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Article
Cite This: Cryst. Growth Des. XXXX, XXX, XXX-XXX
pubs.acs.org/crystal
Three Types of Lanthanide Coordination Polymers with
Methylmalonate and Isonicotinate as Coligands: Structures,
Luminescence, and Magnetic Properties
Zhong-Yi Li,† Yuan-Qing Cao,† Jing-Yu Li,‡ Xiang-Fei Zhang,† Bin Zhai,*,† Chi Zhang,† Fu-Li Zhang,†
and Guang-Xiu Cao*,†
†
Henan Key Laboratory of Biomolecular Recognition and Sensing, College of Chemistry and Chemical Engineering, Shangqiu
Normal University, Shangqiu 476000, P. R. China
‡
School of Business Administration, Zhengzhou University of Aeronautics, Zhengzhou 450046, P. R. China
S Supporting Information
*
ABSTRACT: Three types of lanthanide coordination polymers based on mixed
methylmalonic acid (H2MMA) and isonicotinic acid (HINA), two-dimensional (2D)
[Ln2(MMA)2(INA)2(H2O)3]n (Ln = Eu (1); Gd (2)) and [Ln(MMA)(INA)(H2O)2]n
(Ln = Gd (3); Tb (4)) as well as one-dimensional (1D) [Dy(MMA)(INA)(H2O)2]n (5),
have been hydrothermally synthesized, which can be controlled by the usage amount of
H2MMA or the type of Ln3+ ion. Complexes 1 and 2 contain two kinds of 1D lanthanide
chain units (wave and linear), which are alternately linked by the MMA2− and INA−
ligands to form a 2D layer structure. Complexes 3 and 4 also have a 2D layer structure,
consisting of 1D linear lanthanide chain units, MMA2− and INA− linkers. Compound 5
shows a 1D linear chain structure, in which the neighboring Dy3+ ions are fastened by the
carboxylate groups from MMA2− and INA− ligands. The magnetic studies reveal the
presence of ferromagnetic Gd···Gd coupling in the 1D chain units of 2 and 3, which
display significant cryogenic magnetocaloric effects with a maximum −ΔSm value of 34.32
J kg−1 K−1 at 3 K and 36.02 J kg−1 K−1 at 2 K for ΔH = 7 T, respectively. Furthermore,
the solid-state photophysical properties of 1 and 4 exhibit strong characteristic Eu3+ and Tb3+ photoluminescent emission in the
visible region, indicating that Eu- and Tb-based luminescences are sensitized effectively by the energy transfer from the INA−
ligand to the metal centers.
■
INTRODUCTION
The rational design and assembly of novel lanthanide
coordination polymers (Ln-CPs) have attracted great interest
over the past two decades, due to not only their various
intriguing architectures, but also their potential applications
such as cryogenic magnetic refrigeration, high-density information storage, luminescent sensing, and magnetic resonance
imaging (MRI) contrast agents fields.1−4 For photoluminescence in both visible and near-infrared regions, most trivalent
lanthanide ions are usually selected as luminescent centers
because of their characteristic narrow line-like emissions for
pure colors.3,5−8 However, the direct excitation of the
lanthanide ions is very inefficient owing to the weak absorption
coefficient of Laporte forbidden f−f transitions.8−11 Therefore,
suitable organic ligands with strong absorbing chromophores
are usually incorporated as adjacent antennas or sensitizers,
which can stimulate the optical absorption by transferring
energy to lanthanide ions to enhance their fluorescence
intensity.8,10,12,13
Apart from the excellent photophysical properties, the
magnetic properties of Ln-CPs are unusual because of the
diverse local magnetic anisotropy and the large-spin multiplicity
of the spin ground-state of Ln3+ cations, which can be used to
© XXXX American Chemical Society
construct either single-molecule magnets (SMMs) and singlechain magnets (SCMs), especially for highly anisotropic Tband Dy-based systems,14−16 or as low-temperature molecular
magnetic coolers for isotropic Gd-containing entities.12,17−21
Particularly, molecule-based magnetic refrigerants, as alternatives to rare and expensive He-3 in ultralow-temperature
refrigeration, have drawn increasing attention in recent years
because of the energy-efficient and environmentally friendly
advantages.22−24 The refrigeration effect was appraised by the
magnetocaloric effect (MCE), which represents the change of
isothermal magnetic entropy (−ΔSm) and adiabatic temperature (ΔTad) in change of the applied magnetic field.17,25,26 To
obtain larger −ΔSm, it is usually necessary that a molecular
includes the features of a large spin ground state S, negligible
magnetic anisotropy, low-lying excited spin states, weak
coupling, and high magnetic density (or a large metal/ligand
mass ratio).18,27−29 In this perspective, Gd-containing CPs with
light and multidentate organic ligands may be promising
candidates because the isotropic Gd3+ ion has a large spin value
(S = 7/2) and usually displays weak superexchange interactions,
Received: September 20, 2017
Published: October 16, 2017
A
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
Article
Table 1. Crystal Data and Structure Refinement of 1−5
formula
Mr
T (K)
cryst. system
space group
a/Å
b/Å
c/Å
α/°
β/°
γ/°
V (Å3)
Z
dcalcd., g/cm3
μ (mm−1)
F(000)
reflections collected/unique
R(int)
GOF on F2
R1a (I > 2σ(I))
wR2b (all data)
a
1
2
3
4
5
C20H22Eu2N2O15
844.90
299(2)
monoclinic
Pc
12.4771(11)
11.0531(9)
9.5062(8)
90
110.918(4)
90
1224.60(18)
2
2.291
5.450
808
42709/5647
0.1009
1.054
0.0247
0.0580
C20H22Gd2N2O15
834.32
298(2)
monoclinic
Pc
12.4830(15)
11.0884(13)
9.5317(12)
90
110.787(4)
90
1233.5(3)
2
2.246
5.119
804
22341/5186
0.0452
1.064
0.0254
0.0602
C10H12GdNO8
431.46
298(2)
monoclinic
P2(1)/c
13.2754(6)
10.7721(6)
9.3473(5)
90
93.383(2)
90
1334.37(12)
4
2.148
5.007
828
23164/3063
0.0527
1.038
0.0301
0.0651
C10H12TbNO8
433.13
299(2)
monoclinic
P2(1)/c
13.213(2)
10.771(2)
9.3696(17)
90
93.329(6)
90
1331.2(4)
4
2.161
5.349
832
18759/2303
0.0253
1.037
0.0162
0.0487
C10H12DyNO8
436.71
298(2)
monoclinic
P2(1)/c
11.4560(5)
13.0070(6)
9.1208(4)
90
98.958(2)
90
1342.50(10)
4
2.161
5.602
836
19274/2360
0.0500
1.024
0.0245
0.0560
R1 = ∑(||Fo| − |Fc||)/∑ |Fo|. bwR2 = {∑w [(Fo2 − Fc2)]/∑w [(Fo2)2]}0.5.
