Inorganica Chimica Acta 363 (2010) 15561560

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Inorganica Chimica Acta

journal homepage: www.elsevier.com/locate/ica

New synthetic route of polyoxometalate-based hybrids in choline chloride/urea

eutectic media
Shi-Ming Wang, Yun-Wu Li, Xiao-Jia Feng, Yang-Guang Li *, En-Bo Wang *
Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Renmin Street No. 5268,
Changchun, Jilin 130024, PR China

a r t i c l e

i n f o

Article history:
Received 25 June 2009
Received in revised form 5 November 2009
Accepted 7 December 2009
Available online 4 January 2010
Keywords:
Polyoxometalates
Eutectic mixture
Choline chloride
Urea
Green synthesis route

a b s t r a c t
The deep eutectic solvents synthetic method was initially explored as a facile synthesis route to prepare
new polyoxometalate (POM)-based hybrids. Such a method can not only avoid poor solubility, lower
yields and the potential explosion, but also act as a new type of noxious, convenient and environmental
friendly organic reagents. Using the choline chloride/urea eutectic mixture as the deep eutectic solvents,
two new compounds, [(CH3)3N(CH2)2OH]4[b-Mo8O26] (1) and {(N2H5CO)[(CH3)3N(CH2)2OH]2}[CrMo6O24H6]4H2O (2), were successfully obtained at room temperature. Both compounds were fully characterized by elemental analyses, IR, UVVis, TG analyses, cyclic voltammetry and single-crystal X-ray
diffraction. The crystal structures of both compounds exhibit 3-D supramolecular assembly based on
the extensive hydrogen bonding interactions between organic cations and polyoxoanions. Compounds
1 and 2 represent the rst POM-based hybrids prepared by the deep eutectic solvents synthetic method.
2009 Elsevier B.V. All rights reserved.

1. Introduction
In the eld of polyoxometalate (POM) chemistry, the exploration of new POM species possessing novel structures and properties is a permanent aim that researchers have been pursuing all
along [111]. One of the most fundamental and important research
directions is to seek new and suitable synthesis methods, which is
still a realistic and great challenge nowadays. Generally, there are
two main ways to synthesize new POMs. The rst method is the
conventional synthesis. As an old and classic method, numerous
new POMs have been prepared by this way [1214]. Nevertheless,
there are still some disadvantages for conventional synthesis, for
example, the highest temperature of the reaction system usually
cannot exceed 100 C due to the limitation of boiling points of most
available solvents. Further, some chemicals for example the transitional metal oxides have poor solubility in most of such solvents.
The second method is the hydrothermal or solvothermal synthesis.
Such methods provide high-temperature and high-pressure environments, overcoming the solubility problems of various organic
and inorganic precursors [1517]. But the limitation of such methods have also gradually been discovered, such as the low yields and
insolubility of nal products, the hardness of repetition and controlment, the unclarity of reaction mechanism, and the potential
explosion of organic solvent and organic reactants. In order to

* Corresponding authors. Tel./fax: +86 431 85098787.

E-mail addresses: liyg658@nenu.edu.cn (Y.-G. Li), wangeb889@nenu.edu.cn,
wangenbo@public.cc.jl.cn (E.-B. Wang).
0020-1693/$ - see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2009.12.012

avoid these disadvantages of above two methods, new method

has been explored, i.e., the ionothermal method. New polyoxometalate-based hybrids can be synthesized in good quality by this
method [18,19]. However, its widespread applications will be limited by toxicological, economic and purity issues [20,21]. It is reported that the longer of the alkyl chain of imidazolium ionic
liquids, the greater toxicity it will be [22]. Therefore, a green and
facile synthesis route to synthesize new POM species is appealing.
Since eutectic mixtures were introduced to synthesize coordination polymers and zeolite materials, especially the SiMo12 O4
40
and BMo6 O9
24 were also detected in the KFK2MoO4SiO2 and
KFK2MoO4B2O3 system [23,24], the deep eutectic solvents methods have now attracted more and more attention [25,26]. Eutectic
mixture can decrease the temperature for molten salt applications
and the deep eutectic solvents method possesses incomparable
superiority. For example, the eutectic mixture of urea and choline
chloride, which is liquid at ambient temperatures (the freezing
point is 12 C) and exhibits unusual solvent properties compared
with conventional liquids [27]. On the one hand, its non-volatile
property results in higher reaction temperature under atmospheric
pressure than those under the hydrothermal or solvothermal conditions, which can avoid the occurrence of explosion. On the other
hand, it possesses higher solubility that many inorganic and organic chemicals can be dissolved and even some insoluble transitional metal oxides were found to have signicant solubility in
eutectic mixture [18,19]. Moreover, it also shows some advantages
in contrast to the room temperature ionic liquids. Usually, choline
chloride/urea eutectic mixture is easy to prepare in a pure state
only by mechanical mixing choline chloride and urea together

