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ARTICLE

Solvent-induced formation of two gadolinium clusters

Dalton Transactions Accepted Manuscript

demonstrated for strong magnetocaloric effects and ferroelectric
Received 00th January 20xx,
Accepted 00th January 20xx
properties
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DOI: 10.1039/x0xx00000x Yu-Xia Wang,a Qiutong Xu,a Peng Ren,b Wei Shi*a and Peng Cheng*a,c
www.rsc.org/ Abstract Two gadolinium clusters, [Gd2(H3L)2(NO3)2](NO3)2 (1) and [Gd3(HL)(H2L)(NO3)4]·C2H5OH (2) (H4L = N,N,N’,N’-
tetrakis(2-hydroxyethyl)ethylenediamine), were synthesized and characterized with different solvents. Magnetic
properties of 1 and 2 were recorded and studied in detail. 1 is a centrosymmetric binuclear Gd2 cluster, adopting a P–1
space group (point group –1), and exhibits a strong magnetocaloric effect entropy (MCE) with –ΔSm of 27.50 J kg–1 K–1. 2
crystallizes in the Pna21 space group (polar point group mm2) through solvent modulation and contains an asymmetric
trinuclear Gd3 cluster. Magnetic and ferroelectric investigations of 2 reveal a large change in the magnetocaloric effect
entropy with –ΔSm of 30.22 J kg–1 K–1, ferroelectric hysteresis and dielectric anomalies.

and large MCE (3d = CrIII, MnIII, FeII, CoII, NiII, CuII, ZnII),3-12 such
Introduction as {Co10Gd42},9 {Ni10Gd42},9 {Ni12Gd36},10 {Cu5Gd4}11 and
{ZnGd5}.12 The other category comprises pure GdIII-based
Lanthanide molecules with high-spin isotropic carriers
clusters, such as {GdF3},13 {Gd2},14 {Gd7},15 {Gd16},16 {Gd24},17
exhibiting a strong magnetocaloric effect (MCE) are becoming
{Gd48},18 {Gd60},19 {Gd104},20 which often have a larger entropy
a promising solution to magnetic refrigeration for the purpose
change than 3d-GdIII clusters in terms of the prerequisites
of reducing the use of expensive and rare helium-3.1,2 The
mentioned above owing to the large mass ratio of
choice of spin carriers is an important factor of realizing a
mental/ligands, especially for some GdIII salts. However, the
strong MCE of magnetic refrigeration materials. The
easy dissolution and low thermal stability of some GdIII salts,
prerequisites for a strong MCE are (1) a ground state S with
let alone the sophisticated synthetic routes in some cases,
large total spin (where the theoretical maximum total spin is
certainly prevent the applications of those salts.21 It remains a
Rln(2S + 1)), (2) molecular isotropy that readily permits
great challenge for chemists to synthesize new molecules with
polarization of the net molecular spin, resulting in a large
a strong MCE to overcome the drawback of simple gadolinium
change in entropy change, (3) the existence of low-lying
salts.22
excited states that strengthen the field-dependent effect, (4)
Compared with well-studied magnetic properties, the electric
ferromagnetic coupling that favors a large S value, resulting in
properties of lanthanide complexes have rarely been
a large magnetic entropy change, and (5) a high magnetic spin
documented.23 Electric properties have been explored initially
density (or a small MW/NGd ratio).1 Herein, GdIII-based clusters,
for some magnetically anisotropic lanthanide coordination
which have a larger isotropic spin (s = 7/2) than any other spin
clusters,24 and the magnetodielectric effect on account of spin-
carrier and promote weak intramolecular interactions, are
lattice coupling has also been observed.24e The progress of
good candidates.2
studies on the electric properties of highly anisotropic
Well-known GdIII-based clusters with large magnetic entropy
lanthanide coordination clusters has shown the way to
change can be divided into two categories. One category
synthesize molecule-based nanoscale materials with
comprises high nuclear 3d-GdIII clusters with various structures
simultaneous distinct magnetic and electric properties. The
electric properties of high-spin isotropic carriers have never
a Department of Chemistry, Key Laboratory of Advanced Energy Materials been involved in such work.
Chemistry (MOE), College of Chemistry, Nankai University, Tianjin 300071, China.
E-mail: shiwei@nankai.edu.cn, pcheng@nankai.edu.cn The present paper reports centrosymmetric
b School of Science, Harbin Institute of Technology (Shenzhen), Shenzhen 518055,
[Gd2(H3L)2(NO3)2](NO3)2 (1) and asymmetric
China.
c Key Laboratory of Advanced Energy Materials Chemistry (MOE), College of
[Gd3(HL)(H2L)(NO3)4]·C2H5OH (2) coordination clusters
Chemistry, Nankai University, Tianjin 300071, China. obtained using the same raw materials but in different
Electronic supplementary information (ESI) available: additional characterization solvents (Scheme 1); these clusters have a strong MCE and
and physical measurements and X-ray crystallographic data for 1 and 2 (CIF). CCDC
1886461 (1), 1886462 (2_200K), 1886463 (2_293K), 1886464 (2_353K), 1886465 high thermal stability. Additionally, 2 crystallizes in a polar
(2_383K). For ESI and crystallographic data in CIF or other electronic format see
DOI: 10.1039/x0xx00000x