and the light ligands could favor a large metal/ligand mass
ratio.28,30 Up to now, a large amount of Gd-based molecular
magnetorefrigerants have been built under this principle.17−30
Compared with Gd-based cluster complexes and one-dimensional (1D) CPs, the Gd-based two- (2D) and threedimensional (3D) CPs may be better for obtaining materials
with promising MCEs, when considering the improved
magnetic density because of the sharing of bridging ligands
between magnetic centers and that the nonmagnetic guest or
solvent molecules are more difficult to trap in such
structures.23,31 However, the high-dimensional Gd-based CPs
with remarkable MCEs are still limited, and further systematic
investigation to discover their potential applications is very
necessary.6,23,26
As mentioned above, to build high-dimensional Ln-CPs
behaving as dual magneto-optical materials, an effective
synthetic strategy may be the selection of mixed flexible
small-size and rigid multidentate organic ligands containing
carboxylate groups. On the one hand, besides comparable
stability, the multifarious coordination and bridging modes of
carboxylate groups can result in interesting topological
architectures, magnetic coupling, and fluorescence properties.4,32 On the other hand, the introduction of a rigid ligand as
a multidentate connector can be more beneficial to form
porous 2D or 3D CPs, on which the rigid ligand may also
endow rigidity and stability as well as improved fluorescence.33
Flexible methylmalonic acid and rigid isonicotinic acid both
could display diverse bridging modes and have been
demonstrated to be excellent ligands for building CPs.34,35
Herein, on the basis of mixed methylmalonic acid (H2MMA)
and isonicotinic acid (HINA), three types of lanthanide
coordination polymers, 2D [Ln2(MMA)2(INA)2(H2O)3]n (Ln
= Eu (1); Gd (2)) and [Ln(MMA)(INA)(H2O)2]n (Ln= Gd
(3); Tb (4)) as well as 1D [Dy(MMA)(INA)(H2O)2]n (5),
were successfully prepared, and their structures and magnetic
and photophysical properties were discussed.
■
EXPERIMENTAL SECTION
Materials and Physical Measurements. All chemicals were
obtained from commercial sources and used without further
purification. Elemental analyses were determined by a Vario EL III
elemental analyzer. Fourier transform infrared (FT-IR) spectra were
collected in the range of 4000−400 cm−1 on a JASCO FT/IR-430
spectrometer with KBr pellets. Powder X-ray diffraction (PXPD)
measurements were executed on a Bruker D8 ADVANCE X-ray
diffractometer using Cu Kα (λ = 1.5418 Å) at room temperature. Solid
state luminescence properties were performed using a F-7000 FL
spectrophotometer. Thermogravimetric analyses were carried out
under a flow of nitrogen (40 mL/min) at a ramp rate of 10 °C/min,
using a NETZSCH STA 449F3 instrument. Magnetic measurements
were performed on a Quantum Design SQUID magnetometer MPMS
XL-7. The data were corrected for the sample holder and the
diamagnetic contributions.
Synthesis of 1 and 2. Complexes 1 and 2 were synthesized under
the same conditions. A total of 0.4 mL of Ln(NO3)3 (1 M, 0.4 mmol;
Ln = Eu; Gd) aqueous solution, 0.2 mL of H2MMA (1 M, 0.2 mmol)
aqueous solution, 0.049 g of HINA (0.4 mmol), and 2 mL of
deionized water were placed in a 15 mL vial. 1 M NaOH aqueous
solution was added dropwise to adjust the pH value of the resulting
solution to about 5.0 under stirring. The vial was sealed and heated at
90 °C in an oven for 2 days and then cooled to room temperature.
Block colorless crystals of the products were obtained.
[Eu2(MMA)2(INA)2(H2O)3]n (1). Yield, 22% based on HINA. Anal.
Calcd for C20H22Eu2N2O15: C, 28.79; H, 2.66; N, 3.36%. Found: C,
28.75; H, 2.69; N, 3.32%. IR (KBr pellet, cm−1): 3339 s, 1596 s, 1408
s, 1326 m, 1225 w, 1125 w, 1071 w, 939 w, 875 w, 779 w, 679 w, 550
w.
[Gd2(MMA)2(INA)2(H2O)3]n (2). Yield, 20% based on HINA. Anal.
Calcd for C20H22Gd2N2O15: C, 28.43; H, 2.62; N, 3.31%. Found: C,
28.45; H, 2.58; N, 3.33%. IR (KBr pellet, cm−1): 3344 s, 1596 s, 1406
s, 1326 m, 1227 w, 1127 w, 1074 w, 941 w, 875 w, 776 w, 683 w, 550
w.
Synthesis of 3 and 4. The following is the general synthetic
progress for complexes 3 and 4. 0.4 mL Ln(NO3)3 (1 M, 0.4 mmol;
Ln = Gd; Tb) aqueous solution, 0.4 mL H2MMA (1 M, 0.4 mmol)
aqueous solution, 0.049 g of HINA (0.4 mmol) and 2 mL of deionized
water were placed in a 15 mL vial. 1 M NaOH aqueous solution was
added dropwise to adjust the pH value of the resulting solution to
B
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
Article
about 5.0 under stirring. The vial was sealed and heated at 90 °C in an
oven for 2 days and then cooled to room temperature. Spindly block
colorless crystals of the products were collected.
[Gd(MMA)(INA)(H2O)2]n (3). Yield, 21% based on HINA. Anal.
Calcd for C10H12GdNO8: C, 27.84; H, 2.80; N, 3.24%. Found: C,
27.81; H, 2.78; N, 3.26%. IR (KBr pellet, cm−1): 3183 s, 1591 s, 1413
s, 1286 m, 1227 w, 1061 w, 1001 w, 923 w, 710 m, 676 w, 544 w.
[Tb(MMA)(INA)(H2O)2]n (4). Yield, 22% based on HINA. Anal.
Calcd for C10H12TbNO8: C, 27.73; H, 2.79; N, 3.23%. Found: C,
27.75; H, 2.77; N, 3.25%. IR (KBr pellet, cm−1): 3163 s, 1552 s, 1412
s, 1286 m, 1227 w, 1067 w, 1001 w, 921 w, 710 w, 683 w, 557 w.
Synthesis of 5. A total of 0.2 mL of Dy(NO3)3 (1 M, 0.4 mmol)
aqueous solution, 0.4 mL of H2MMA (1 M, 0.4 mmol) aqueous
solution, 0.049 g of HINA (0.4 mmol), and 2 mL of deionized water
were placed in a 15 mL vial. 1 M NaOH aqueous solution was added
dropwise to adjust the pH value of the resulting solution to about 5.0
under stirring. The vial was sealed and heated at 90 °C in an oven for 2
days and then cooled to room temperature. Spindly block colorless
crystals of the products were prepared.