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1557

2. Experimental

2.3.2. Synthesis of {(N2H5CO)[(CH3)3N(CH2)2OH]2}[CrMo6O24H6]4H2O

(2)
Na2MoO42H2O (0.6 g, 2.48 mmol) and concentrated hydrochloric acid (0.30 mL, 12 mol L1) were successively added to 5 mL eutectic mixture (urea and choline chloride) with stirring for one
minute. Then, Cr(NO3)39H2O (0.2 g, 0.5 mmol) was added to the
above solution. The resulting solution was stirred for 1 h in air at
30 C and generated a little amount of light purple precipitate.
After being cooled to room temperature (20 C), the light purple
suspension was ltered and the ltrate kept at room temperature.
The light purple crystalline products of 2 were isolated after one
week (yield 76% based on Cr). Elemental Anal. Calc. for the compound 2 (wt.%). Found: C, 9.27 (9.45); H, 3.46 (3.30); N, 4.12
(4.03); Cr, 4.12 (4.05); Mo, 42.35 (42.17). IR (KBr disk, cm1):
3340 (br), 1976 (m), 1590 (s), 1473 (s), 1174 (m), 932 (w), 909
(s), 890 (s), 771 (s).

2.1. Materials and measurements

2.4. X-ray crystallography

All chemicals were commercially purchased and used without

further purication. Elemental analyses of Mo for 1 and Mo and
Cr for 2 were performed by a Leaman inductively coupled plasma
(ICP) spectrometer. Elemental analyses of C, H and N atoms for 1
and 2 were performed on a PerkinElmer 2400 CHN elemental analyzer. IR spectra were recorded in the range of 4004000 cm1 on
an Alpha Centaurt FT/IR Spectrophotometer with pressed KBr pellets. Diffuse reectance UVVis spectra (BaSO4 pellet) were obtained with a Varian Cary 500 UVVis NIR spectrometer. The
UVVis spectra of both compounds are recorded in aqueous
solution at a concentration of 1.0  103 mol L1. Water contents
in 2 were determined by TG analyses on a PerkinElmer TGA7
instrument in owing N2 with a heating rate of 10 C min1. The
electrochemical measurements were carried out on a CHI 660 electrochemical workstation at room temperature (2530 C). The 1H
NMR of compound 2 was recorded on a INOVA-500 instrument
at room temperature. DMSO was used as the solvent.

The crystallographic data were collected at 150 K (for 1 and 2)

on a Rigaku R-axis Rapid IP diffractometer using graphite monochromatic Mo Ka radiation (k = 0.71073 ). The structures of 1
and 2 were solved by the direct method and rened by the full-matrix least-squares method on F2 using the SHELXTL-97 crystallographic software package [29,30]. All non-hydrogen atoms in the
crystal data of 12 were rened anisotropically. H-atoms on their
parent C and N atoms were xed in geometrically calculated positions, while the H-atoms on water molecules in compound 2 cannot be determined from the difference Fourier maps due to the
limited quality of the data. All H-atoms on water molecules were
directly included in the nal molecular formula based on the
charge-balance consideration. Further details of the X-ray structural analysis are given in Table 1. Selected bond lengths and angles of 12 are listed in Tables S1S4, respectively.

2.2. Electrochemical experiment

3.1. Synthesis

A CHI 830 electrochemical workstation connected to a PentiumIV personal computer is used for the control of the electrochemical
measurements and for data collection. A conventional three-electrode system is used. The working electrode is a glassy carbon, a
Ag/AgCl is employed as the reference electrode and platinum wire
as a counter electrode. Thrice-distilled water is used throughout
the experiments. A 0.2 M Na2SO4 + H2SO4 buffer solution with pH
3.0 is used as the media. A pHS-25B type pH meter is used for
pH measurement. All the experiments are conducted at room temperature (2530 C).

