Magnetic and thermal properties of three ionothermally synthesized metal-carboxylate frameworks of [M3(ip)4][EMIm] 2 (M = Co, Ni, Mn, H2ip = isophthalic acid, EMIm = 1-ethyl-3-methyl imidazolium)

Article abstract of DOI:10.1039/c1dt10070j

Three metal-organic frameworks, [M₃(ip)₄][EMIm] ₂ (M = Co 1, Ni 2, Mn 3, H₂ip = isophthalic acid, EMIm = 1-ethyl-3-methyl imidazolium) were prepared from an ionic liquid medium. All the compounds feature the same (4²⁴)(6⁴) topology based on linear trinuclear clusters as eight-connected nodes. Compounds 1 and 2 are isostructural, while compound 3 exhibits a different structure due to the slight difference in the arrangement of M₃(OOCR)₈ SBUs. Magnetic property measurements reveal that all the compounds display anti-ferromagnetic coupling, where compounds 2 and 3 show isotropic exchange interactions of -0.10 cm^-1 for 2 and -1.6 cm^-1 for 3. Investigation of the thermal diffusivity shows that the thermal diffusivity of 1 is higher than that of 3, while that of 3 is higher than that of 2. The Royal Society of Chemistry 2011.

Full text of DOI:10.1039/c1dt10070j

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PAPER
Magnetic and thermal properties of three ionothermally synthesized
metal–carboxylate frameworks of [M (ip) ][EMIm] (M = Co, Ni, Mn,
3
4
2
H ip = isophthalic acid, EMIm = 1-ethyl-3-methyl imidazolium)†
2
Wen-Xian Chen, Gui-Lin Zhuang, Hai-Xia Zhao, La-Sheng Long,* Rong-Bin Huang and Lan-Sun Zheng
Received 14th January 2011, Accepted 9th May 2011
DOI: 10.1039/c1dt10070j
Three metal–organic frameworks, [M
3
(ip)
4
][EMIm]
2
(M = Co 1, Ni 2, Mn 3, H ip = isophthalic acid,
2
EMIm = 1-ethyl-3-methyl imidazolium) were prepared from an ionic liquid medium. All the
2
4
4
compounds feature the same (4 )(6 ) topology based on linear trinuclear clusters as eight-connected
nodes. Compounds 1 and 2 are isostructural, while compound 3 exhibits a different structure due to the
slight difference in the arrangement of M
3
(OOCR) SBUs. Magnetic property measurements reveal that
8
all the compounds display anti-ferromagnetic coupling, where compounds 2 and 3 show isotropic
-
1
-1
exchange interactions of -0.10 cm for 2 and -1.6 cm for 3. Investigation of the thermal diffusivity
shows that the thermal diffusivity of 1 is higher than that of 3, while that of 3 is higher than that of 2.
Introduction
or the cation and anion of the ILs on the structures of ionothermal
materials, the effect of metal centers in ionothermal reactions
remains largely unexplored. On the other hand, although ILs are
known to possess a high thermal capacity, investigation of the
thermal diffusivity of ionothermally synthesized metal–organic
frameworks has never been performed.
Significant efforts have been expended towards construction of
various functional coordination materials through traditional
hydro/solvothermal reactions, resulting in important develop-
ments in the past years. However, developing novel solid-state
polymeric architectures through new synthetic strategies is still a
challenge. Ionothermal synthesis as a promising synthetic tech-
1,2
Utilizing the derivative of isophthalic acid as the supporting
ligand, we have reported the syntheses of 4f and 3d–4f heterometal-
3
nique especially for the preparation of zeotypes and coordination
9
lic frameworks under ionothermal conditions. As an expansion
4
polymers is of particular interest. Firstly, the peculiar physic-
of our study, we report herein three ionothermally synthesized
ochemical properties of ionic liquids (ILs) such as low melting
points, high thermal stability and negligible vapor pressure, allows
materials [M
3
(ip)
4
][EMIm]
2
(M = Co 1, Ni 2, Mn 3, H ip = isoph-
2
5
thalic acid) generated under the same reaction conditions. Crystal
structural analysis reveals that all the three compounds feature
ionothermal synthesis to be more environmentally-friendly and
safer than hydro/solvothermal reactions. Moreover, the cations of
the ionic liquid not only act in a charge-compensating and space-
fillingroleinthematerials, butalsodirecttheformationofdifferent
structural patterns from those obtained using a routine synthetic
approach, despite the same organic ligand being employed.
