ChemPhysMater 1 (2022) 247–251

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ChemPhysMater
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Short Communication

Tridecanuclear Gd(III)-silsesquioxane: Synthesis, structure, and magnetic

property
Kai Sheng a,b,∗, Ran Wangc, Alexey Bilyachenko d, Victor Khrustalev e, Marko Jagodič f,
Zvonko Jagličić f,∗, Zhaoyang Li g, Likai Wang h, Chenho Tung b, Di Sun b,∗
a
School of Aeronautics, Shandong Jiaotong University, Jinan 250037, China
b
School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China
c
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University,
Liaocheng 252000, China
d
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow 119991, Russia and Peoples’ Friendship University of Russia,
Moscow 117198, Russia
e
Peoples’ Friendship University of Russia, Moscow 117198, Russia and Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia
f
Institute of Mathematics, Physics, and Mechanics, Ljubljana 1000, Slovenia
g
School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
h
School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255049, China

a r t i c l e i n f o a b s t r a c t

Keywords: Polynuclear metal clusters, particularly those with aesthetically appealing structures, are of increasing interest. In
Gd-silsesquioxane this study, by employing C4 symmetrical macrocyclic silsesquioxane ligand, a novel tridecanuclear Gd(III) cluster
Crystal structure (Gd13) with a {Gd13 O8 } core featuring unprecedent body-centered Archimedean cuboctahedron conformation
Archimedean solid
is realized using an efficient solvothermal method instead of conventional Schlenk techniques. To the best of our
Magnetic property
knowledge, Gd13 cluster is thus far the highest nuclearity of lanthanide-silsesquioxane. Moreover, a magnetic
Magnetocaloric effects
study reveals a weak antiferromagnetic interaction between adjacent Gd ions in the cluster. In addition, Gd13
exhibits cryogenic magnetocaloric effects with a maximum −ΔSM value of 20 J kg−1 K−1 at 2 K and ΔH = 7.0 T.

1. Introduction other metal-based metallasilsesquioxanes because of their excellent op-

Metallasilsesquioxanes (including clusters or cages), assembled from
incompletely condensed silsesquioxane ligands and metal species, have
garnered increasing attention in the past decades, not only owing to
their unique structure and fascinating physicochemical properties but
also because they are regarded as ideal theoretical molecular models
for silica-supported materials [1–10]. Because the basic building block
silsesquioxane (with the general formula [RSiO1.5 ]n ) can appear with
numerous possible fragments differing in number n and composition R,
and owing to the high affinity of multiple terminal O atoms toward metal
ions, various interesting metallasilsesquioxane architectures, including
s- and d-block metal ions such as Li+ , K+ , Mg2+ , Cu2+ , Co2+ , Mn2+/3+ ,
Fe2+/3+ , Ni2+ , Zn2+ , and Ti3+/4+ have been developed [11–17]. Despite
those considerable efforts that have been dedicated, the chemistry on
f-elements metallasilsesquioxanes is much less behind mostly owing to
the certain challenges in the synthesis, for instance, uncontrollable hy-
drolysis of Ln(III) ion and difficulties in crystallization [4,18–20]. In fact,
lanthanide-based metallasilsesquioxanes are much more attractive than
tical, magnetic, and catalytic properties originating from the intrinsic
character of lanthanide ions. Therefore, the development of lanthanide
silsesquioxanes is of practical importance.
Among polynuclear lanthanide clusters, gadolinium (Gd) clusters are
of particular interest because of their potential applications in single-
molecule magnets and magnetocaloric effect (MCE) materials in which
Gd(III) ions have a large spin ground state (S) combined with negligi-
ble magnetic anisotropy and low-lying excited spin states [21–25]. As
is well known, the surrounding ligands play an important role in modu-
lating the magnetic properties, particularly ligands with multinegative
charges and high coordination numbers [21,24,26,27]. In this regard, it
is interesting and meaningful to investigate silsesquioxane-ligand pro-
tected polynuclear Gd(III) clusters.
Notably, conventional metallasilsesquioxanes are typically obtained
in an inert atmosphere requiring sophisticated equipment and skilled
technicians, which in part limits their flourishing [28–34]. We have
recently successfully applied a more efficient solvothermal technique
to construct polynuclear metallasilsesquioxanes in air [6,35-37]. Fol-
lowing our synthetic strategy, the solvothermal reaction of the pre-