[Dy(MMA)(INA)(H2O)2]n (5). Yield, 18% based on HINA. Anal.
Calcd for C10H12DyNO8: C, 27.50; H, 2.77; N, 3.21%. Found: C,
27.52; H, 2.79; N, 3.20%. IR (KBr pellet, cm−1): 3149 s, 1591 s, 1425
s, 1287 m, 1227 w, 1067 w, 1007 w, 922 w, 710 m, 676 w, 550 w.
X-ray Crystallography. Crystallographic data of complexes 1−5
were collected on a Bruker D8 Quest CMOS area detector system
with graphite-monochromated Mo−Kα (λ = 0.71073 Å) radiation.
Data reduction and unit cell refinement were performed with SmartCCD software. The structures were solved by direct methods and
refined by full-matrix least-squares methods using SHELXL-97.36 For
1−5, All non-hydrogen atoms were refined anisotropically. Hydrogen
atoms on organic ligands were placed in idealized positions and refined
using a riding model. Hydrogen atoms on the terminal water
molecules were initially found on Fourier difference maps and then
restrained by using the DFIX instruction. A summary of the important
crystal and structure refinement data of 1−5 is given in Table 1.
Selected bond lengths and angles for 2, 3, and 5 were listed in Tables
S1, S2, and S3, respectively.
Scheme 1. Schematic Representation of the Synthetic
Procedures for 1−5
might be favorable for the formation of the structure of type I,
which has a tighter arrangement with the eight- and ninecoordinate Ln3+ ions. In contrast, the Ln3+ ion with a
comparative small radius (such as Dy3+) is suitable for the
construction of the 1D analogue, in which the Ln3+ ions are
eight-coordinate. In contrast, the Ln3+ ions with a middle radii
(such as Tb3+) may promote the formation of the 2D structure
of type II, in which the Ln3+ ions are nine-coordinate.
Interestingly, the Gd3+ ion with a proper radius can be used
to construct the 2D structure of type I and II by controlling the
usage amount of H2MMA over the synthetic process.
Crystal Structures of 1 and 2. Single crystal X-ray diffraction
analyses reveal that complexes 1 and 2 are isostructural, and
only the structure of 2 is discussed in detail. 2 crystallizes in the
monoclinic Pc space group and has a 2D layer structure. As
shown in Figure 1a, the asymmetric unit of 2 contains two Gd3+
ion, two MMA2− ligands, two INA− ligands, and three
coordinated water molecules. The two Gd3+ ions display
distinct different coordination environments. The coordination
geometry of the nonacoordinate Gd1 ion can be described as a
monocapped square antiprism, featuring coordination by nine
oxygen atoms (O1, O2A, O3, O4, O4B, O6B, O8, O13, and
O14) from two INA− ligands, three MMA2− ligands, and two
terminal water molecules (Figure 1b). In contrast, Gd2 ion is
eight-coordinated and has a distorted square antiprismatic
geometry, completed by eight oxygen atoms (O5, O7C, O9,
O9C, O10, O11, O12D, and O15) from two INA− ligands,
three MMA2− ligands, and one terminal water molecule. The
bond lengths of Gd−O and the angles of O−Gd−O are in the
range of 2.312(4)−2.819(4) Å and 66.38(14)−154.36(17)°,
respectively, which are comparable to those in the reported Gdcontaining compounds.12,17,18,37
In the structure, the two symmetric independent MMA2−
ligands present similar μ3-η1:η2:η1:η1 coordination modes
(Scheme 2, I and II), which uses one tridentate bridging
carboxylic group and one bidentate bridging carboxylic group
to connect three Gd3+ ions. However, one links two Gd1 and
one Gd2 ions (mode I), and the other links one Gd1 and two
Gd2 ions (mode II). Around every Gd1 or Gd2 ion, there are
three MMA2− ligands. The neighboring Gd1 ions are
connected together by one tridentate bridging carboxy and
■
RESULTS AND DISCUSSION
Synthesis. On the basis of flexible or aromatic multicarboxylate ligands, our group has designed and synthesized
series of Ln-CPs with interesting luminescent and magnetic
properties.17,18 As a continuous work, in this context, flexible
H2MMA and rigid HINA were chosen as coligands to
synthesize Ln-CPs because of their various bridging modes
and excellent affinity to metal ions.34,35 As a result, the 2D
[Ln2(MMA)2(INA)2(H2O)3]n (Ln = Eu (1); Gd (2)),
[Ln(MMA)(INA)(H2O)2]n (Ln = Gd (3); Tb (4)), and 1D
[Dy(MMA)(INA)(H2O)2]n (5) were successfully synthesized
under hydrothermal conditions. After the synthetic processes of
these systems were deeply researched, the following findings
were obtained and are detailed in Scheme 1. (1) Gd(NO3)3,
H2MMA, and HINA with a molar ratio of 2:1:2 can produce
the 2D structure of type I, while a 2:2:2 molar ratio results in
the 2D architecture of type II. Given the same pH value of
about 5.0, the usage amount of H2MMA may play an important
role in the formation of the two Gd-containing systems. (2)
Tb(NO3)3, H2MMA, and HINA with a molar ratio of 2:2:2 can
lead to the 2D structure of type II. However, pure 2D structure
of type I cannot be gained after a thorough study of the
synthesis condition. (3) For the Eu- and Dy-containing
analogues, the 2D structure of type I and the 1D structure
can be obtained solely, respectively, regardless of whether the
molar ratio of 2:1:2 or 2:2:2 was used.
The results indicate that the formation of the three family
polymers is sensitive to the radii of Ln3+ ions. A large radius
C
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
Article
Figure 1. (a) The asymmetric unit of 2. (b) Coordination environments of the Gd3+ ions in 2. Symmetry codes: A, x, 2 − y, 0.5 + z; B, x, 2 − y, −0.5
+ z; C, x, 1 − y, 0.5 + z; D, x, 1 − y, −0.5 + z. (c) View of the 2D layer structure unit built from Gd3+ ions and MMA2− ligands in 2 along the a axis.
(d) View of the 2D structure in 2 along the b axis.
Scheme 2. Coordinate Modes of MMA2− and INA− Ligands in 2.
one η1-O atom of the bidentate bridging carboxy of the MMA2−
ligand (mode I) to result in a 1D wave Gd1 chain. The Gd1···
Gd1 distance is 4.84(1) Å and the Gd1−Gd1−Gd1 angle is
158.68(1)°. Similarly, the 1D linear Gd2 chain is also formed
by the adjacent Gd2 ions and the MMA2− ligand (mode II)
with a Gd2···Gd2 distance of 4.78(1) Å and Gd2−Gd2−Gd2
angle of 168.71(1)°. As shown in Figure 1c, the Gd1 and Gd2
chains are alternately linked by the other η1-O atoms of the
bidentate bridging carboxys of the MMA2− ligands (mode I and
II) to lead to a 2D layer structure unit with the shortest
interchain Gd1···Gd2 distance of 5.94(1) Å. The 2D layer unit
is further fastened by the INA− ligands (Scheme 2, III and IV)
to produce a 2D structure (Figure 1d). The INA− ligands bear
two similar bridging μ2-η1:η1 modes. However, one INA− ligand
bridges two Gd1 ions, while the other bridges two Gd2 ions.