Finally, tuning the solvent properties by combining the cations
and the anions in various ways, could be an approach to design
24
4
(
4 )(6 ) topology based on the M
3
(OOCR) clusters as eight-
8
connected nodes. Magnetic property measurements indicate that
all compounds display anti-ferromagnetic coupling. Investigation
of the thermal diffusivity shows that the thermal diffusivity of 1 is
higher than that of 3, while that of 3 is higher than that of 2.
6
7
Experimental
the structures of coordination polymers. With these properties,
ionothermal synthesis has experienced a drastic development in
the past several years. Although extensive research efforts have
Materials and physical measurements
8
been devoted to studying the influence of the cation or the anion,
All the reagents and solvents employed were commercially avail-
able and used as received without further purification. The C,
H, and N microanalyses were carried out with a CE instruments
EA 1110 elemental analyzer. The FT-IR spectra were recorded in
the range of 4000–400 cm with a Nicolet AVATAR FT-IR360
spectrometer. The X-ray powder diffractometry (XRPD) study
was performed on Panalytical X-Pert pro diffractometer with
Cu-Ka radiation. The thermogravimetric analysis (TGA) was
performed with a NETZSCH STA 449C instrument. Thermal
diffusivity was measured by NETZSCH LFA 457 NanoFlash.
State Key Laboratory of Physical Chemistry of Solid Surface and Depart-
ment of Chemistry, College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen, 361005, China. E-mail: lslong@xmu.edu.cn; Fax: +86
-
1
5
92 218 3047
†
Electronic supplementary information (ESI) available: X-ray crystallo-
graphic files in cif format for complexes 1–3, program XMMAG and X-ray
powder diffraction for the residual products of 1 to 3. CCDC reference
numbers 809087–809089. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c1dt10070j
This journal is © The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 10237–10241 | 10237

View Article Online
Table 1 Crystal data and details of the data collection and refinement for compounds 1 to 3
Complex
1
2
3
Formula
Mr
C
44
H
38
N
4
O
16 Co
3
C
44
H
38
N
4
O
16 Ni
3
44 38 4 3
C H N O16Mn
1055.57
Orthorhombic
Pbca
15.414(3)
11.877(2)
24.154(5)
90
1054.91
Orthorhombic
Pbca
15.491(2)
11.669(3)
23.750(2)
90
90
90
4293.1(3)
4
1.632
1043.6
Monoclinic
P2 /c
Crystal system
Space group
1
a/A˚
13.092(3)
14.490(3)
12.640(3)
90
116.85(3)
90
2139.3(7)
2
1.620
b/A˚
c/A˚
◦
a ( )
◦
b ( )
90
90
◦
g ( )
V/A˚
3
4421.7(15)
4
1.586
Z
-
3
D
c
/g cm
m/mm
No. of data/parameter
-1
1.190
1.382
0.952
4335/306
3.14–26.00
2418
4206/350
2.78–26.00
2569
4195/304
3.23–26.00
2903
◦
q range/
Obs reflns
R
1
[I > 2s(I)]
2
0.0637
0.1758
0.0389
0.0702
0.0579
0.1795
wR
(all data)
ꢀꢀF
| - |F
ꢀ/ꢀ
|F
|. wR
= [ꢀ
w(F
- F
) /
ꢀw(F
) ] .
2
2
2
2
2
1/2
R
1
=
o
c
o
2
o
c
o
Magnetic susceptibility was measured by a Quantum Design
MPMS superconducting quantum interference device (SQUID).
Compound 3 was prepared under similar ionothermal condi-
tions as illustrated for 1, except that Mn(OOCCH O was
3
)
2
·4H
2
used. Colorless crystals were obtained in about 37.6.% yield (based
on isophthalic acid). Anal. calcd (found) for Mn C H O N (%):
X-Ray crystallography
3
44
38 16
4
C, 50.60(50.54); N, 5.37(5.28); H, 3.64(3.61). IR Spectra for 3 (KBr,
Data collections were performed on a Rigaku R-AXIS RAPID
IP diffractometer at 293 K for 1, 173 K for 3 and on an Oxford
Gemini S Ultra CCD area detector at 173 K for 2. Absorption
corrections were applied by using the analytical program Tompa-
analytical for 1, 3 and multiscan program CrysAlis Red for 2.