∗
Corresponding authors.
E-mail addresses: shengkai@sdjtu.edu.cn (K. Sheng), zvonko.jaglicic@imfm.si (Z. Jagličić), dsun@sdu.edu.cn (D. Sun).

https://doi.org/10.1016/j.chphma.2022.04.008
Received 3 April 2022; Received in revised form 24 April 2022; Accepted 26 April 2022
Available online 18 May 2022
2772-5715/© 2022 The Authors. Publishing Services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY
license (http://creativecommons.org/licenses/by/4.0/)
K. Sheng, R. Wang, A. Bilyachenko et al. ChemPhysMater 1 (2022) 247–251

Scheme 1. The schematic representation of synthesis route for Gd13 and the optical image of the crystals.

Fig. 1. (a) The main frame structure of the Gd13 cluster. The structure that removing DMF ligands (b) and (Ph4 Si4 O8 )4− ligands (c), respectively. (d) The Gd13
structure with magnified thirteen Gd atoms. (e) (f) The cuboctahedron arrangement of the inner core structure that belongs to one of the Archimedean solids with
alternating six quadrilateral and eight triangular faces. All hydrogen atoms are omitted for clarity. Colour code: Gd, cyan; Si, yellow; N, blue; O, red; C, grey.

organized (Ph4 Si4 O8 )4− ligand and Gd(NO3 )3 in 3:2 CH3 CN/DMF in
the presence of Et3 N at 100 ◦ C yields polyhedral colorless crystals of
Gd13. To the best of our knowledge, this is the highest-nuclearity Gd-
silsesquioxane cluster (Scheme 1). Interestingly, Gd13 displays an un-
precedented Archimedean arrangement, which has never been reported
in lanthanide clusters.
2. Results and discussion
As the tetraanionic multidentate scaffold offering four dangling O
atoms in a convergent manner, the macrocyclic (Ph4 Si4 O8 )4− ligand can
be a good candidate for binding multiple metal ions to form a polynu-
clear cluster. The synthesis of (Ph4 Si4 O8 )4− ligands requires precise con-
trol of the amount of precursor PhSi(OMe)3 , base, and water, as well
as the type of hydroxylic solvent. Moreover, the alkaline environment
facilitates the subsequent hydrolysis of gadolinium ions. Therefore, it
was anticipated that a polynuclear metallasilsequioxane cluster would
be constructed from the (Ph4 Si4 O8 )4− ligand and Gd(III).
Single-crystal X-ray diffraction results suggest that Gd13 crystallizes
in the tetragonal space group I4/m. The main framework is an anion
[Gd13 O8 (Ph4 Si4 O8 )6 (DMF)12 ]− with [Et3 NH]+ as the counter cation,
and its asymmetric unit contains one-eighth of the cluster. Crystallo-
graphic information is listed in Tables S1 and S2 (Supporting Infor-
mation). Fig. 1 shows the main frame structure of Gd13 consisting
of {Gd13 O8 } as the inner core and six tetrapodal (Ph4 Si4 O8 )4− lig-
ands and 12 terminal DMF molecules as the surrounding organic en-
velope. The symmetry of the cluster maintains the fourfold symmetry
of the ligand, with a C4 axis crossing the center of two (Ph4 Si4 O8 )4−
ligands (one front side and one back side) and the central Gd1 atom
(Fig. S1). The four terminal O atoms of each of the bulky (Ph4 Si4 O8 )4−
ligands exhibit 𝜇 2 binding, capturing four Gd atoms with the Gd–
O distance in the 2.414(5)∼2.419(5) Å range (Fig. S2), and the six
(Ph4 Si4 O8 )4− ligands symmetrically enclose the metal-oxo core, leav-
ing the rest room for residing DMF molecules with Gd–O distance in
the range of 2.464(9)∼2.480(6) Å. Notably, if we changed the DMF to
DMA solvent, the Gd13 cluster could not be obtained, possibly owing
to steric hindrance from the size of the carbonyl group, indicating that
the less-hindered DMF solvent also plays a vital role in the formation
of the cluster. Notably, the yield of Gd13 cluster could be significantly
improved when an additional component (2,2’-bipyridine) was present