The neighboring 2D structures further link to each other by the
O15−H15A···N1 and O14−H14B···N2 hydrogen bonds to
give a supramolecular 3D arrangement (Figure 2 and Table
S4).
Crystal Structures of 3 and 4. Complexes 3 and 4 are also
isostructural. 3 crystallizes in the monoclinic P2(1)/c space
group and processes a 2D layer structure. As shown in Figure
3a, the asymmetric unit of 3 consists of one Gd3+ ion, one
MMA2− ligand, one INA− ligand, and two coordinated water
molecules. The Gd3+ ion is nine-coordinated and displays a
distorted monocapped square antiprismatic coordination
Figure 2. Supramolecular 3D arrangement in 2 viewed along the c axis
(H bonding: light orange dotted lines).
geometry, completed by nine oxygen atoms (O1, O2A, O3,
O3A, O4, O5B, O6B, O7, and O8) from two INA− ligands,
three MMA2− ligands and two terminal water molecules. The
bond lengths of Gd−O and the angles of O−Gd−O fall in the
range of 2.315(3)−2.788(3) Å and 49.09(9)−153.91(11)°,
respectively, which are close to those in 2.
D
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
Article
Figure 3. (a) Coordination environment of the asymmetric Gd3+ ion in 3. Symmetry codes: A, x, 1.5 − y, 0.5 + z; B, 1 − x, 0.5 + y, 0.5 − z. (b)
Coordination modes of MMA2− and INA− ligands in 3. (c) View of the 2D layer structure unit built from Gd3+ ions and MMA2− ligands in 3 along
the a axis. (d) View of the 2D structure in 3 along the b axis.
Figure 4. (a) Coordination environment of the asymmetric Dy3+ ion in 5. Symmetry codes: A, x, 0.5 − y, −0.5 + z; B, x, 0.5 − y, 0.5 + z. (b)
Coordination modes of MMA2− and INA− ligands in 5. (c) View of the 1D linear chain structure of 5.
settled by the μ2-η1:η1 INA− ligands (Figure 3d). The
neighboring 2D structures are connected with each other by
the O8−H8A···N1 hydrogen bond to result in a supramolecular
3D framework (Figure S1 and Table S5).
Crystal Structure of 5. Compound 5 crystallizes in the
similar monoclinic P2(1)/c space group as 3, but has a distinct
1D linear chain structure (Figure 4). The asymmetric unit of 5
includes one Dy3+ ion, one MMA2− ligand, one INA− ligand,
and two coordinated water molecules (Figure 4a). The Dy3+
ion is eight-coordinated and has a distorted square antiprismatic {O8} donor set, completed by eight oxygen atoms
(O1, O2A, O3, O3B, O4B, O6, O7, and O8) from two INA−
Each of the MMA2− ligands in 3 uses one tridentate bridging
carboxylic group and one chelating bidentate bridging
carboxylic group to connect three Gd3+ ions (Figure 3b).
The coordination mode could be described as μ3-η1: η2: η1: η1.
Around every Gd3+ ion, there are three MMA2− ligands. The
adjacent Gd3+ ions are linked together by one tridentate
bridging carboxy of the MMA2− ligand to result in a 1D linear
chain with a intrachain Gd···Gd distance of 4.68(1) Å and the
Gd−Gd−Gd angle of 175.59(1)°. The neighboring chains are
connected by the other carboxy of the MMA2− ligands to give a
2D layer structure unit with the shortest interchain Gd···Gd
distance of 6.86(1) Å (Figure 3c). The 2D structure is further
E
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
Article
15.96 and 8.04 cm3 mol−1 K at 2 K. The increase of χMT values
in low-temperature region suggests the existence of dominant
weak ferromagnetic interactions between adjacent Gd 3+
ions.17,37
To evaluate the exchange coupling, the dominant interaction
pathways in 2 and 3 should be identified. According to the
crystal structure of 3 described above, the Gd···Gd distance
within the uniform chain is 4.68(1) Å, shorter than those
between adjacent chains through the MMA2− bridge (longer
than 7.2 Å). Thus, the main exchange interactions can be
assumed to be 1D chain model, and the following expressions
deduced by Fisher could be used to quantitatively analyze the
interaction between adjacent Gd3+ ions with S = 7/2.3,38,39
ligands, two MMA2− ligands, and two terminal water molecules.
The bond lengths of Dy−O and the angles of O−Dy−O are in
the range of 2.262(3)−2.632(3) Å and 50.86(10)−
152.55(16)°, respectively.
Every MMA2− ligand in 5 adopts a μ2-η1: η2: η1 coordination
mode and bridges two Dy3+ ions by using its tridentate bridging
and monodentate bridging carboxylic groups (Figure 4b).
While the INA− ligand adopts a similar μ2-η1:η1 bridging mode
as that in 3 to connect two Dy3+ ions. Around every Dy3+ ion,
there are two MMA2− and two INA− ligands. The neighboring
Dy3+ ions are linked together by the MMA2− and INA− ligands
to result in a 1D linear chain structure (Figure 4c). The
intrachain Dy···Dy distance is 4.62(1) Å, and the Dy−Dy−Dy
angle is 161.02(1)°.
Thermal Analysis and PXRD Patterns. The thermal
stabilities of 1−5 were investigated on the crystalline samples
under the N2 atmosphere from 25 to 900 °C (Figure S3). Their
thermogravimetric (TG) curves are similar, and two mass loss
steps are observed. For 1 and 2, the first weight losses in the
range of 25−260 °C are 6.78% and 6.29%, respectively,
corresponding to the release of three coordinated water
molecules for per formula unit (calcd.: 6.40% for 1 and
6.48% for 2). Above 260 °C, the weight losses may be ascribed
to the collapse of the frameworks. For 3−5, the first weight
losses are 8.18% and 8.36% for 3 and 4 in the range of 25−235
°C, and 8.39% for 5 in the range of 25−250 °C, which are
ascribed to the release of two coordinated water molecules for
per formula unit (calcd.: 8.35% for 3, 8.32% for 4 and 8.25% for
5). Then, the following weight losses may be attributed to the
complete decomposition of the polymers. The purity of the
polycrystalline powder samples of 1−5 was determined by the
PXRD data (Figure S4−S6), and the results suggested that the
experimental data are in agreement with the simulated data
from their single-crystal structures.
