,
3); gx = 0.004, gy = 0.007, gz = 19.640 (mJ = ±15/2, 4). In spite of
higher than previous reported results of high-performed Dy(III)-
SIM, such small gx and gy suggested the nominal criterion for
slow magnetic magnetization in zero field of four
complexes.17,18 The predominant mJ values of the ground states
and first excited states are mostly composed by ±15/2 and
±13/2 for four complexes (Table 1). The distinct differences of g
tensors put forward to the conclusion that complex 4 possesses
more Ising-type axial anisotropy of ground doublets than 3. In
accordance with the calculated results of the first excited
energy, the experimental energy barriers of 102.0 K (1), 167.0 K
(2), 141.1 K (3) and 240.0 K (4) are closed to the theoretically
calculated results of 148.2 K (1), 187.5 K (2), 166.9 K (3) and
225.5
K (4). The much smaller shortcut value of the
experimental datum of 69.4 K in zero dc field than the
calculated value of 148.2 K for 1 suggests that such a relaxation
does not reach the first excited state in this complex due to fast
under-barrier relaxation caused by anharmonic phonons.
Based on the theoretically calculated orientation of the
magnetic easy axis (Fig. 6), those planes containing two nitrogen
atoms of auxiliary ligands that are vested in the equatorial plane
assume to be nearly perpendicular to the main magnetic axis.
The above studies have essentially determined the more axial
of KDs in 2 (4) than 1 (3). Previously reported results have shown
the preference of excess of axial electrostatic repulsion of high-
performance SMMs around the central Dy(III) ions. As a result,
the more charge distribution in the equatorial plane has the
opposite effect. The slightly larger values of NBO charge on
coordinated nitrogen atoms in 3 (1) than 4 (2) seemingly shows
the variant electron donor effect and the influence on
electrostatic potential in equatorial plane (Fig. S17†). So, the
almost twofold higher effective energy barrier of 4 than that of
3 is mainly originates from the stronger conjugation effects of
Table 1. Wave functions with definite projection of the total moment | mJ > for the
lowest two KDs for complexes 1, 2, 3 and 4.
E/cm-1
0.0
wave functions
94.9%|±15/2>
1
2
3
4
102.9
0.0
46.7%|±13/2>+11.2%|±3/2>+11.1%|±11/2>
93.0%|±15/2>
133.9
0.0
57.6%|±13/2>+27.1%|±9/2>+9.4%|±11/2>
95.2%|±15/2>
115.9
0.0
55.0%|±13/2>+15.8%|±11/2>+13.8%|±9/2>
95.2%|±15/2>
Fig. 6 The ab initio calculated orientations of the local main magnetic axes of the
ground KDs on Dy(III) ions for complexes 1 (a), 2 (b), 3 (c) and 4 (d), respectively.
Colour code: Dy, light-blue; O, red; N, blue; C, grey; F, green; S, yellow.
156.6
71.9%|±13/2>+16.0%|±9/2>
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J. Name., 2013, 00, 1-3 | 7
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ARTICLE
Journal Name
benzene rings than thiophene rings and furtherly enhance
electrostatic potential in equatorial plane.35 As a consequence,
the Dy-N bond distances of 4 are longer than 3. For complex 2,
the anthracene group and phenanthroline group in the ligand
are isolated by the intermediate benzene group, which resulting
in the nearly orthorhombic configuration between anthracene
and benzene rings with a dihedral angle of 59.44, and
resistance effect for charge flowing. Naturally, 2 take possession
of relatively less electrostatic potential than 1 in equatorial
plane, which conforms to both the experimental data and ab
initio calculations (see ESI†). However, the role of
intermolecular hydrogen bonds interactions should be the
dominant factor in modulating the magnetic dynamic of 1 and
2 by contrasting with the impact of electrostatic potential.
