DOI: 10.1002/asia.

201701032 Focus Review

Magnetic Properties

Recent Developments in Lanthanide Single-Molecule Magnets

Jingjing Lu,[a, b] Mei Guo,[a, c] and Jinkui Tang*[a]

Chem. Asian J. 2017, 12, 2772 – 2779 2772 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Abstract: Single-molecule magnets (SMMs) exhibiting slow
relaxation of magnetization of purely molecular origin are
highly attractive owing to their potential applications in
spintronic devices, high-density information storage, and
quantum computing. In particular, lanthanide SMMs have
been playing a major role in the advancement of this field
1. Introduction
The discovery of the [Mn12O12(OAc)16(H2O)4] (Mn12Ac) complex,
which displays slow relaxation (SR) of magnetization at the
molecular level,[1] and currently qualifies as the first single-mol-
ecule magnet (SMM),[2] has sparked worldwide research inter-
est owing primarily to potentially multifarious applications in
molecular spintronic devices, high-density information storage,
and quantum computations.[3] The effective barrier (Ueff) and
blocking temperature (TB) are two key parameters commonly
used to evaluate the success (or not) of a SMM. In the last two
decades, extraordinary efforts have been directed towards in-
creasing Ueff and TB.[4] Indeed, early research was merely con-
fined to strong-coupling 3d SMMs, for which maximizing the
spin value of the ground state (S) was regarded as the most ef-
ficient way to obtain SMMs with high Ueff. Nevertheless, later
theoretical study demonstrated that large ground-state spin (S)
and strong magnetic anisotropy (D) within one molecule could
not be obtained simultaneously.[5] Lanthanide ions were then
identified as superior spin carriers for SMMs thanks to their
large magnetic moments and strongly inherent magnetic ani-
sotropies caused by strong spin–orbit coupling.[6] In particular,
the observation of SR behavior in mononuclear lanthanide spe-
cies, as in the example of double-decker phthalocyanine (Pc)
complexes [LnPc2]@ (Ln = Tb, Dy),[4a] really ignited intensive ex-
ploration of lanthanide SMMs. However, the blossoming of
pure polynuclear lanthanide SMMs dates back to the presenta-
tion of the triangular Dy3 cluster, with fascinating toroidal ar-
rangement of magnetic moments.[7] To date, some remarkable
results have been presented: experimentally, the record effec-
tive energy barrier to magnetic relaxation (Ueff) and blocking
temperatures (TB) have increased up to 1837 and 60 K, respec-
tively, in dysprosium(III)-based single-ion magnets (SIM),[8] and
the SR time is up to 1500 s at 10 K[9] in some diluted com-
[a] J. Lu, M. Guo, Prof. Dr. J. Tang
State Key Laboratory of Rare Earth Resource Utilization
Changchun Institute of Applied Chemistry
Chinese Academy of Sciences
Changchun 130022 (P.R. China)
E-mail: tang@ciac.ac.cn
[b] J. Lu
University of Science and Technology of China
Hefei 230026 (P.R. China)
[c] M. Guo
University of Chinese Academy of Sciences
Beijing 100049 (P.R. China)
The ORCID identification number(s) for the author(s) of this article can be
found under https://doi.org/10.1002/asia.201701032.
Chem. Asian J. 2017, 12, 2772 – 2779 www.chemasianj.org
Focus Review
because of the large intrinsic magnetic anisotropy of lantha-
nide metal ions. Herein, some recent breakthroughs that are
changing the perspective of the field are highlighted, with
special emphasis on synthetic strategies towards the design
of high-performance SMMs.
plexes. Theoretically, several models and design strategies also
provide a more intuitive method to achieve high-performance
lanthanide SMMs.[10]
Despite these outstanding achievements, it remains chal-
lenging to put SMM-based technology into use given that the
peculiar properties of SMMs can currently only be attained
under liquid-helium cooling.[11] Therefore, it is critical to ration-
ally design efficient SMMs with operating temperatures as
close as possible to that of the practical application. In view of
the dominant position of lanthanide SMMs in molecular mag-
netism, it is of enormous interest to examine the synthetic
strategy for further improvement of their SMMs properties.