Magnetic Properties. The magnetic susceptibilities of 2−5
have been studied in the temperature range of 2−300 K under
an applied direct current (dc) magnetic field of 1000 Oe
(Figure 5). At 300 K, the χMT values of 2 and 3 are 15.83 and
7.92 cm3 mol−1 K, which are in agreement with the expected
value of 15.76 cm3 mol−1 K (calculated for two spin-only Gd3+
(S = 7/2, g = 2) ions) and 7.88 cm3 mol−1 K (calculated for one
Gd3+ (S = 7/2, g = 2) ion), respectively. With lowering the
temperature, the χMT values of 2 and 3 remain almost constant
before 44 and 38 K, respectively, and then increase slightly to
Ng 2β 2 1 + u
S(S + 1)
3kT 1 − u
(1)
where u = cth(JS(S + 1)/kT) − kT/JS(S + 1)
χchain
χM =
1 − (zJ ′χchain /Ng 2β 2)
(2)
χchain =
In the equation, N is Avogadro’s number, β is the Bohr
magnetron, k is the Boltzmann constant, J is the exchange
coupling parameter between adjacent intrachain spins, and the
interchain interaction (zJ′) is treated by the molecular field
approximation. The best-fit parameters are g = 1.99(1), J =
0.0209(1) cm−1, zJ′ = −0.0324(1) cm−1, and R = 2.41 × 10−5,
where R is calculated from Σ[(χMT)obsd − (χMT)calcd]2/
Σ[(χMT)obsd]2. The positive and small J value is in good
agreement with the reported values for other carboxyl-bridged
Gd-containing complexes,3,17,37,39 suggesting the presence of
weak Gd−Gd ferromagnetic coupling interaction in the 1D
chain in 3.
In contrast, the magnetic interaction pathways in 2 are too
complicated to find a proper 2D model to fit the data
accurately. However, as shown in Scheme 3, because of the
similar Gd···Gd distances in (between) the alternating Gd1 and
Gd2 chains, the intrachain Gd−Gd exchange coupling
parameter can be treated as J1, and the interchain ones as J2.
Therefore, the following equations for a simplified 2D layer
model could be used to quantitatively analyze the magnetic
interaction.38,40,41
χchain =
Ng 2β 2 (1 + u1) (1 + u 2)
S(S + 1)
3kT (1 − u1) (1 − u 2)
(3)
where, u1 = cth(J1S(S + 1)/kT) - kT/J1S(S + 1), u2 = cth(J2S(S
+ 1)/kT) - kT/J2S(S + 1)
χchain
χM =
1 − (zJ ″χchain /Ng 2β 2)
(4)
The zJ″ represents the interplayer interaction treated by the
molecular field approximation. The best fitting results give g =
2.02(1), J1 = 0.0552(1) cm−1, J2 = −0.0548(1) cm−1, zJ″ =
−0.0323(1) cm−1, and R = 2.92 × 10−5 (R is calculated from
Σ[(χMT)obsd − (χMT)calcd]2/Σ[(χMT)obsd]2), indicating that the
intra- and interchain Gd−Gd coupling are ferromagnetic and
antiferromagnetic, respectively. When considering the magnetostructural relationship, the ferromagnetic behaviors in the 1D
chain units of 2 and 3, which are bridged by the η2-O atom of
the carboxy of the MMA2− ligand, may be mainly ascribed to
the larger Gd−O−Gd angle (ca. 135.46° for 2 and 127.84(1)°
for 3) and Gd−Gd bond length (ca. 4.81 Å for 2 and 4.68(1) Å
Figure 5. Temperature dependence of the χMT values for 2−5 at 1000
Oe dc magnetic field. The red solid lines represent the best fit to the
data.
F
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
Article
Scheme 3. View of the Magnetic Exchange Pathways in the Simplified 2D Layer Model
Figure 6. Field dependence of the magnetization plots of 2 (a) and 3 (b) at the indicated temperatures. −ΔSm calculated from the magnetization
data of 2 (c) and 3 (d) at various fields and temperatures.
the metal ions, the progressively thermal depopulation of the
ground-state Ln 3+ sublevels as well as the magnetic
anisotropy.17,31,43
Magnetization measurements for 2 and 3 were performed at
a field of 0−7 T between 2 and 7 K (Figure 6a,b). The M
versus H data show a steady increase in magnetization to come
up to a maximum value of 13.97 Nβ for 2 and 7.01 Nβ for 3 at
7 T and 2 K, which are close to the expected value of 7 and 14
Nβ for two and one uncoupled Gd3+ (S = 7/2, g = 2) ions,
respectively. To evaluate the MCE, the magnetic entropy
change of 2 and 3 can be obtained from the magnetization
change as a function of applied field and temperature (Figure
6c,d) by using the Maxwell equation ΔSm(T) = ∫ [∂M(T,H)/
for 3), as reported that a large Gd−O−Gd angle (>110°) and
Gd···Gd distance (>4.0 Å) usually tend to a ferromagnetic
coupling interaction for the chain-like polymers.3,37,42
For 4 and 5, the χMT values at room temperature are 11.68
and 14.24 cm3 mol−1 K, which are essentially consistent with
the expected values, 11.81 cm3 mol−1 K for 4 (one isolated
Tb3+ (S = 3, L = 3, g = 3/2) ion) and 14.18 cm3 mol−1 K for 5
(one Dy3+ (S = 5/2, L = 5, g = 4/3) ion). Upon cooling, for 4,
the χMT values decrease gradually to 9.97 cm3 mol−1 K around
25 K and then decrease abruptly to 5.92 cm3 mol−1 K at 2 K.
For 5, the χMT values decrease continuously to 10.80 cm3
mol−1 K at 2 K. The decrease of χMT values may be attributed
to a combination of the antiferromagnetic interactions between
G
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
Article
∂T]H dH.3,44 For 2, the resulting maximum −ΔSm is 34.32 J
K−1 kg−1 for ΔH = 7 T at 3.0 K, which is a considerable large
value among molecular magnetic coolants, and comparable with
those for the reported impressive Gd-based polymers.28,29,37
Theoretically, the full entropy change per mole of complex
corresponding to two Gd3+ ions is 40.92 J K−1 kg−1, as
calculated from eq 2 R ln(2S + 1) with S = 7/2. The difference
of −ΔSm between the theoretical and experimental values may
be due to the MW/NGd ratio of 422 (where MW is the molecular
mass of 844.90 g mol−1 and NGd is the number of Gd3+ ion in
per mole of 2) and the weak magnetic interaction in 2.18,29,45
For 3, the maximum value of −ΔSm is 36.02 J K−1 kg−1 at 2.0 K
and ΔH = 7 T, smaller than the expected maximum −ΔSm of
40.07 J K−1 kg−1, calculated from R ln(2S +1). Interestingly,
this value is slightly bigger than that of 2, although 3 has a
greater MW/NGd ratio (431). Considering the similar dominant
weak ferromagnetic coupling between the Gd3+ ions in 2 and 3,
this phenomenon may be related to the fact that the structure
of 3 has higher symmetry.