The structures were solved by direct methods, and non-hydrogen
-
1
cm ): 1614.2 s, 1576.1 s, 1383.3 s, 752 s, 712.7 s, 1478.8 m, 1430.0
m, 1172.1 m, 822.1 m, 437.4 m, 3430.4 w, 3115.4 w, 1265 w, 1072.9
w, 655.5 w.
Results and discussion
2
Compound 1 crystallized in the orthorhombic space group Pbca.
Crystal structure analysis reveals that the asymmetric unit consists
of one and half Co(II) ions, two ip ligands, and one EMIm ion. The
coordination environment of the Co(II) ions is best described as a
distorted octahedron. Co1 is six coordinated by six monodentate
carboxylates, respectively from six ip ligands. Co2 is coordinated
by two chelate carboxylates and two monodentate carboxylates,
respectively from four ip ligands. The Co–O distances range from
atoms were refined anisotropically by least-squares on F using
10
the SHELXTL program. The hydrogen atoms of organic ligands
˚
˚
were generated geometrically (C–H, 0.96 A; N–H, 0.90 A). Crystal
data as well as details of data collection and refinement for the
compounds are summarized in Table 1. CCDC number of 809087
to 809089 for 1 to 3.
Synthesis
˚
1
.991(4) to 2.386(4) A, comparable to those in the reported Co-
Compound 1 was ionothermally synthesized as follows: a mixture
11
complex. Each independent Co1 center bridged two adjacent
Co2 ions via two carboxylate groups in a syn–syn fashion and
one carboxylate group in chelating/bridging mode generates a
of 0.249 g Co(OOCCH
g ionic liquid 1-ethyl-3-methyl imidazolium bromide was sealed to
a 25 mL Teflon-lined Parr at 140 C for about a week and then
cooled to room temperature at the rate of 3 C h . The dark-purple
crystals were obtained in 39.2% yield (based on isophthalic acid).
3
)
2
·4H
2
O, 0.166 g isophthalic acid and 1.2
◦
trinuclear unit M
3
(OOCR) as shown in Fig. 1c. The Co ◊ ◊ ◊ Co
8
◦
-1
˚
distance separated by the carboxylate group is 3.528 A. Such a
trinuclear unit is further linked to eight neighboring trinuclear
units through eight ip ligands, leading to a three-dimensional
open framework. The EMIm cations of the ionic liquid, acting
as charge-compensating agents, are located in the voids of the
anionic framework. The overall structure of the 3D network can be
Anal. calcd (found) for Co
3
C
44
H
38
O
16
N (%): C, 50.02(49.71); N,
4
-
1
5
1
3
.31(5.28); H, 3.60(3.64). IR Spectra for 1 (KBr, cm ): 1607.4 s,
383 s, 749.3 s, 714.2 s, 1579.4 m, 1480.6 m, 1171.3 m, 448.2 m,
149.9 w, 3119.3 w, 3082 w, 1264.5 w, 1073.7 w, 824.3 w.
Compound 2 was prepared under similar ionothermal condi-
described as a 8-connected net linked by M
3
(OOCR)
8
SBUs as 8-
tions as described for 1, except that Ni(OOCCH
used. Green crystals were obtained in about 40.7% yield (based on
isophthalic acid). Anal. calcd (found) for Ni (%): C,
0.05(49.49); N, 5.31(5.46); H, 3.60(3.27). IR Spectra for 2 (KBr,
3
)
2
·4H
2
O was
connected nodes (Fig. 1e). The 8-connected net in 1 shown in Fig.
24
4
1
f can be further specified by the Schl a¨ fli symbol (4 )(6 ) where the
shortest rings meeting at the twenty four and four angles of the
-connected vertices, are 4- and 6-membered rings respectively.
Compound 2 is isostructural to 1. The bond lengths of Ni–O
3
C
44
H
38
O
16
N
4
5
8
-
1
cm ): 1619.7 s, 1549.1 s, 1379.1 s, 751.3 s, 717.6 s, 1401.2 m, 1169.7
m, 828.6 m, 446.3 m, 3146.6 w, 3119.7 w, 3075.8 w, 1266.4 w, 1073.6
w, 657.1 w.
˚
are 1.962(2)–2.239(2) A, comparable to those in the reported Ni-
12
˚
complex. The Ni ◊ ◊ ◊ Ni distance is 3.444 A.