With this in mind, we observed some eye-catching progress
with regard to slow magnetic relaxation, quantum tunneling
effects, magnetic coupling, and toroidal magnetic moments,
with the hope of shedding light on several approaches to-
wards synthesizing novel lanthanide SMMs in the future.
2. Synthetic Strategy and Recent Develop-
ments
In general, the effective crystal-field Hamiltonian of lanthanide
ions based on Stevens notation[6, 12] can be written as shown in
Equation (1):
X X
k X X
k
6 5
^ CF ðJÞ ¼
H Bqk Oqk ¼ ak Aqk r k Oqk
k¼2;4;6 q¼@k k¼2;4;6 q¼@k
in which Okq are termed as the operator equivalents of the
crystal-field potential; in particular, the Ok0 terms are most
dominant in determining the energy order of the mJ states,
whereas the Okq (q ¼ 6 0) terms are responsible for generating
avoided level crossings, which are usually regarded as the
main origin of quantum tunneling of magnetization (QTM).[13]
The Bkq or Akq < rk > terms are the crystal-field parameters relat-
ed to the symmetry of coordinate system, which determine
the existence or not of Okq (q ¼ 6 0). Notably, the Okq (q ¼6 0)
terms always vanish in some highly symmetric coordination
environment, such as C1v, D1h, D4d, D5h, and D6d.[14] Therefore
increasing the ligand-field symmetry has been widely adopted
to enhance the properties of SMMs.
In 2011, Long and Rinehart proposed the qualitative electro-
static model,[10a] which gave the relationship between the coor-
dination environment of lanthanide ions and the magnetic ani-
sotropy of the complex; thus we can match an appropriate
ligand field to maximize magnetic anisotropy on the basis of
the shapes (oblate or prolate) of the 4f-shell electron density
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distributions. The sandwich-type crystal field is greatly favora-
ble to stabilize the ground states, with the largest magnetic
moment for ions possessing oblate electron density distribu-
tions, such as dysprosium(III) and terbium(III) ions, as con-
firmed by bis(phthalocyaninate) complexes.[4a] However, the
equatorially coordinated geometry is indispensable for those
ions with prolate electron density distributions, such as erbiu-
m(III) and ytterbium(III), as revealed in the first equatorially
three-coordinate erbium(III) SIM reported by our group.[15] As
shown in Figure 1, the central erbium(III) ion is bonded by
Figure 1. Top: The electrostatic model: depictions of low- and high-energy
configurations of the f-orbital electron density with respect to the crystal
field environment for a 4 f ion of oblate (left) and prolate (right) electron
density. Reproduced from ref. [10a] with permission from the Royal Society
of Chemistry. Bottom: The molecular structures of [LnPc2]@ (left) and Er[N(-
SiMe3)2]3 (right) reported in refs. [4a, 15], respectively. Copyright American
Chemical Society.
three sterically hindered ligands with a ligand field of perfect
C3v symmetry. Moreover, it exhibits a higher anisotropy barrier
of 122 K and butterfly-shaped magnetic hysteresis. Here, the
equatorially coordinating crystal field with C3v symmetry signifi-
cantly enhances the axial anisotropy of the erbium(III) ion,
which is responsible for excellent SMM behavior. Ab initio cal-
culations reveal an unprecedented magnetic relaxation path-
way through the fourth excited state.[16] Remarkably, the quan-
titative electrostatic calculations method of the above model
has proved successful for finding the anisotropy axis direction
in some low-symmetry systems,[17] as well as polynuclear sys-
tems.[18]
In addition, another way to obtain strong uniaxial anisotropy
of lanthanide ions is to achieve only one very short chemical
bond, with the metal ion dominating over all other bonds,
which corresponds to the effective coordination number of
one.[10c, 19] As revealed in the ideal axial symmetric diatomic
molecule [DyO] + , all electronic states of which display aniso-
tropy axes parallel to the Dy@O bond, with only the mJ = : 1/2
excited doublets exhibiting transverse anisotropy (g ? ¼ 6 0),
which is responsible for the energy barrier of magnetization re-
versal exceeding 3000 K.[20] Recently, we reported a typical ex-
Chem. Asian J. 2017, 12, 2772 – 2779 www.chemasianj.org
Focus Review
ample of a DyNCN complex containing a localized Dy@C bond
(Figure 2),[21] which exhibits strict C2v symmetry and the C2 axis
passes along the Dy@C chemical bond direction. In particular,
the carbon atom is closest to the dysprosium(III) ion, relative
to other coordination atoms, which renders the strongest elec-
trostatic interaction between them. Accordingly, the strong ax-
iality and collinearity of anisotropy axes in the two lowest
Kramers doublets lead to unprecedented relaxation mediated
via the second excited state. This novel relaxation mechanism
demonstrated that a perfect axial ligand field facilitates relaxa-
tion through higher energy levels; thus low-coordinate lantha-
nide complexes offer exciting opportunities to develop high-
barrier SMMs.