For the Tb- and Dy-containing complexes 4 and 5,
alternating-current susceptibility measurements were measured
at zero direct-current (dc) field (Figures S8 and S9); however,
no frequency-dependent out-of-phase signal was observed,
which suggests that none of them exhibits slow relaxation of the
magnetization.
Luminescent Properties. The luminescence spectra of
complexes 1, 4, and 5 were investigated in the solid state at
room temperature to explore the photophysical behavior in the
visible range under ultraviolet (UV) irradiation and are shown
in Figures 7, 8 and S10. Upon excitation at 395 nm, complex 1
Figure 8. Solid-state photoluminescence spectrum of 4 excited at 370
nm. Inset: photograph of green emissive 4 excited at 265 nm.
to the 4F9/2 → 6HJ (J = 15/2, 13/2, and 11/2) transitions of
Dy3+ ions (Figure S10).8,43 Obviously, the characteristic
emission for the INA− ligand was not observed in the three
complexes, suggesting that the INA− as an antenna can
effectively transfer the energy to Ln3+ centers during photoluminescence.18,27 Thus, the photoluminescence studies of the
three complexes suggest that the HINA can be used as an
excellent sensitive reagent for effectively sensitizing the
luminescence of Ln3+, especially for Eu3+ and Tb3+ ions,
which may be promising candidates for photoluminescent
materials.10,18,46
■
CONCLUSION
■
ASSOCIATED CONTENT
In summary, three types of lanthanide-based coordination
polymers with 2D layer (1/2 and 3/4) or 1D chain (5)
structures have been successfully prepared based on mixed
MMA2− and INA− ligands under hydrothermal conditions.
Magnetic studies suggest that the Gd-containing complexes 2
and 3 display ferromagnetic Gd···Gd coupling in the chain units
and significant cryogenic MCEs with a maximum −ΔSm value
of 34.32 at 3 K and 36.02 J kg−1 K−1 at 2 K for ΔH = 7 T,
respectively. Additionally, the Eu- and Tb-based polymers
exhibit strong characteristic Ln-centered emission in the visible
region. These results suggest that the mixed-ligand strategy may
be a promising way to construct Ln-CPs with interesting
magnetic and luminescent properties.
Figure 7. Solid-state photoluminescence spectrum of 1 excited at 395
nm. Inset: photograph of red emissive 1 excited at 265 nm.
S Supporting Information
*
exhibits red luminescence with characteristic Eu3+ bands at 593,
618, 652, and 698 nm (Figure 7), which are ascribed to the 5D0
→ 7FJ (J = 1, 2, 3, 4) transitions of Eu3+ centers. The most
intense emission is centered at 618 nm and corresponds to the
hypersensitive transition 5D0 → 7F2, which is consistent with
the Eu3+ complexes reported previously.8,12 When excited at
370 nm, 4 displays a strong Tb3+ characteristic emission with
four typical narrow peaks at 491, 545, 584, and 622 nm, which
corresponds to the 5D4 → 7FJ (J = 6, 5, 4, and 3) transitions of
the Tb3+ centers.27,38 The emission spectrum is dominated by
the most intense band at 544 nm assigned to 5D4 → 7F5, giving
in the complex strong bright-green emission (inset of Figure 8).
On excitation at 352 nm, compound 5 displays three relatively
weak emissions at 485, 574, and 662 nm, which are attributed
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.cgd.7b01341.
Crystal data, additional crystallographic diagrams, magnetic diagrams, IR spectra, TG curves, and PXRD
patterns (PDF)
Accession Codes
CCDC 1567439−1567443 contain the supplementary crystallographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
H
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
■
Article
Dorcet, V.; Golhen, S.; Cador, O.; Maury, O.; Guyot, Y.; Decurtins, S.;
Liu, S. X.; Ouahab, L. Inorg. Chem. 2015, 54, 5384−5397.
(14) (a) Liu, Y.; Chen, Z.; Ren, J.; Zhao, X. Q.; Cheng, P.; Zhao, B.
Inorg. Chem. 2012, 51, 7433−7435. (b) Zhu, M.; Mei, X. L.; Ma, Y.; Li,
L. C.; Liao, D. Z.; Sutter, J. P. Chem. Commun. 2014, 50, 1906−1908.
(c) Wang, K.; Chen, Z. L.; Zou, H. H.; Zhang, Z.; Sun, W. Y.; Liang, F.
P. Cryst. Growth Des. 2015, 15, 2883−2890. (d) Li, Z. Y.; Yang, J. S.;
Liu, R. B.; Zhang, J. J.; Liu, S. Q.; Ni, J.; Duan, C. Y. Dalton Trans.
2012, 41, 13264−13266.
(15) Ungur, L.; Lin, S. Y.; Tang, J. K.; Chibotaru, L. F. Chem. Soc.
Rev. 2014, 43, 6894−6905.
(16) (a) Zhang, P.; Zhang, L.; Wang, C.; Xue, S. F.; Lin, S. Y.; Tang,
J. K. J. Am. Chem. Soc. 2014, 136, 4484−4487. (b) Wang, Y. L.; Han,
C. B.; Zhang, Y. Q.; Liu, Q. Y.; Liu, C. M.; Yin, S. G. Inorg. Chem.
2016, 55, 5578−5584.
(17) Li, Z. Y.; Zhai, B.; Li, S. Z.; Cao, G. X.; Zhang, F. Q.; Zhang, X.
F.; Zhang, F. L.; Zhang, C. Cryst. Growth Des. 2016, 16, 4574−4581.
(18) Li, Z. Y.; Chen, Y.; Dong, X. Y.; Zhai, B.; Zhang, X. F.; Zhang,
C.; Zhang, F. L.; Li, S. Z.; Cao, G. X. Cryst. Growth Des. 2017, 17,
3877−3884.
(19) (a) Liu, S. J.; Zhao, J. P.; Tao, J.; Jia, J. M.; Han, S. D.; Li, Y.;
Chen, Y. C.; Bu, X. H. Inorg. Chem. 2013, 52, 9163−9165. (b) Guo, F.
S.; Chen, Y. C.; Mao, L. L.; Lin, W. Q.; Leng, J. D.; Tarasenko, R.;
Orendác,̌ M.; Prokleška, J.; Sechovský, V.; Tong, M. L. Chem. - Eur. J.
2013, 19, 14876−14885. (c) Wu, M.; Jiang, F.; Kong, X. J.; Yuan, D.;
Long, L. S.; Al-Thabaiti, S. A.; Hong, M. Chem. Sci. 2013, 4, 3104−
3109.