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point group and has ferroelectric hysteresis at room
temperature and dielectric anomalies.
Experimental Section
Materials and Physical Measurements. All raw materials of the
chemicals and solvents reagents were purchased without further
purification. Elemental analyses (C, H and N) were conducted on a
PerkinElmer 240 CHN elemental analyzer. Powder X-ray diffraction
Synthesis of [Gd3(HL)(H2L)(NO3)4]·C2H5OH (2). 2 was prepared
View Article Online
in a similar raw to 1, replacing the acetonitrile with ethanol.
DOI: 10.1039/C8DT04267E
Yield: 46% (based on Gd). Formula, C22H49Gd3N8O21. Elemental
analysis calcd (%) for 2: C, 21.42; H, 4.00; N, 9.08. Found: C,
21.43; H, 4.15; N, 9.04. IR (KBr) for 2: 3447(m), 2978(m, sh),
2862(s, sh), 1514(s), 1380(w), 1155(w, sh), 1092(m, sh), 1061(s,
sh), 915(m, sh), 816(m, sh), 746(m, sh), 629~396(w, sh).
Results and discussion

Dalton Transactions Accepted Manuscript

(PXRD) measurements were recorded on a D/Max-2500 X-ray
diffractometer using Cu-K radiation (Fig. S1, ESI†). Infrared (IR) Characterization of 1
spectra were recorded (400–4000 cm–1) on a Bruker TENOR 27
spectrophotometer using KBr pellets. Thermogravimetric analysis
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(TGA) was carried out using a Rigaku PTC-10ATG-DTA analyzer.