248
K. Sheng, R. Wang, A. Bilyachenko et al.
Fig. 2. Temperature dependent susceptibility of Gd13 in magnetic field of 1
kOe and product 𝜒T (inset). Full green line in inset is a result of fit as described
in text.
in the reaction media. Meanwhile, 2,2’-bipyridine components were not
included in the composition of the resulting complex. Such effects of
“silent witness” ligands that do not participate in the composition of the
final product have been observed in previous reports [38, 39].
In the metal-oxo core, eight 𝜇 4 -O connect one central Gd(III) atom to
12 Gd(III) centers, forming an unprecedented truncated octahedron with
alternating six quadrilateral and eight triangular faces (Fig. 1(e)(f)).
This aesthetically appealing structure is one of the Archimedean solids.
In contrast to the central eight-oxygen-coordinated Gd atom, all the
other twelve Gd atoms were surrounded by four O atoms from two
(Ph4 Si4 O8 )4− ligands, two 𝜇 4 -O atoms, and one O atom from the DMF
molecule (Fig. S3), exhibiting a seven-coordinated mono-capped trigo-
nal prism geometry. All Gd atoms are in the +3 oxidation state based
on bond valence sum analyses and consideration of the coordination
environments. The Gd•••Gd separation is approximately 3.74 Å, which
is the same as the diameter of the pseudo-spheroidal Ga12. The crystal
packing structure (Fig. S4) exhibits a three-dimensional arrangement of
the clusters, and there is no special interaction between them. Fig. S5
shows the infrared spectrum of Gd13 clusters. The bands at 2895∼3041
cm−1 were assigned to C–H vibrations. The peak at approximately 2360
cm−1 was attributed to the stretching vibration of CO2 from air. The
intense peak located at 1654 cm−1 is attributed to the C=O vibration
of DMF. The bands at 1008 and 967 cm−1 were ascribed to the asym-
metric and symmetric vibrations of Si–O bonds from Si–O–Si, respec-
tively. The peak at 702 cm−1 originated from the vibration of the Si–
O bond from Si–O–Gd. The peaks at 454∼496 cm−1 were related to
the Gd–O bands. As shown in Fig. S6, the ultraviolet-visible diffuse re-
flectance spectra of the solid-state Gd13 crystal possessed two main ab-
sorption bands with maxima at approximately 346 and 418 nm. We
infer that these two bands correspond to the ligand-to-metal charge
transfer band and internal transition of the partially filled 4f shell of
Gd(III). Based on the well-known Kubelka–Munk function, the bandgap
of Gd13 cluster was extrapolated as 3.79 eV. Moreover, the thermal be-
havior of Gd13 was investigated by thermogravimetric analysis (TGA).
As shown in Fig. S7, the TGA curve displays the first weight loss of
approximately 10.2% from 20 to 205 ◦ C, putatively involving the re-
moval of solvent molecules (calcd. 9.6%). Between 205 and 450 ◦ C, the
second weight loss of 13.3% corresponded to the loss of coordinated
DMF molecules (calcd. 12.3%). Subsequently, the framework begins to
decompose.
The magnetic properties of the polycrystalline sample were investi-
gated using a Quantum Design MPMS 3 SQUID magnetometer. Suscep-
249
ChemPhysMater 1 (2022) 247–251
Fig. 3. Magnetization curves M(H) between 10 K and 2 K of Gd13 and the
magnetic entropy change ΔSM (inset).
tibility was measured between 2 and 300 K in a constant magnetic field
of 1 kOe while isothermal magnetization curves up to 70 kOe were ob-
tained between 10 and 2 K in steps of 0.5 K. All data shown in Figs. 2
and 3 were corrected for the contribution of a sample holder and for the
temperature-independent diamagnetism of inner shell electrons accord-
ing to Pascal’s tables [40].
The magnetic susceptibility of Gd13 increased monotonically from
300 to 2 K (Fig. 2). The temperature-dependent susceptibility does not
perfectly follow the Curie 1/T law, as observed in the inset of the same
figure, where the product 𝜒T decreases considerably below 100 K. For
temperatures above 150 K, the product 𝜒T is almost constant and has
a value of 102 emu K/mol. This value is in excellent agreement with
the expected value of 104 emu K/mol for 13 gadolinium ions with spin