(20) (a) Meng, Y.; Chen, Y. C.; Zhang, Z. M.; Lin, Z. J.; Tong, M. L.
Inorg. Chem. 2014, 53, 9052−9057. (b) Gao, H. L.; Jiang, L.; Liu, S.;
Shen, H. Y.; Wang, W. M.; Cui, J. Z. Dalton Trans. 2016, 45, 253−264.
(21) (a) Li, Z. Y.; Zhu, J.; Wang, X. Q.; Ni, J.; Zhang, J. J.; Liu, S. Q.;
Duan, C. Y. Dalton Trans. 2013, 42, 5711−5717. (b) Li, Z. Y.; Wang,
Y. X.; Zhu, J.; Liu, S. Q.; Xin, G.; Zhang, J. J.; Huang, H. Q.; Duan, C.
Y. Cryst. Growth Des. 2013, 13, 3429−3437.
(22) (a) Wang, S. Y.; Wang, W. M.; Zhang, H. X.; Shen, H. Y.; Jiang,
L.; Cui, J. Z.; Gao, H. L. Dalton Trans. 2016, 45, 3362−3371. (b) Liu,
S. J.; Xie, X. R.; Zheng, T. F.; Bao, J.; Liao, J. S.; Chen, J. L.; Wen, H.
R. CrystEngComm 2015, 17, 7270−7275. (c) Biswas, S.; Mondal, A. K.;
Konar, S. Inorg. Chem. 2016, 55, 2085−2090.
(23) Liu, S. J.; Cao, C.; Xie, C. C.; Zheng, T. F.; Tong, X. L.; Liao, J.
S.; Chen, J. L.; Wen, H. R.; Chang, Z.; Bu, X. H. Dalton Trans. 2016,
45, 9209−9215.
(24) Zheng, Y. Z.; Zhou, G. J.; Zheng, Z. P.; Winpenny, R. E. P.
Chem. Soc. Rev. 2014, 43, 1462−1475.
(25) Zheng, Y. Z.; Evangelisti, M.; Tuna, F.; Winpenny, R. E. P. J.
Am. Chem. Soc. 2012, 134, 1057−1065.
(26) Liu, F.; Huang, H. H.; Gao, W.; Zhang, X. M.; Liu, J. P.
CrystEngComm 2017, 19, 3660−3665.
(27) Zhang, L.; Zhao, L.; Zhang, P.; Wang, C.; Yuan, S. W.; Tang, J.
K. Inorg. Chem. 2015, 54, 11535−11541.
(28) Chen, Y. C.; Qin, L.; Meng, Z. S.; Yang, D. F.; Wu, C.; Fu, Z.
D.; Zheng, Y. Z.; Liu, J. L.; Tarasenko, R.; Orendác,̌ M.; Prokleška, J.;
Sechovský, V.; Tong, M. L. J. Mater. Chem. A 2014, 2, 9851−9858.
(29) (a) Zhang, S. W.; Duan, E. Y.; Cheng, P. J. Mater. Chem. A 2015,
3, 7157−7162. (b) Peng, J. B.; Kong, X. J.; Zhang, Q. C.; Orendác,̌ M.;
Prokleška, J.; Ren, Y. P.; Long, L. S.; Zheng, Z. P.; Zheng, L. S. J. Am.
Chem. Soc. 2014, 136, 17938−17941.
(30) Hou, Y. L.; Xiong, G.; Shi, P. F.; Cheng, R. R.; Cui, J. Z.; Zhao,
B. Chem. Commun. 2013, 49, 6066−6068.
(31) Qiu, J. Z.; Chen, Y. C.; Wang, L. F.; Li, Q. W.; Orendác,̌ M.;
Tong, M. L. Inorg. Chem. Front. 2016, 3, 150−156.
(32) (a) Wang, L.; Zhao, R.; Xu, L. Y.; Liu, T.; Zhao, J. P.; Wang, S.
M.; Liu, F. C. CrystEngComm 2014, 16, 2070−2077. (b) Wang, X.; Li,
X. B.; Yan, R. H.; Wang, Y. Q.; Gao, E. Q. Dalton Trans. 2013, 42,
10000−10010.
(33) (a) Akintola, O.; Ziegenbalg, S.; Buchholz, A.; Görls, H.; Plass,
W. CrystEngComm 2017, 19, 2723−2732. (b) Yang, Y. Y.; Lin, Z. J.;
Liu, T. T.; Liang, J.; Cao, R. CrystEngComm 2015, 17, 1381−1388.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: zhaibin_1978@163.com. (B.Z.).
*E-mail: guangxiucao@163.com. (G.-X.C.).
ORCID
Zhong-Yi Li: 0000-0003-0597-9054
Bin Zhai: 0000-0002-2866-1121
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (NSFC) (Grant Nos. 21401126,
21371114, 21571123, 21601119, 21501117), Scientific and
Technological Projects of Science and Technology Department
of Henan province (172102210437).
■
REFERENCES
(1) (a) Tranchemontagne, D. J.; Mendoza-Cortés, J. L.; O’Keeffe,
M.; Yaghi, O. M. Chem. Soc. Rev. 2009, 38, 1257−1283. (b) Feng, J.;
Zhang, H. J. Chem. Soc. Rev. 2013, 42, 387−410. (c) Heffern, M. C.;
Matosziuk, L. M.; Meade, T. J. Chem. Rev. 2014, 114, 4496−4539.
(d) Cui, Y. J.; Yue, Y. F.; Qian, G. D.; Chen, B. L. Chem. Rev. 2012,
112, 1126−1162. (e) Aromı, G.; Aguila, D.; Gamez, P.; Luis, F.;
Roubeau, O. Chem. Soc. Rev. 2012, 41, 537−546. (f) Bottrill, M.;
Kwok, L.; Long, N. J. Chem. Soc. Rev. 2006, 35, 557−571.
(2) (a) Han, Y. F.; Li, X. Y.; Li, L. Q.; Ma, C. L.; Shen, Z.; Song, Y.;
You, X. Z. Inorg. Chem. 2010, 49, 10781−10787. (b) Tuna, F.; Smith,
C. A.; Bodensteiner, M.; Ungur, L.; Chibotaru, L. F.; Mcinnes, E. J. L.;
Winpenny, R. E. P.; Collison, D.; Layfield, R. A. Angew. Chem., Int. Ed.
2012, 51, 6976−6980. (c) Colacio, E.; Ruiz, J.; Mota, A. J.; Palacios,
M. A.; Cremades, E.; Ruiz, E.; White, F. J.; Brechin, E. K. Inorg. Chem.
2012, 51, 5857−5868. (d) Yamashita, A.; Watanabe, A.; Akine, S.;
Nabeshima, T.; Nakano, M.; Yamamura, T.; Kajiwara, T. Angew.