2.1. Lanthanide SIMs
The smallest magnet-like molecules containing only a single
spin center are usually called SIMs;[22] these afford the opportu-
Jingjing Lu received her BSc degree in chemis-
try from Luoyang Normal University, P.R.
China, in 2014. She is currently undertaking
her PhD research under the supervision of
Prof. Jinkui Tang at Changchun Institute of
Applied Chemistry, Chinese Academy of Scien-
ces (CAS). Her research interest is molecular
magnetism.
Mei Guo obtained her BSc degree in chemistry
from Inner Mongolia University, P.R. China, in
2013. Now she is conducting her PhD research
at Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, focusing on
lanthanide-based molecular magnetism under
the direction of Prof. Jinkui Tang.
Jinkui Tang received his PhD degree in 2001
from Nankai University under the supervision
of Prof. Dai-Zheng Liao and then worked as a
postdoctoral fellow at Universit-t Karlsruhe
(TH) in the research group of Prof. Annie K.
Powell and at Universiteit Leiden with Prof.
Jan Reedijk, before initiating his independent
career at Changchun Institute of Applied
Chemistry, Chinese Academy of Sciences, in
2007. His research interests center around the
design and characterization of coordination
compounds with interesting magnetic proper-
ties.
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Figure 2. The molecular structure and possible relaxation pathways of low-lying doublet states for DyNCN. KD = Kramers doublet. Reprinted with permission
from Macmillan Publishers Ltd., copyright 2014.[21]
nity to gain a better understanding of magnetostructural cor-
relation and to modulate their SIM behavior.[22c] Nevertheless,
so far, SIMs are heavily dominated by square-antiprism (SAP)
complexes with D4d symmetry, the most foremost species are
Pcs,[4a] polyoxymetalates (POM),[23] and b-diketone[22a, 24] com-
plexes.
Recently, our group published a series of mononuclear dys-
prosium SMMs of the type [DyLz2(o-vanillin)2]·X·solvent (X = Br@
(1), NO3@ (2), CF3SO3@ (3); Lz = 6-pyridin-2-yl-[1,3,5]triazine-2,4-
diamine), in which all dysprosium(III) featured a pseudo-D4d co-
Figure 3. The cis and trans configurations of [DyLz2(o-vanillin)2] + (left) and
magnetic hysteresis of complex 2 (right). Reprinted with permission from
ref. [25]. Copyright 2016 Royal Society of Chemistry.
Chem. Asian J. 2017, 12, 2772 – 2779 www.chemasianj.org
Focus Review
ordination environment; this provides an intriguing illustration
that not only the ligand-field symmetry, but also the likely cis–
trans isomerism of coordinating atoms, could regulate the re-
laxation behavior.[25] As shown in Figure 3, complex 2 is charac-
teristic of the two Lz ligands situated in the trans position,
compared with that of the cis position in complexes 1 and 3.
Magnetic measurements reveal that all complexes exhibit out-
standing SMMs behavior; in particular, complex 2 shows a re-
markable thermal energy barrier of 615 K and the magnetic
blocking temperature reaches up to 7 K. These results may be
attributed to the relative axial extension of the SAP coordinat-
ing plane in complex 2, which is expected to increase molecu-
lar symmetry and further lead to magnetic relaxation, probably
passing through the fourth and even fifth Kramer doublet
states.