S = 7/2 and no orbital contribution, L = 0. [41] The temperature depen-
dence of the product 𝜒T between 20 and 300 K can be well described
by considering crystal field effects.
A fit obtained with PHI software [42] is shown as a green line in
the inset of Fig. 2. The best fit with the experimental data above 20 K
was achieved with a Landé g-factor g = 2.0, which is in agreement with
L = 0, and crystal field parameters D = 22 cm−1 and E = 0.49 cm−1 .
The simulation of the model with the obtained fitting parameters
from 300 down to 2 K is shown in the inset of Fig. 2. A significant
disagreement between the simulation and measurements was observed
from 20 to 2 K, with the simulated 𝜒T values being significantly larger.
This difference may be due to a weak antiferromagnetic interaction be-
tween the 13 Gd ions in the cluster. For comparison with a previous
study that concerns phenylsiloxide complexes of single Gd ion, the trend
of temperature-dependent susceptibility is similar to that in the previous
study, whereas there is no interaction between the Gd centers owing to
the long intermolecular distance [43].
Elemental gadolinium and numerous other gadolinium compounds
are well-known magnetocaloric material [44–46]. For room tempera-
ture magnetic refrigeration, materials that exhibit a large temperature
dependence of magnetization at room temperature are required. Com-
pound Gd13 behaves approximately as a paramagnet and exhibits a
large temperature dependence of magnetization M(T) or susceptibility
𝜒(T) only below 20 K. Fig. 3 shows the magnetization curves measured
between 0 Oe and 70 kOe in the interval between 10 and 2 K. The change
in the magnetic part of entropy ΔSM is shown in the inset of Fig. 3. It
increases with decreasing temperature and reaches a value of 20 J kg−1
K−1 at 2 K. This value is comparable to the value of 24 J kg−1 K−1 ,
recently obtained for another Gd cluster [46,47].
K. Sheng, R. Wang, A. Bilyachenko et al.
3. Conclusions
In conclusion, a novel tridecanuclear Gd-silsesquioxane cluster was
successfully constructed through a facile solvothermal reaction of a
versatile preorganized (Ph4 Si4 O8 )4− ligand with gadolinium(III) ni-
trate without the Schlenk technique or inert atmosphere. The six
(Ph4 Si4 O8 )4− ligands behave like six cups capping the metal-oxo core
using tetradentate terminal O atoms, and 12 DMF molecules further sta-
bilize the overall structure. As expected, the Gd13 cluster maintained
the C4 symmetry of the (Ph4 Si4 O8 )4− ligand. Interestingly, the inner
{Gd13 O8 } core can be described as a semi-regular Archimedean solid,
namely, a cuboctahedron formed by 12 Gd centers connected to one cen-
tral Gd atom. Moreover, a magnetic study revealed the presence of anti-
ferromagnetic interactions between Gd(III) ions. The MCE of the cluster
leads to a change in the magnetic entropy of 20 J kg−1 K−1 at 2 K for
ΔH = 70 kOe. We believe that our synthetic strategy can be extended to
the synthesis of other functional metallasilsesquioxanes.
Declaration of Competing Interest
The authors declare no competing financial interest.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (Grant Nos. 22171164, 91961105,
21822107, and 21805170), Natural Science Foundation of Shandong
Province (Nos. ZR2020MB004, ZR2020ZD35, ZR2019ZD45, JQ201803,
ZR2017MB061, and ZR2020MA061), Taishan Scholar Project of Shan-
dong Province of China (Nos. tsqn201812003 and ts20190908), Slove-
nian Research Agency (Grant No. P2-0348), the Minsitry of Science
and Higher Education of the Russian Federation (No. 075-03-2020-223
(FSSF-2020-0017)), and the INEOS RAS with the support of Ministry of
Science and Higher Education of the Russian Federation for providing
the access to electronic scientific resources.
Data availability
The data supporting the findings of this study are available from the
corresponding author upon reasonable request.
Supplementary materials
Supplementary material associated with this article can be found in
the online version, at doi:10.1016/j.chphma.2022.04.008.
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