Chem., Int. Ed. 2011, 50, 4016−4019. (e) Liu, Q. Y.; Wang, W. F.;
Wang, Y. L.; Shan, Z. M.; Wang, M. S.; Tang, J. K. Inorg. Chem. 2012,
51, 2381−2392. (f) Wang, Y.; Cheng, P.; Chen, J.; Liao, D. Z.; Yan, S.
P. Inorg. Chem. 2007, 46, 4530−4534.
(3) Zhang, S. W.; Shi, W.; Li, L. L.; Duan, E. Y.; Cheng, P. Inorg.
Chem. 2014, 53, 10340−10346.
(4) Wang, S. N.; Cao, T. T.; Yan, H.; Li, Y. W.; Lu, J.; Ma, R. R.; Li,
D. C.; Dou, J. M.; Bai, J. F. Inorg. Chem. 2016, 55, 5139−5151.
(5) Pointillart, F.; le Guennic, B.; Cador, O.; Maury, O.; Ouahab, L.
Acc. Chem. Res. 2015, 48, 2834−2842.
(6) Akhtar, M. N.; Chen, Y. C.; AlDamen, M.; Tong, M. L. Dalton
Trans. 2017, 46, 116−124.
(7) Shen, H. Y.; Wang, W. M.; Bi, Y. X.; Gao, H. L.; Liu, S.; Cui, J. Z.
Dalton Trans. 2015, 44, 18893−18901.
(8) Li, H. N.; Li, H. Y.; Li, L. K.; Xu, L.; Hou, K.; Zang, S. Q.; Mak,
T. C. W. Cryst. Growth Des. 2015, 15, 4331−4340.
(9) (a) Duan, J.; Higuchi, M.; Foo, M. L.; Horike, S.; Rao, K. P.;
Kitagawa, S. Inorg. Chem. 2013, 52, 8244−8249. (b) De Bettencourt
Dias, A.; Viswanathan, S. Chem. Commun. 2004, 1024−1025.
(10) Li, Y.; Yu, J. W.; Liu, Z. Y.; Yang, E. C.; Zhao, X. J. Inorg. Chem.
2015, 54, 153−160.
(11) Feng, X.; Ma, L. F.; Liu, L.; Wang, L. Y.; Song, H. L.; Xie, S. Y.
Cryst. Growth Des. 2013, 13, 4469−4479.
(12) Zhao, J.; Zhu, G. H.; Xie, L. Q.; Wu, Y. S.; Wu, H. L.; Zhou, A.
J.; Wu, Z. Y.; Wang, J.; Chen, Y. C.; Tong, M. L. Dalton Trans. 2015,
44, 14424−14435.
(13) (a) Sabbatini, N.; Guardigli, M.; Lehn, J. M. Coord. Chem. Rev.
1993, 123, 201−228. (b) Lapadula, G.; Trummer, D.; Conley, M. P.;
Steinmann, M.; Ran, Y. F.; Brasselet, S.; Guyot, Y.; Maury, O.;
Decurtins, S.; Liu, S. X.; Copéret, C. Chem. Mater. 2015, 27, 2033−
2039. (c) Pointillart, F.; Jung, J.; Berraud-Pache, R.; Le Guennic, B. L.;
I
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
Article
(34) (a) Pasan, J.; Sanchiz, J.; Lloret, F.; Julve, M.; Ruiz-Perez, C.
CrystEngComm 2007, 9, 478−487. (b) Deniz, M.; HernandezRodriguez, I.; Pasan, J.; Fabelo, O.; Canadillas-Delgado, L.; Yuste,
C.; Julve, M.; Lloret, F.; Ruiz-Perez, C. Cryst. Growth Des. 2012, 12,
4505−4518.
(35) (a) Wang, K.; Yi, X. C.; Wang, X.; Li, X. B.; Gao, E. Q. Dalton
Trans. 2013, 42, 8748−8760. (b) Banerjee, D.; Wang, H.; Plonka, A.
M.; Emge, T. J.; Parise, J. B.; Li, J. Chem. - Eur. J. 2016, 22, 11816−
11825.
(36) (a) Sheldrick, G. M. SHELXS-97, Program for X-ray Crystal
Structure Determination; University of Göttingen: Germany, 1997.
(b) Sheldrick, G. M. SHELXL-97, Program for X-ray Crystal Structure
Refinement; University of Göttingen: Germany, 1997.
(37) Guo, F. S.; Leng, J. D.; Liu, J. L.; Meng, Z. S.; Tong, M. L. Inorg.
Chem. 2012, 51, 405−413.
(38) Fisher, M. E. Am. J. Phys. 1964, 32, 343−346.
(39) Hou, Y. L.; Cheng, R. R.; Xiong, G.; Cui, J. Z.; Zhao, B. Dalton
Trans. 2014, 43, 1814−1820.
(40) Maji, T. K.; Sain, S.; Mostafa, G.; Lu, T. H.; Ribas, J.; Monfort,
M.; Chaudhuri, N. R. Inorg. Chem. 2003, 42, 709−716.
(41) (a) Curély, J. Europhys. Lett. 1995, 32, 529−534. (b) Curély, J.
Phys. B 1998, 245, 263−276. (c) Curély, J. Phys. B 1998, 254, 277−
297. (d) Curély, J.; Rouch, J. Phys. B 1998, 254, 298−321.
(42) Cañadillas-Delgado, L.; Pasán, J.; Fabelo, O.; Julve, M.; Lloret,
F.; Ruiz-Pérez, C. Polyhedron 2013, 52, 321−332.
(43) (a) Eliseeva, S. V.; Bünzli, J. C. G. Chem. Soc. Rev. 2010, 39,
189−227. (b) Kurmoo, M. Chem. Soc. Rev. 2009, 38, 1353−1379.
(44) (a) Evangelisti, M.; Luis, F.; de Jongh, L. J.; Affronte, M. J.
Mater. Chem. 2006, 16, 2534−2459. (b) Evangelisti, M.; Brechin, E. K.
Dalton Trans. 2010, 39, 4672−4676. (c) Wang, W. M.; Zhang, H. X.;
Wang, S. Y.; Shen, H. Y.; Gao, H. L.; Cui, J. Z.; Zhao, B. Inorg. Chem.
2015, 54, 10610−10622.
(45) Hu, F. L.; Jiang, F. L.; Zheng, J.; Wu, M. Y.; Pang, J. D.; Hong,
M. C. Inorg. Chem. 2015, 54, 6081−6083.
(46) Biswas, S.; Jena, H. S.; Goswami, S.; Sanda, S.; Konar, S. Cryst.
Growth Des. 2014, 14, 1287−1295.
J
DOI: 10.1021/acs.cgd.7b01341
Cryst. Growth Des. XXXX, XXX, XXX−XXX
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