Conclusions
View Article Online
DOI: 10.1039/D0DT02864A
In summary, we have synthesized five new eight-coordinate Dy-
β-diketones complexes of 1, 2, 3, 4 and 5 by modulating
auxiliary ligand. They all perform as SIMs with Ising-type ground
states and demonstrate that stronger electron conjugation
effect of auxiliary ligands and intermolecular hydrogen bonds
interactions results in deterioration of magnetic anisotropic
barriers. The further in-depth research of relaxation mechanism
was elucidated by cooperating experiment with theoretical
studies, as a result of which the diverse SIM behaviours with
various degree of QTM process are responsible for the subtle
modification of coligands. In this work, we demonstrate that the
slight modulating of the auxiliary ligand can not only regulate
charge conjugation effect, but also simultaneously change the
local symmetry of Dy(III) ion and intermolecular interactions, by
which generate the variation of energy sublevels to bring
different dynamic magnetic behaviours into existence. Overall,
we provide a fresh perspective in certifying the authenticity and
significance of electron-donating effect and intermolecular
interactions of auxiliary ligand for modulating the magnetic
properties.
23d,23e
Fabrice Pointillart
has revealed that the hydrogen bond
interaction in non-alkylated imidazole ring result in the absence
of SMM property. By comparing the experimental energy
barrier of 1 with 2, the depravation of SMM property in 1 may
be on account of the distinct intermolecular hydrogen bonds
that are made up of only two OH O-H···Nimidazole interactions
2
between adjacent molecules, than 2 whose hydrogen bonds
form a circulation by feat of multiple Nimidazole-H···OH O, OH O
-
2
2
H···OCH OH
,
OCH OH-H···OCH OH
and
OCH OH-H···Nimidazole
3
3
3
3
interactions (Fig. 2). To elucidate the speculation of hydrogen
bond influence, complex 5 with main structure similar to 1 has
been synthesized by dissolving complex 1 in ethanol solvent
along with addition of two drops of trifluoroacetic acid (TFA)
(see ESI†). As shown in Fig. S10†, the lattice solvent of 5 was
only water while water and ethanol molecules were found in 1.
Meanwhile, the hydrogen bond interactions display distinct
modes. In 5, all the N and H atoms located in imidazole ring form
Nimidazole-H···OH2O or Nimidazole···H-OH2O hydrogen bonds. However,
only one type of hydrogen bond interaction exists in 1.
Furthermore, the coordination bond distances are slightly
variable (Table S17†). Thus, complex 5 have the nearly identical
structure with 1 except for the intermolecular hydrogen bond
interaction. As shown in Figs. S13 and S14†, the independence
of out-of-phase ('') versus  and tails of out-of-phase ('')
versus T plots of 1 and 5 at low temperature indicates the
presence of strong QTM. However, the peaks of out-of-phase
('') in the lower frequency regions of 5 demonstrates the
slower magnetic relaxation than 1. The magnetic energy
barriers of 45.0 K (1) and 70.6 K (5) are achieved by fitting the
high-temperature data using Arrhenius law. The pure quantum
regime with  values are 0.0003 (1) and 0.0006 (5), which
indicates the relatively faster relaxation in 1 (Figs. S15 and S16†).
From these results, it is suggested that after dealing with TFA,
the new complex 5, with distinct hydrogen bond interaction
comparing with 1 shows modest improvement of SMM
property. We then perform a theoretical CASSCF calculation of
5 through MOLCAS 8.4 with the same method as 1 for
comparison. The calculated results are shown in Table S18 and
S19, Figs. S17 and S18†. It is obvious that the calculated
parameters of 5 are nearly the same as 1, which accounts for
the nearly same coordination environment. Therefore, the
experimental difference of magnetic dynamic can be ascribed
to the distinction of hydrogen bond interactions. Based on the
experimental and theoretical analyses, we point out that in this
system the hydrogen bond interactions play an important role
in manipulating magnetic dynamic.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We thank the National Key R&D Program of China
(2017YFA0303203 and 2018YFA0306004) and the National
Natural Science Foundation of China (21571097, 21973038 and
21973046).
Notes and references
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DOI: 10.1039/D0DT02864A
Four perturbed eight-coordinated mononuclear -diketone based Dy(III) SIMs with
distinct hydrogen bonds interaction and electron delocalization are noteworthily
modulated by the aromatous groups of auxiliary ligands.