The use of choline chloride/urea eutectic mixture as the reaction media not only avoids poor solubility, lower yields, the potential explosion, but also can be regarded as an additional noxious,
convenient and environmental friendly organic reagents. During
the synthesis, a series of parallel experiments show that the key
factors for the formation of compound 1 is the acidity and for 2
is the proportion of the initial reactants (Cr:Mo). During the formation of 1, the crystalline compounds can only be successfully obtained by adding 4.004.50 mL concentrated hydrochloric acid
(12 mol L1). If the volume of the HCl is less than 4.00 mL or more
than 4.50 mL, no crystals were obtained. During the preparation of
compound 2, it can be obtained in a molar proportion of Cr:Mo
from 1:3.5 to 1:6.5. However, if the proportion is close to 1:4.96,
the crystals can be isolated in the shortest time with the highest
yield.

[22]. Further, it cannot react with water but can be degraded by

bios. Moreover, its toxicological properties have been well characterized (the choline chloride is vitamin B4 and is produced on the
Mtonne p.a. scale as an additive for chicken feed, while the urea
is a common used fertilizer) [28]. However, to the best of our
knowledge, the synthesis of POMs using choline chloride/urea eutectic mixture as solvent has not been reported to date. Based on
the aforementioned considerations, we tried to introduce this
green and facile chemical way to synthesize new POM species. In
this work, two new POM-based hybrids, [(CH3)3N(CH2)2OH]4[bMo8O26] (1) and {(N2H5CO)[(CH3)3N(CH2)2OH]2}[CrMo6O24H6]
4H2O (2), has been successfully synthesized with high yields by
this method for the rst time.

2.3. Synthesis
2.3.1. Synthesis of [(CH3)3N(CH2)2OH]4[b-Mo8O26] (1)
Na2MoO42H2O (1 g, 4.13 mmol) was dissolved in 5 mL eutectic
mixture (urea and choline chloride). Then, the concentrated hydrochloric acid (0.45 mL, 12 mol L1) was added to above solution,
stirring for 3 h in air at 30 C. After being cooled to 20 C, the white
suspension was ltered and the ltrate kept at room temperature
(20 C). Colorless block crystals of 1 were isolated after one
week (yield 73% based on Mo). Elemental Anal. Calc. for the compound 1 (wt.%). Found: C, 15.02 (15.29); H, 3.50 (3.63); N, 3.50
(3.41); Mo, 47.96 (47.68). IR (KBr disk, cm1): 3417 (br), 1470
(m), 1336 (w), 1131 (w), 1041 (m), 1008 (w), 912 (s), 842 (s),
707 (s), 553 (m).

3. Results and discussion

3.2. Crystal structure of compounds 12

3.2.1. [(CH3)3N(CH2)2OH]4[b-Mo8O26] (1)
Single-crystal X-ray diffraction analysis shows that compound 1
crystallizes in the triclinic space group P-1. The basic structural
unit of 1 contains one b-octamolybdate isopolyanion [b-Mo8O26]4
and four choline cations (see Fig. 1). The basic structural feature of
b-[Mo8O26]4 is similar to those previously reported [3135]. As
shown in Fig. S1, this polyoxoanion consists of eight edge-sharing
{MoO6} octahedra and displays the characteristic b-octamolybdate

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Table 1
Crystal data and structure renement for 12.
Compounds

Empirical formula
Formula weight
k ()
T (K)
Crystal system
Space group
a ()
b ()
c ()
a ()
b ()
c ()
V (3)
Z
Dcalc/Mg m3
l/mm1
F(0 0 0)
Crystal size (mm)
h range ()
Limiting indices
reections

C20H56Mo8N4O30
1600.21
0.71073
150(2)
Triclinic
P-1
12.308(3)
12.536(3)
22.167(4)
80.30(3)
85.14(3)
81.45(3)
3327.6(12)
3
2.396
2.283
2340
0.28  0.26  0.23
3.0225.00
14 6 h 6 14
14 6 k 6 14
23 6 l 6 26
25 933/11 602
[R(int) = 0.0641]
Empirical
Full-matrix leastsquares on F2
11 602/0/839