1
0238 | Dalton Trans., 2011, 40, 10237–10241
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Fig. 1 Coordination environments of the trinuclear cluster in 1 and 2 (a), and 3 (b); Two different trinuclear structures in 1 and 2 (c), and 3 (d); A
24 4
schematic view of the connections of one node (e); The 4 6 topological network of 1–3 (f).
Different from 1 and 2, compound 3 crystallized in the mono-
clinic space group P2 /c. Crystal structure analysis reveals that 3
has the same topology as that of 1 and also exhibits a 3D anionic
framework consisting of trinuclear units M (OOCR) (Fig. 1d)
as 8-connected nodes (Fig. 1e). However, the arrangement of
(OOCR) SBU in 3 is significantly different from these in 1
M
3
(OOCR)
8
SBU in 1 and 2 adopted a similar arrangement
1
with that in 3. Consistently, although the same organic ligand
was employed, and even the same topology was adopted,
the structures of 1 and 2 are very different from that of the
Co(II)-based framework obtained from solvothermal reactions,
while the structure of 3 is similar to that of the Co(II)-based
13
14
3
8
M
3
8
and 2 (Fig. 2), which is attributed to the radius of the manganese
ion being larger than those of the cobalt and nickel ions, and
because repulsion between ip ligands and EMIm ions in the anonic
framework would be greatly increased if the arrangement of the
framework obtained from solvothermal reactions, due to the fact
+
that the H
2
N(CH
3
)
2
in the Co(II)-based framework obtained from
solvothermal reactions is significantly smaller than the EMIm ions
in present work. It was mentioned that, although the solvent-
accessible volumes and pore volume ratios of three compounds
1
5
3
˚
calculated through the PLATON program are 1653.9 A (37.4%)
3
3
˚
˚
for 1, 1584.0 A (36.9%) for 2 and 717.6 A (33.5%) for 3,
respectively, utilization of the anionic frameworks to perform
cation exchange was a failure, due to the pore window being too
small to allow the EMIm ions to be removed from the pores.
Magnetic properties of 1–3 were investigated through variable-
temperature susceptibility measurements in the temperature range
from 2.0 to 300 K with an applied magnetic field of 1000
3
Oe. For 1, the c T value at room temperature is 9.45 cm
M
-
1
mol K, which is considerably larger than the spin-only value
of 5.63 cm mol K calculated for three high-spin Co(II) ions
3
-1
(
S = 3/2, g = 2) due to the orbital contribution from single Co(II)
ions (Fig. 3a). Upon lowering the temperature, the c
continuously decreases to a minimum value of 6.50 cm mol
M
3
T value
-1
K
(
5 K), indicating dominant intramolecular antiferromagnetic
interactions. Compound 1 behaves as a Curie–Weiss paramagnet
above 100 K, which can be fitted with a Weiss constant of
3
-1
16
-
11.15 K and a Curie constant of 9.83 cm mol K. Attempts
to simulate the magnetic susceptibility by spin-Hamiltonian with
the help of our program XMMAG (Supporting information S1†)
failed, because six-coordinate Co(II) ions present considerable
first-order orbital momentum, and the spin-Hamiltonian must
be supplemented by the orbital-dependent exchange interactions
17
and spin–orbit coupling effects. It should be mentioned here that
the coordination polymer [H N(CH [Co (ip) O previously
2
3
)
2
]
2
3
4
]·H
2
14
reported by Zheng et al., which features the same topology
of the 3D network and bridging mode of the trinuclear unit
as that of 1, displays ferromagnetic interactions. Scrutinizing
˚
Fig. 2 3D network of 1 and 2 (a), and 3 (b) along the a axis.
This journal is © The Royal Society of Chemistry 2011
their structure reveals that the Co ◊ ◊ ◊ Co distance (3.528 A) and
Dalton Trans., 2011, 40, 10237–10241 | 10239

View Article Online
program XMMAG in which isotropic exchange interactions (J)
and inter-unit interaction (zJ) were taken into account. The best-
-
1
-1
fit gives a set of parameters: J = -0.10 cm , g = 2.28, zJ = -0.19 cm
-
4
-1
-1
and R = 2.0 ¥ 10 for 2; J = -1.60 cm , g = 2.00, zJ = -0.02 cm
and R = 3.0 ¥ 10 for 3, where R is calculated from [(c
ꢀ
-
5
M
T)obs
-
ꢀ
2
2
(
c
M
T)calcd] / [(c
M
T)obs] . The negative J value exclusively reveals
low antiferromagnetic exchange between metal ions. The negative
zJ value also indicates antiferromagnetic exchange between the
adjacent units.