The pentagonal bipyramidal complexes with D5h symmetry
are also highly attractive based on crystal-field theory and
some experimental achievements in this respect.[26] Notably,
the dysprosium(III) SIM [Dy(OtBu)2(py)5] + (py = pyridyl) present-
ed by Zheng et al. represents great progress in D5h-symmetric
complexes with a large anisotropy energy barrier (Figure 4).[27]
Interestingly, the dysprosium(III) ion is surrounded by two
strong anionic oxygen donors in the axial position and five rel-
atively weak pyridine nitrogen donors in the equatorial plane.
It should be noted that the axial Dy@O bonds of 2.1 a are the
shortest observed in seven-coordinate dysprosium complexes;
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Figure 4. The crystal structure and variable-temperature out-of-phase mag-
netic susceptibility of [Dy(OtBu)2(py)5] + . Reprinted with permission from
ref. [27]. Copyright 2016 Wiley-VCH.
this value is significantly shorter than the Dy@N bonds (2.5 a).
Clearly, the alternating current (ac) susceptibility data display
robust frequency and temperature dependence, and the tem-
perature of the c’’ peak at 1500 Hz is higher than 100 K. The
shorter chemical bond, together with the compressed pentag-
onal bipyramidal geometry of the dysprosium(III) ion, contrib-
utes to the superior SMM behavior, resulting in a magnetic
blocking temperature of 14 K and high energy barriers of
1815 K.
In addition, planar cyclooctatetraene (COT) systems play sig-
nificant roles in lanthanide SIMs, owing to high rotational sym-
metry. Early research can be dated back to 2011, when Gao
et al. demonstrated that SR occurred in a sandwich erbium(III)
complex.[22b] Subsequently, some other metallocene systems
were also explored by their and other groups.[4c, 28] Strikingly,
recent work by the Layfield and the Mills groups represents
the newest developments, namely, the monometallic dysprosi-
um SMM [(Cpttt)2Dy][B(C6F5)4] (Cpttt = 1,2,4-tri(tert-butyl)cyclo-
pentadienide) demonstrates an unprecedentedly large aniso-
tropy barrier, high magnetic blocking temperature, and high
coercivity.[8] As can be seen from Figure 5, the central dyspro-
sium(III) ion is bonded to two Cpttt ligands with a Cpc-Dy-Cpc
angle of 152.8458 (Cpc = ligand centroid). Notably, ac suscepti-
bility studies indicate that the c’’ peaks were observed at tem-
peratures of 72–110 K at zero applied field, with a record effec-
tive barrier of 1837 K. More remarkably, the magnetic hystere-
sis loops open up to 60 K, which represents the highest block-
ing temperature reported in the field of SMMs to date.
Figure 5. The crystal structure and magnetic properties of [(Cpttt)2Dy][B(C6F5)4]. Reprinted with permission from ref. [8a]. Copyright 2017 Wiley-VCH.
Chem. Asian J. 2017, 12, 2772 – 2779 www.chemasianj.org
Focus Review
2.2. Polynuclear Lanthanide SMMs
Because of the radially contracted nature of 4f orbitals, any su-
perexchange interactions between lanthanide centers tend to
be very weak, leading to large effective energy barriers in the
majority of polynuclear lanthanide SMMs that are often as-
cribed to the single-ion magnetism.[11] However, magnetic in-
teractions between lanthanide ions is of great importance for
enhancing the SMM performance in the low-temperature
region. For example, when the magnetic interactions are
higher than the temperature domain of the QTM, the QTM can
be suppressed effectively.[3b, 29] In addition, the nonlinear con-
nection of single-ion anisotropy axes from different lanthanide
centers will result in some special magnetic phenomenon,
such as multiple relaxation processes[29a, 30] and spin chirali-
ty.[7, 31]
2.2.1. Magnetic Interactions
The most effective way to improve the magnetic interaction is
to introduce radical ligands.[32] In 2011, Long et al. probed the
magnetism of a series of N23@-radical-bridged dilanthanide
complexes.[33] As shown in Figure 6, the magnetic interaction
was J = @27 cm@1 in the N23@-bridged Gd2 complex; this repre-
sents the highest magnetic coupling observed for gadolinium
complexes. The dysprosium and terbium analogues also exhib-
it strong magnetic interactions, and the cT values exhibit
sudden drops at low temperature. Notably, the ln t versus 1/T
plots over the entire measured temperature ranges show a
perfectly linear relationship, which suggests a single dominant
Orbarch process that is indicative of the effective suppression
of the QTM. More importantly, the Tb2 SMM exhibits considera-
ble magnetic hysteresis without steps at temperatures of 14 K.