C11H47CrMo6N4O31
1359.17
0.71073
150(2)
Monoclinic
C2/c
13.707(3)
22.113(4)
13.194(3)
90
109.73(3)
90
3764.5(13)
4
2.398
2.319
2660
0.28  0.26  0.23
3.1625.00
15 6 h 6 16
26 6 k 6 26
15 6 l 6 15
14 336/3319
[R(int) = 0.0908]
Empirical
Full-matrix leastsquares on F2
3319/0/242

0.960

1.087

R1 = 0.0512
wR2 = 0.1160
R1 = 0.0894
wR2 = 0.1402
0.845/0.957

R1 = 0.0539
wR2 = 0.1323
R1 = 0.0727
wR2 = 0.1434
1.565/1.561

Reections collected/
unique
Absorption correction
Renement method
Data/restraints/
parameters
Goodness-of-t (GOF)
on F2
Final R indices
[I > 2r(I)]a
R indices (all data)b

Dqmax,min/e 3
a
b

R1 = R||Fo|  |Fc||/R|Fo|.
h
i h
i1=2
wR2 R wF 2o  F 2c 2 =R wF 2o 2
.

geometry with different distortion extents. The +VI oxidation state

is also conrmed by bond valence sum calculations [34]. Four
kinds of oxygen atoms exist in the b-isomer, that is, the terminal
oxygen Ot, double-bridging oxygen O (l2), three-bridging oxygen
O (l3), and ve-bridging oxygen O (l5). The bond lengths of Mo
O are in the range of 1.674(8)2.500(6) and the bond angles of
OMoO vary from 68.9(2) to 176.1(2). Both of them are in good
agreement with those of molybdate compounds previously reported, respectively [3135]. It is noteworthy that in the structure
of 1, there are four choline moieties that serve as the cations,
which, as far as we known, have never been met before in POMsbased hybrid materials chemistry. As shown in Fig. 2 , two different
types of hydrogen contacts have been found: the H-atom of
hydroxide group of the choline with the terminal oxygen of the
polyanion (O(choline)H  Ot, the distance is ca. 2.12 ); the H-atom
of hydroxide group of the choline with the bridging oxygen of the
polyanion (O(choline)HO2, the distance is ca. 2.48 ). Based on this
arrangement, the polyoxoanions and the choline cations are wellarranged into a 3-D supramolecular assembly (as shown in Fig. 2).
3.2.2. {(N2H5CO)[(CH3)3N(CH2)2OH]2}[CrMo6O24H6]4H2O (2)
Single-crystal X-ray diffraction analysis reveals that compound
2 crystallizes in the monoclinic space group C2/c. In the basic structural unit of 2, there is one Anderson anion cluster [CrMo6O24H6]3,
two choline molecules, one protonated urea molecule [37,38] and
four water molecules (see Fig. 3). The [CrMo6O24H6]3 cluster retains the well-known B-type Anderson structure and exhibits a
centrosymmetric arrangement, i.e., six slightly distorted {MoO6}
octahedral edge-sharing units surrounding the central {Cr(OH)6}
octahedron. The six OH groups are conrmed by the BVS [36]
(see Table S5) and 1H NMR (see Fig. S9). The central Cr is coordinated by six l3-OH units, while each Mo atom is coordinated by
two Ot, two l2-O and two l3-OH units. The central CrO distances
vary from 1.967(5) to 1.987(5) and the bond angles of OCrO
vary from 83.4(2) to 180.0(3). The bond lengths of MoO are in
the range of 1.689(6)2.324(5) and the bond angles of OMoO
vary from 69.39(19) to 161.8(3). Both of them are in good accordance with other previously reported values, respectively [4246].
All molybdenum centers and Cr center exhibit +VI and +III oxidation state, respectively, which are also conrmed by bond valence
sum calculations [36]. Compound 2 also exists hydrogen bonding
interaction between the terminal oxygen atom of the Anderson
cluster and the urea molecules (N(urea)H  Ot, the distance is ca.
2.03 ) (see Fig. 4). Based on this arrangement, the polyoxoanions
and the urea molecules are well-arranged into a 3-D supramolecular assembly (as shown in Fig. 4). This structure is also observed for
the rst time in POM elds.
3.3. FT-IR and UVVis spectroscopy

Fig. 1. Polyhedral and ball-and-stick representation of compound 1.