Magnetic data were recorded for microcrystalline samples using a
Quantum Design MPMS XL-7 SQUID magnetometer. Both the
diamagnetic contribution of the sample holder and the
diamagnetism estimated using Pascal’s constants were corrected.
Ferroelectric measurements were made on a single crystal using a
Radiant Technologies Premier Precision II ferroelectric tester. The
temperature dependence of permittivity and dielectric loss were
collected on a wafer (diameter ~ 10 mm, thickness ~ 1 mm) of
polycrystalline powder sample using a Precision LCR Meter (HP
4284A).
X-ray Crystallographic Data Collection and Refinements.
Single-crystal X-ray data of 1 and 2 were collected at 120 and
200–383 K on an Oxford SuperNova diffractometer equipped
with graphite-monochromated Mo-Kα radiation (λ = 0.71073
Å). The structures were solved employing the direct method
and refined employing the full-matrix least-squares method on
F2 with anisotropic thermal parameters for all non-hydrogen
atoms. Hydrogen atoms were located geometrically and
refined isotropically. CCDC 1886461 (1), 1886462 (2_200K),
1886463 (2_293K), 1886464 (2_353K), 1886465 (2_383K).
Fig. 1. (a) Molecular structure of 1. H atoms and NO3– groups are omitted. Atom color
codes: green Gd, red O, blue N, black C. (b) Coordination geometry of GdIII in 1. (c)
Supramolecular structure of 1. Blue dashed lines are the selected strong hydrogen
bonds.
Characterization of 1. The high thermal stability (Fig. S2, ESI†)
of 1 is essential for the application of magnetic refrigeration
materials. The structure of 1, as confirmed by single-crystal X-
ray diffraction, belongs to the triclinic space group P–1. The
structural unit consists of one binuclear [Gd2(H3L)2(NO3)2] unit
(Fig. 1a) and two free NO3–. The binuclear unit is constructed
by the connection of two equivalent [Gd(H3L)(NO3)] subunits
through two μ2-O(2) atoms from H3L. Gd1 adopts a nine-
coordinated distorted spherical capped square antiprism
geometry, bonding to four O atoms and two N atoms from H3L,
one O atom from the other H3L and two O atoms from one
NO3–, with Gd1–O distances of 2.309(6)–2.568(7) Å and Gd1–N
distances of 2.638(7) and 2.696(8) Å (Fig. 1b). The
configuration of Gd3+ ions were confirmed by continuous
shape measures (CSM) calculations (Table S2, ESI†).25 A 3D
supramolecular framework is constructed by the strong O-
H···O and C-H···O hydrogen bonding interactions between the
binuclear clusters and nitrate ions. The hydrogen bond
distances of O-H···O and C-H···O are 2.5985–3.2983 Å and
3.0832–3.5085 Å (Fig. 1c).

Scheme 1. Synthetic routes of 1 and 2.

Synthesis of [Gd2(H3L)2(NO3)2](NO3)2 (1). Colorless crystals

were obtained from a 20-mL acetonitrile solution of
Gd(NO3)3·6H2O (0.226g), H4L (0.273 g) and LiOH·H2O (0.210 g)
in a vial for few hours’ stirring and then under a solvothermal
condition of 100 °C 3 days later. Yield: 10% (based on Gd).
Formula, C20H44Gd2N8O20. Elemental analysis calcd (%) for 1: C,
23.30; H, 4.30; N, 10.87. Found: C, 23.25; H, 4.49; N, 11.05. IR
(KBr) for 1: 3443(m), 2975(m, sh), 2860(s, sh), 1510(s), 1381(w),
1154(w, sh), 1060(s, sh), 816(m, sh), 740(m, sh). Fig. 2. (a) Triangular structure of 2. H atoms and the C2H5OH solvents are omitted.
Atom color codes: green Gd, red O, blue N, black C. (b)–(d) Coordination geometry of