Thermogravimetric analysis (TGA) studies were performed in
◦
-1
an air atmosphere at a heating rate of 10 C min for 1–3. As
shown in Fig. 5, the TGA diagrams of 1–3 display no weight loss
◦
◦
◦
before the temperature of 360 C for 1, 380 C for 2 and 350 C
for 3. As the temperature further increases, 1–3 rapidly decompose
◦
and the weight loss is steep until the temperature reaches 473 C
for 1, 456 C for 2 and 476 C for 3, indicating the removal of
◦
◦
counter ions and organic ligands. The residual weight of 22.5%,
2
1.7% and 21.8% respectively for 1 to 3 is consistent with the
calculated values of 22.8% for Co in 1, 21.2% for NiO in 2
and 22.7% for Mn in 3 respectively. The residual products were
3
O
4
2
O
3
proved by X-ray powder diffraction (Supporting information, Fig.
S1 to S3†).
-1
Fig. 3 Plot of c
(b), 3 (c).
M
T vs. T (denoted o) and c
M
vs T (denoted ꢀ) for 1 (a),
2
Fig. 4 Thermal diffusivity for 1–3.
◦
Co–O–Co angle (108.08 ) in the unit of 1 are very close to those
◦
˚
(
3.533 A, 108.47 ) in [H
2
N(CH
3
)
2
]
2
[Co
3
(ip)
4
]·H
2
O, implying that
the magnetic difference may be attributed to the presence of
18
different guest molecules.
For 2 and 3, the resulting c
Fig. 3c respectively. The c T value at room temperature (300 K)
M
T vs. T plot is given in Fig. 3b and
M
3
-1
3
-1
is 3.85 cm mol K for 2 and 12.39 cm mol K for 3, consistent
with the value expected for three independent metal ions in the
16
2+
2+
molecule, following a Curie law with (Ni , g = 2.26 for 2; Mn ,
g = 1.95 for 3). As the temperature decreases, the value of c
M
-1
T for
3
3
decreases slowly and reaches the minimum 4.37 cm mol K at
2
K, while for 2 it does not decrease slowly until 18 K and then
3
-1
decreases abruptly and reaches the minimum 2.49 cm mol
at 2 K. Furthermore, the linear fit was performed for c
following the Curie–Weiss law,
of parameters: C = 3.90 cm mol K, q = -0.81 K for 2 and C =
K
vs. T
-
1
◦
M
Fig. 5 TG curves from room temperature to 800 C for 1–3.
16
c
M
-1
= C/(T - q), which gives a set
3
Owing to ILs possessing high thermal capacity, it is expected
that compounds 1 to 3 have lower thermal diffusivity and function
as new heat-resistant materials. Accordingly, the Flash Method
was used to perform thermal diffusivity measurements of 1 to 3 on
the basis of their pellet samples. The resulting thermal diffusivity
of 1 to 3 at different temperatures are shown in Fig. 4. The
3
-1
13.10 cm mol K, q = -17.63 K for 3. These results indicate that
2
and 3 in general exhibit antiferromagnetic coupling between two
2
1
2
metal ions through m :h ,h -carboxylate bridges.
In order to elucidate the magnetic exchange interactions in 2
and 3, the magnetic susceptibilities were fitted with the help of our
1
0240 | Dalton Trans., 2011, 40, 10237–10241
This journal is © The Royal Society of Chemistry 2011

View Article Online
thermal diffusivity values at room temperature are 0.157, 0.139
2 (a) E. Tang, Y.-M. Dai, J. Zhang, Z.-J. Li, Y.-G. Yao, J. Zhang and
X.-D. Huang, Inorg. Chem., 2006, 45, 6276; (b) M. P. Suh, Y. E. Cheon
and E. Y. Lee, Chem.–Eur. J., 2007, 13, 4208; (c) W.-X. Chen, S.-T. Wu,
L.-S. Long, R.-B. Huang and L.-S. Zheng, Cryst. Growth Des., 2007, 7,
1171.
3 (a) E. R. Cooper, C. D. Andrews, P. S. Wheatley, P. B. Webb, P. Wormald
and R. E. Morris, Nature, 2004, 430, 1012; (b) E. R. Parnham, P. S.