arrangement, a classical isomer of eight octamolybdate clusters, in

which two centrosymmetrically related cyclic {Mo4O13} units are
cross-linked by bridging oxygen atoms. All molybdenum sites
exhibit +VI oxidation state, possessing octahedral coordination

The IR spectrum of compound 1 is shown in Fig. S3. Four characteristic peaks at 912, 842, 707 and 553 cm1 are attributed to
m(MoOt) and m(MoOb) vibrations of the polyanion, which are
similar to those in Refs. [3135]. In addition, the other peaks at
1474, 1336, 1131, 1041 and 1008 cm1 are regarded as the characteristic vibrations of the cationic choline. The IR spectrum of compound 2 is shown in Fig. S4. Four characteristic peaks at 932, 909,
890 and 771 cm1 are attributed to m(MoOt), m(MoOb) and m(Mo
Oc) vibrations of the polyanion, which in good agreement with
those of compounds previously reported [4246]. In addition, the
other peaks at 1677, 1632, 1473 and 1174 cm1 are assigned to
the vibrations of the cationic choline and urea.
The UVVis spectrum of compound 1 is recorded in aqueous
solution at a concentration of 1.0  103 mol L1. The resulting
spectrum is shown in Fig. S5. Two main peaks at 240 nm and
293 nm are attributed to the O ? Mo LMCT bands [3135]. The

S.-M. Wang et al. / Inorganica Chimica Acta 363 (2010) 15561560

1559

Fig. 2. The three-dimensional hydrogen-bonded supramolecular framework of compound 1.

Fig. 3. Polyhedral and ball-and-stick representation of compound 2.

Fig. 4. The three-dimensional hydrogen-bonded supramolecular framework of compound 2.

UVVis spectrum of compound 2 is recorded in aqueous solution at

a concentration of 1.0  103 mol L1. The resulting spectrum is
shown in Fig. S6. Two main peaks at 211 nm and 235 nm are also
ascribed to the O ? Mo LMCT bands [4246].

3.4. Thermal analysis

The TG curve of compound 1 is shown in Fig. S7, there is only
one obvious weight loss step. The weight loss in the range of

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S.-M. Wang et al. / Inorganica Chimica Acta 363 (2010) 15561560

ing Foundation and Science and Technology Creation Foundation of

Northeast Normal University (Grant NENU-STC07009).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.ica.2009.12.012.
References

Fig. 5. Cyclic voltammograms of 4  103 M 1 in the pH 3.0 (0.2 M H2SO4 + Na2SO4)

buffer solution at the scan rate of 10 mV s1.

211554 C corresponds to the release of the four free choline cations. The loss-weight of 27.40% is accordance to the calculated value 26.00%. For compound 2 is shown in Fig. S8, there are two
obvious weight loss steps. The rst weight loss of 5.20% in the temperature range of 95120 C corresponds to the loss of lattice water
molecules. The second weight loss of 27.8% in the temperature
range of 155540 C is attributed to the loss of free choline cations,
urea molecule and composed water molecules. The whole weight
loss of 32.00% is in good agreement with the calculated value
32.50%.
3.5. Electrochemical analyses
The electrochemical property of compound 1 is shown in Fig. 5.
The cycle voltammetry (CV) of compound 1 was recorded in the pH
3.0 (0.2 M H2SO4 + Na2SO4) buffer solution at the scan rate of
10 mV s1. Three reversible redox peaks appear in the potential
range from +0.5 to 0.2 V versus SCE as shown in Fig. 5. The mean
potentials E1/2 = (Epa + Epc)/2 are 0.312, 0.203 and 0.066 V, respectively. The three redox peaks II0 , IIII0 and IIIIII0 might be ascribed
to the three consecutive two electrons processes of MoVI/MoV.[32
41]. For compound 2, no electrochemical signal was recorded. Such
a phenomenon has ever been observed and discussed in reported
in Ref. [8].
4. Conclusion
In summary, two polyoxometalates were successfully synthesized in a green and facile synthesis method. It is the rst time that
new polyoxometalate-based hybrids are obtained by using convenient and environmental friendly eutectic mixture to date. The successful synthesis of such two POM-based hybrids may suggest a
new feasible synthetic route for searching and exploring other novel polyoxometalates-based hybrid materials.
Acknowledgments
This work was supported by the National Natural Science Foundation of China (No. 20701005/20701006), the Post-doc station
Foundation of Ministry of Education (No. 20060200002), the Test-

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