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the three GdIII in 2. (e) Supramolecular structure of 2. Dashed cyan lines represent the
selected hydrogen bonds.
Characterization of 2. TGA data reveal almost no weight loss
till 251 °C. Above 251 °C, a weight loss of 3.47% was observed
in the temperature range of 251–276 °C, corresponding to the
loss of free ethanol solvent (calculated 3.73%) (Fig. S2, ESI†).
Single-crystal X-ray analysis shows that 2 adopts the
orthorhombic space group Pna21 (200–383 K) (Table S1,
ESI†)which is the isostructure of our reported ferroelectric
dysprosium SMM.24c
Taking the data at 200 K as an example, the skeleton of 2
consists of one trinuclear [Gd3(HL)(H2L)(NO3)4] unit (Fig. 2a)
and one free C2H5OH. The trinuclear unit forms through the
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linking of three crystallographic independent GdIII ions bridged
by two μ2-O (O3, O4) and two μ3-O (O1, O2) atoms from the
ligands. Interestingly, three GdIII ions have two types of
coordination geometry. Gd1 has nine-coordinated spherical
capped square antiprism geometry bonding to four O atoms
and two N atoms from the HL ligand, one O atom from the H2L
ligand and two O atoms from one NO3–, with Gd1–O and Gd1–
N distances of 2.314(6)–2.549(8) Å and 2.595(8)–2.672(7) Å,
respectively (Fig. 2b). In the coordination polyhedron of Gd1,
two bottom planes of the square antiprism, showing a dihedral
angle of 8.5°, are constituted by the O2, O5, O6, O19 group
and O1, O4, N3, N4 group. The standard deviations from their
least-squares are 0.156 and 0.123 Å. The distances between
Gd1 and the bottom surfaces are 0.924 and 1.450 Å.
Additionally, the plane made up by the O2, O5, O6, O19 group
was covered by O18 on the cap position with a distance of
1.557 Å between O18 and the plane. The data exhibit severely
distorted monocapped square antiprism. Gd2 is located in the
eight-coordinated square antiprism, completed by one O atom
from the HL ligand, three O atoms from the H2L ligand and four
O atoms from two NO3– groups, with Gd2–O distances of
2.233(5)–2.526(7) Å (Fig. 2c). Meanwhile, the nine-coordinated
Gd3 adopts the same geometry as the Gd1, which is defined by
one O atom from the HL ligand, four O atoms and two N atoms
from the H2L ligand and two O atoms from one NO3– group.
The distances of Gd3-O and Gd3-N are in the range of
2.309(7)–2.600(8) Å and 2.600(9)–2.682(7) Å (Fig. 2d). The
detailed configurations of the three Gd3+ ions and continuous
shape measures (CSM) calculations results were listed in Table
S2.25 The high thermal stability are benefited from O-H···O and
C-H···O hydrogen bonds with distances of 2.440(11)–2.908(11)
and 3.127(12)–3.472(13) Å for O···O and C···O. Consequently,
all these hydrogen-bonding interactions afford a 3D
supramolecular framework (Fig. 2e). The selected bonds and
angles are shown in Table S3.
Magnetic properties of 1. Variable-temperature direct current
(dc) susceptibilities of the polycrystalline sample of 1 were
recorded in the range of 2–300 K under a 0.1 T magnetic field
(Fig. 3a). For 1, χMT value is detected to be 15.93 cm3 K mol–1
at 300 K, very close to the expected value (15.75 cm3 K mol–1)
for two uncoupled GdIII ions. Upon cooling, χMT stays almost
stable until 20 K and then rapidly falls to a minimum value of
9.30 cm3 K mol−1 at 2.0 K. Such magnetic behavior indicates a
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weaker antiferromagnetic interaction between Gd III ions in 1.
View Article Online
The susceptibilities obey the Curie–Weiss law well with C =
DOI: 10.1039/C8DT04267E
15.97 cm3 K mol−1 and ɵ = –1.21 K. To quantitatively analyze
the magnetic interactions between GdIII ions, the simple
isotropic Heisenberg spin Hamiltonian expressed as H = –
2JSGd1SGd2 (1) in which SGd1 = SGd2 = 7/2, is introduced..26 The
isotropic interaction parameter J and assumed isotropic Lande
factor g are respectively −0.032 cm–1 and 2.01. The negative
value of J indicates the antiferromagnetic interaction between
adjacent GdIII ions. The plots of magnetization versus H in the
Dalton Transactions Accepted Manuscript
temperature range of 2–10 K are illustrated in Fig. 3b. Under
strong magnetic fields at 2 K, the magnetization reaches a
saturated value of 14.04 Nβ for 1 at 7 T. The antiferromagnetic
coupling between neighboring GdIII ions in 1 was also
confirmed with that the presents of the Brillouin function for