Wheatley and R. E. Morris, Chem. Commun., 2006, 380; (c) E. R.
Parnham and R. E. Morris, J. Am. Chem. Soc., 2006, 128, 2204; (d) E.
R. Parnham and R. E. Morris, Chem. Mater., 2006, 18, 4882; (e) E. A.
Drylie, D. S. Wragg, E. R. Parnham, P. S. Wheatley, A. M. Z. Slawin,
J. E. Warren and R. E. Morris, Angew. Chem., Int. Ed., 2007, 46, 7839.
2
-1
and 0.151 mm S K for 1 to 3 respectively and decrease with the
increase of temperature. Such low thermal diffusivity values are
close to that of plastic, indicating that ionothermally synthesized
compounds may be good candidates for heat-resistant materials.
Since 1 and 2 are isostructural, the observed thermal diffusivity
of 1 which is higher than that of 2 indicates that it is the density
of the framework that plays a key contribution to their thermal
diffusivity, and the higher the density of the framework, the lower
the thermal diffusivity. This result is different from that reported
by J. M. Devi and coworkers, in which the thermal diffusivity of
the complexes increases with the decrease in the mass and increase
4
(a) K. Jin, X. Huang, L. Pang, J. Li, A. Appel and S. Wherland, Chem.
Commun., 2002, 2872; (b) D. N. Dybtsev, H. Chun and K. Kim, Chem.
Commun., 2004, 1594; (c) Z. Lin, D. S. Wragg and R. E. Morris, Chem.
Commun., 2006, 2021; (d) S. Chen, J. Zhang and X. Bu, Inorg. Chem.,
19
in the free electron density of the metal ion coordinated. It was
mentioned that, although the density of 3 is close to that of 2, and
significantly larger than that of 1, the thermal diffusivity of 3 is
close to that of 1, instead of close to that of 2, which may be due
to the fact that the structure of 3 is different from those of 1 and 2.
2
008, 47, 5567.
5
(a) J. G. Huddleston, A. E. Visser, W. M. Reichert, H. D. Willauer,
G. A. Broker and R. D. Rogers, Green Chem., 2001, 3, 156; (b) R. D.
Rogers and K. R. Seddon, Science, 2003, 302, 792; (c) K. E. Gutowski,
G. A. Broker, H. D. Willauer, J. G. Huddleston, R. P. Swatloski, J. D.
Holbrey and R. D. Rogers, J. Am. Chem. Soc., 2003, 125, 6632; (d) R.
Ludwig and U. Kragl, Angew. Chem., Int. Ed., 2007, 46, 6582.
Conclusions
6 (a) L. Xu, E. Y. Choi and Y. U. Kwon, Inorg. Chem., 2007, 46, 10670.
7
(a) Z. Lin, D. S. Wragg, J. E. Warren and R. E. Morris, J. Am. Chem.
Soc., 2007, 129, 10334; (b) Z. Lin, A. M. Z. Slawin and R. E. Morris,
J. Am. Chem. Soc., 2007, 129, 4880; (c) L. Xu, E. Y. Choi and Y. U.
Kwon, Inorg. Chem., 2008, 47, 1907; (d) L. Xu, S. Yan, E. Y. Choi, J. Y.
Lee and Y. U. Kwon, Chem. Commun., 2009, 3431.
In summary, three metal–organic frameworks based on linear
trinuclear clusters as 8-connected nodes were prepared under
ionothermal conditions. All the compounds feature the same a
2
4
4
(
4 )(6 ) topology. Their structures are significantly different from
8 (a) E. R. Parnham and R. E. Morris, Acc. Chem. Res., 2007, 40, 1005;
(
b) R. E. Morris, Chem. Commun., 2009, 2990.
those obtained from hydrothermal or solvothermal reactions,
indicating that ionic liquids serve as the cationic structure-
directing agent in the formation of the host networks. Magnetic
property measurement reveals that all compounds display anti-
ferromagnetic coupling, while the thermal diffusivity study shows
that their thermal diffusivity is in the order of 1 > 3 > 2.
9
W.-X. Chen, Y.-P. Ren, L.-S. Long, R.-B. Huang and L.-S. Zheng,
CrystEngComm, 2009, 11, 1522.
10 SHELXTL 6.10, Bruker Analytical Instrumentation, Madison, WI,
2000.
1
1
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