Here, the diffuse spin orbitals of radical ligands can penetrate
the core electron density of the lanthanide ions, which ac-
counts for such strong interactions between the lanthanide
ions.
Meanwhile, an asymmetric Dy2 SMM obtained by our group
provides the opportunity to investigate how magnetic interac-
tions between dysprosium(III) ions can influence dynamic mag-
netic properties.[29a] As seen from Figure 7, two dysprosium(III)
ions are situated in different local coordination geometries,
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 Focus Review

ture approaches 2 K, which indicates almost stark

“freezing” of the spins and the effective suppression
of zero-field QTM. The ferromagnetic exchange inter-
action between lanthanide ions is responsible for
the suppression of QTM at low temperatures, where-
as at high temperatures blockage of magnetization
occurs owing to the individual anisotropic centers.
Thus, we were able to separate, for the first time,
two distinct regimes of blockage of magnetization:
one originating from blockage at individual dysprosi-
um sites and the other owing to the exchange inter-
action between sites. Furthermore, to correlate the
relaxation processes with specific metal sites, an
asymmetric Dy2 SMM displaying a well-separated,
two-step relaxation process with anisotropic centers
in fine-tuned local environments was elaborately de-
signed, and a one-to-one relationship between the
metal sites and relaxation processes was evi-
denced.[30]

Figure 6. The crystal structure and static magnetic properties of the N23@-radical-bridged
lanthanide family. Top: Reprinted from ref. [33b] with permission. Copyright 2011, Mac- 2.2.2. Toroidal Magnetic Moments
millan Publishers Ltd. Bottom: Reprinted from ref. [33a] with permission. Copyright 2011,
American Chemical Society. Magnetic complexes behaving as single-molecule
toroics (SMTs), which were defined as a class of bi-
stable molecules with a toroidal magnetic state,
were systematically investigated in our recent tutorial
review.[34] To date, such molecules have been rarely reported to
exhibit the toroidal moment in the ground state; several typi-
cal examples include Dy3 triangles,[7, 35] planar Dy4,[36] cyclic
Dy6,[37] and coupling Dy3[31, 38] complexes. It should be noted
that the coupled Dy3 SMTs constructed by us represent a
major breakthrough in maximizing toroidal moments.[38a] In ad-
Figure 7. The crystal structure, magnetic anisotropic axes, and dynamic mag- dition, a series of isomorphous Dy6 complexes were synthe-
netic properties of the asymmetric Dy2 SMM. Reprinted with permission sized by our group to explore the impact of axial ligands on
from ref. [29a]. Copyright 2011 American Chemical Society.
toroidal magnetic moments.[38b, 39] As shown in Figure 8, the
Dy6 core can be considered as the linkup of two planar Dy3 tri-
with the eight-coordinate Dy1 center revealing a hula hoop- angular units in an edge-to-edge fashion, in which the vertices
like geometry and the seven-coordinate Dy2 center exhibiting of the Dy3 triangular units are linked through bridging phenol
a nearly perfect pentagonal bipyramidal geometry, which is oxygen atoms and hydroxo atoms. Interestingly, the equatorial
probably responsible for the presence of two relaxation pro- coordination sphere of dysprosium(III) ions in all complexes is
cesses, as confirmed by ac magnetic susceptibility data. The ef- almost identical, whereas the axial positions reveal prominent
fective energy barriers are 150 and 198 K for the fast relaxation differences. As a result, the introduction of axial O atoms from
(FR) and SR phases, respectively. It is important to highlight H2O groups, in contrast to the axial coordination of SCN@ and
that both c’ and c’’ signals nearly vanish when the tempera- NO3@ anions, gives rise to changes in the local electronic struc-

Figure 8. The molecular structure with the orientation of anisotropy axes and static magnetic data of Dy6[Br]. Reprinted with permission from ref. [38b]. Copy-
right 2016 Royal Society of Chemistry.