magnetically uncoupled GdIII ions is above the experimental
magnetization curve (S = 7/2, g = 2.0) The exchange
interactions between GdIII ions are weaker than those between
3d ions for the efficient shielding effect of the unpaired
electrons in the 4f orbitals, so that the adjacent GdIII ions can
be assumed to not interact. –∆Sm for gadolinium complexes is
close to nRln(2S + 1), with n representing noninteracting
spins.3,4 The maximum entropy change should be Sm = nRln(2S
+ 1) (2).
Fig. 3. (a) Temperature dependence of χMT (◊) and 1/χM (○) plots for 1. Red lines are
the best fits. (b) M versus H plots from 2 to 10 K. (c) Brillouin functions for magnetically
uncoupled GdIII ions (red line) and two ferromagnetic coupling gadolinium ions (purple
dashed line). (d) Calculated −ΔSm in various fields (1–7 T) for 1.
Meanwhile, the experimental magnetic entropy change ∆Sm
could be calculated according to the Maxwell equation –∆Sm(T)
= ∫[∂M(T, H)/∂T]HdH (3). The expected maximum entropy
change is 33.52 J kg–1 K–1 while the experimental maximum
mass entropy change and volumetric magnetic entropy change
are respectively 27.50 J kg–1 K–1 and 55.88 mJ cm–1 K–1 (T = 2 K,
∆H = 7 T) (Fig. 3d) for 1. The deviation of the theoretical
maximum entropy change from the experimental maximum
entropy change may be due to the antiferromagnetic
couplings within the GdIII ions.
J. Name., 2013, 00, 1-3 | 3
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Fig. 4. (a) Plots of the temperature dependence of magnetization (◊) and the reciprocal
of molecular susceptibility ( ○ ) for 2. Red lines are the best fits. (b) Plots of
magnetization versus magnetic field at various temperatures (2–10 K). (c) Brillouin
functions for magnetically uncoupled GdIII ions (red line) and three ferromagnetic
coupling GdIII ions (purple dashed line). (d) Calculated −ΔSm in various fields (1–7 T) for
2.
Magnetic properties of 2. The dc magnetic data of 2 were
recorded in a manner similar to the measurement for 1 (Fig.
4a). The susceptibility for the product χMT at 300 K is 23.50 cm3
K mol–1, very close to the theoretical value of 23.62 cm3 K mol–
1 for three spin-only GdIII ions (S = 7/ , g = 2). Upon cooling, χ T
2 M
remains constant until 100 K. Further cooling leads to a
gradual decrease in χMT to 21.18 cm3 K mol–1 at 20 K and then
an abrupt decrease to a minimum of 9.37 cm3 K mol–1 at 2 K.
The susceptibility data are analyzed using the isotropic
exchange expression H = –2(J1SGd1SGd2 + J1SGd2SGd3 + J2SGd1SGd3)
(4), where SGd1 = SGd2 = SGd3 = 7/2, g = 2.0, and the coupling
constants of Gd1–Gd2 and Gd2–Gd3 are assumed to be equal
(J1) while the coupling constant of Gd1–Gd3 is J2. The best fits
of the isotropic interaction parameters are respectively –0.11
and –0.02 cm–1. The negative magnetic coupling parameters
are consistent with previously reported values of triangular
gadolinium clusters.26 The plots of 1/χM against T obey the
Curie–Weiss law well in the temperature range of 2–300 K
with best-fit values of C = 23.75 cm3 K mol–1 and ɵ = –2.47 K.
Moreover, the negative value of ɵ supports the presence of
antiferromagnetic coupling between GdIII ions in 2. The
isothermal magnetization of 2 was further measured in the
range of 2–10 K with a magnetic field of 0–7 T. Under a strong
magnetic field at low temperature, the magnetization (M)
increases with a strengthening field. M reaches 20.86 Nβ at 2 K
and 7 T which is approaching the saturation value of 21 Nβ for
three isolated GdIII ions of 2 (Fig. 4b). The Brillouin functions
are shown in Fig. 4c for none magnetically coupled GdIII ions (S
= 7/2, g = 2.0, purple dashed line) and three ferromagnetic
coupling gadolinium ions with S = 21/2 and g = 2.0 (red line),
indicating an antiferromagnetic interaction in 2 that is stronger
than that of reported gadolinium salts, which is consistent with
the larger J values.
For 2, the magnetic/nonmagnetic atom mass ratio (61.97%)
is larger than that for 1 (43.89%). The advisable value is 42.06 J
4 | J. Name., 2012, 00, 1-3
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kg–1 K–1 following equation (2) for 2. The calculatedViewmaximum
Article Online
–∆Sm is 30.22 J kg–1 K–1 at 3 K for ∆H = 7 DOI:
T (Fig. 4d). Moreover,
10.1039/C8DT04267E
a large change in the volumetric magnetic entropy was also
calculated with –∆Sm = 63.92 mJ cm–3 K–1 for ∆H = 7 T. The
maximum value of –∆Sm of 2 is larger than most reported
values for 3d–GdIII complexes and gadolinium clusters.2a,c,e The
deviation from theoretical value is probably due to the
intramolecular antiferromagnetic interactions in 2. Although
the experimental entropy changes of 1 and 2 are not as high as
those for the family of gadolinium salts, the incorporation of
Dalton Transactions Accepted Manuscript
organic ligands leading to high thermal stability is beneficial for
the further application of MCE materials.
Fig. 5. (a) Temperature dependence of the relative dielectric permittivity (r, relative
dielectric constant) and (b) the dielectric loss (tan = "/’) of 2. (c) Temperature-
dependent a.c. conductivities of 2. (d) Ferroelectric hysteresis loop at room
temperature. Inset: Plot of the leakage current versus electric field for 2.
Ferroelectric properties of 2. X-ray single crystal data at
different temperatures show 2 crystallizes in a polar point
group until 383 K (Table S1, ESI†). The relative dielectric
permittivity (εr, relative dielectric constant) and dielectric loss
(tanδ = ε"/ε') were measured as a function of temperature at
various frequencies ranging from 500 Hz to 10 kHz in a wide
temperature range from 300 to 523 K. Fig.s 5a and b shows
curves of the dielectric loss and dielectric constant versus
temperature at different frequencies. Large peaks detected at
about 510 K indicate a ferroelectric (FE) to paraelectric (PE)
phase transition. The low ac conductivity of 2 reveals that the
dielectric anomalism is an intrinsic property of the sample (Fig.
5c). The best-fit results of the plot of 1/εr versus T are Cferro = –
6.6 × 103 and Cpara = 11.4 × 103 K corresponding with T0 = 506 K
according to the Curie–Weiss law (Fig. 5d, inset). It worth
noting that the curves of the dielectric loss and dielectric
constant versus temperature of 2 both have large peaks in
addition to the phase transition peak, possibly on account of
the antivacuum experimental atmosphere or elastic
interactions.27 The spontaneous polarization is an important
factor whereby ferroelectric materials distinguish themselves
from other materials.23b The reversing or switching of the
macroscopic polarization of 2 can be identified from the
ferroelectric hysteresis loop. The polarization (P)–electric field
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(E) hysteresis loop and the leakage current curves of 2 were
measured on a single-crystal sample having dimensions of 0.2
mm × 0.2 mm × 1.5 mm with electrodes made of Pt wire. As
shown in Fig. 5d, a clear hysteresis loop with a large coercive
field value (Er) of about 0.047 µC cm–2 and a spontaneous
polarization (Pr) of 0.018 kV cm–1. The spontaneous
polarization value is of the same order of magnitude as values
observed for reported ferroelectric molecular magnets24b-d and
several molecular ferroelectrics.28
Conclusions
Two gadolinium clusters were constructed with the same raw
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materials but in different solvents. Magnetic studies identified
antiferromagnetic interactions and large entropy changes. The
entropy change of the trinuclear cluster is larger than that of
the binuclear cluster, indicating that a large
magnetic/nonmagnetic atom mass ratio is an important factor
of a strong MCE. Additionally, both types of cluster have high
thermal stability owing to the introduction of a functional
ligand. Interestingly, the trinuclear cluster, as a precursor in
the field of magnetic refrigerator materials, also had dielectric
and ferroelectric properties. We hope incorporating
ferroelectric properties at high temperature for a strong MCE
at low temperature in a singular material will allow the
development of potential multifunctional devices controlled
only by the temperature.
Conflicts of interest
There are no conflicts to declare
Acknowledgements
This research was funded by the National Key R&D Program of
China (grant ref: 2018YFA0306002), National Natural Science
Foundation of China (grant refs: 21622105 and 21501110),
Shenzhen Fundamental Research Project (grant ref:
JCYJ20160525164227350) and National Natural Science
Foundation of Tianjin (grant ref: 18JCJQJC47200).
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A table of contents entry (graphic abstract)

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Large magnetocaloric effects and ferroelectric properties were demonstrated in two

gadolinium clusters obtained via solvent modulation.