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ture and the direction of the easy axes at each dysprosium
site. Accordingly, the Dy6[Br] complex exhibits the toroidal
magnetic moment in the ground state, which is absent in the
other cases.
3. Summary and Outlook
We briefly surveyed the most up-to-date progress in the fasci-
nating and challenging field of lanthanide SMMs and included
notable results, such as the new benchmark in molecular mag-
netism, which was a dysprosium(III) metallocenium SMM with
a record anisotropy barrier of 1837 K and record magnetic
blocking up to 60 K; this pushes the blocking temperature
much closer to that of the temperature of liquid nitrogen and
the rational design of complexes with unique toroidal magnet-
ic moments. These new findings are, without doubt, of interest
for the community of molecular magnetism because they sug-
gest the directions in which further synthetic efforts should be
focused.
First, for lanthanide SIMs, engineering a ligand field in which
the magnetic easy axis is desirably oriented will be an effective
strategy to improve the axial anisotropy of the lanthanide ions,
and thus, reach the limit of the effective energy barrier. The
conventional route for obtaining perfect axial anisotropy is to
modulate the coordination geometries of the crystal fields
through a coordination symmetry approach, as demonstrated
in some particular crystal-field symmetries, such as D4d and D5h.
Another way is to lower the effective coordination number,
which can be achieved through the rational design of the
ligand environment, in which the metal ion interacts much
stronger with one of the ligand atoms. In this case, this strong
chemical bond dominates over all other chemical bonds of the
metal site, resulting in the intrinsically axial nature of the total
ligand field. In particular, linear two-coordinate complexes with
perfect axial anisotropy will be intriguing and challenging for
synthetic chemists.
Second, for polynuclear lanthanide SMMs, the relatively
strong magnetic coupling can effectively reduce the QTM pro-
cess at low temperatures; thus prompting communication be-
tween the spin centers appears to hold great promise in ac-
quiring SMMs with higher blocking temperatures.
Third, the exploration of coupled toroidal moments in SMT
molecules seems to be very appealing, given potential applica-
tions as magnetoelectric and related multiferroic materials.
However, the synthesis of SMT molecules with strong coupling
interactions remains quite difficult.
Finally, the ultimate aim of this research is to prepare elec-
tronic molecular devices for possible applications. Nowadays,
considerable efforts have been devoted to organizing SMMs
on surfaces,[40] developing a novel family of SMMs,[41] as well as
designing molecular spintronics by using SMMs.[42] Preliminary
results suggest that the lanthanide double-decker Pc SMM sys-
tems are more promising for technological applications, mainly
owing to their extraordinarily robust structural and magnetic
properties. However, they are still far from practical applica-
tions because of the low blocking temperatures at which the
magnetic memory effects are observable and the uncontrolled
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Focus Review
orientation of molecules when they are deposited onto surfa-
ces. Recently, the magnetism of single atoms adsorbed on sur-
faces has been extensively studied.[43] Through great progress,
the magnetic remanence was observed in isolated holmium
atoms supported on MgO, which exhibited magnetic hysteresis
up to 30 K.[9] Importantly, a more striking breakthrough is that
the spin states of these atoms can be read out and written
electrically, which paves the road for the development of high-
density magnetic storage media.[44]
Acknowledgements
We thank the National Natural Science Foundation of China
(grants 21525103, 21371166, 21331003, and 21521092) for fi-
nancial support.
Conflict of interest
The authors declare no conflict of interest.
Keywords: coordination modes · lanthanides · magnetic
properties · quantum tunneling · single-molecule magnets
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Manuscript received: July 18, 2017
Revised manuscript received: August 30, 2017
Accepted manuscript online: September 1, 2017
Version of record online: October 16, 2017
T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim