Inorganic Chemistry Communications 13 (2010) 972975

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Inorganic Chemistry Communications

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i n o c h e

Three new polyoxometalate-based hybrids prepared from choline chloride/urea deep

eutectic mixture at room temperature
Shi-Ming Wang, Wei-Lin Chen, En-Bo Wang , Yang-Guang Li , Xiao-Jia Feng, Lin Liu
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 March 2010
Accepted 20 May 2010
Available online 26 May 2010
Keywords:
Deep eutectic mixture
Polyoxometalate
Green routine
Ambient temperature
Ionic liquid

a b s t r a c t
Three new polyoxometalate-based hybrids {[(CH3)3N(CH2)2OH]2(H3O)}[Na2(H2O)6][IMo6O24]H2O 1 , {Na2
[(CH3)3N(CH2)2OH]4}[Al(OH)6Mo6O18]28NH2CONH24H2O 2 and {Na6(H2O)18[(CH3)3N(CH2)2OH]2(CON2
H5)2}[NaMo7O24]24NH2CONH2H2O 3 were successfully synthesized in the choline chloride/urea deep
eutectic mixture at room temperature. Reactant quantities of water presents in the nonaqueous eutectic
mixture solvent may inuence the structure of the products. The three compounds are fully characterized by
elemental analyses, IR, UVvis, TG analyses, power X-ray diffraction and single-crystal X-ray diffraction. The
photocatalytic properties of 1 and 2 are investigated.
2010 Elsevier B.V. All rights reserved.

The exploration of novel polyoxometalate (POM) structures is a

permanent aim that researchers have been pursuing all along [110].
One of the most fundamental and important ways is to seek new and
suitable synthesis methods, which remains a realistic and great challenge
nowadays. Recently, using ionic liquid as a solvent to synthesize new
POMs has gradually become a new strategy in POM synthesis area. Some
POM-based hybrids were synthesized from the imidazole ionic liquids,
such as, (C6H11N2)4(W10O32), (C6H11N2)4(W6O19)(BF4)2, [EMIM]8Na9
[WFe9(3-O)3(2-OH)6O4H2O(SiW9O34)3]7H2O (EMIM=1-ethyl-3methylimidazolium), [EMIM][SiMo12O40]12H2O (EMIM=1-ethyl-3methylimidazolium). [Dmim] 2 Na 3 [SiW 1 1 O 3 9 Fe(H 2 O)]H 2 O
(Dmim=1,3-dimethylimidazole), [Emim]9Na8[(SiW9O34)3{Fe3(2-OH)2
(3-O)}3(WO4)]0.5H2O (Emim=1-ethyl-3-methylimidazole) and
[Dmim]2[HMim]Na6[(AsW9O33)2{MnIII(H2O)}3]3H2O (Dmim=1,3dimethylimidazole; Mim=1-methylimidazole) [1114]. Room temperature eutectic mixture can fall under ionic liquid; it has the general
properties of the ionic liquids, such as, non-volatility, high uidity, low
melting temperature, high boiling temperature and nonammability
[1517]. However, it has its own special properties compared with the
imidazole ionic liquids. For instance, rst, the synthesis of eutectic
mixture is simple. The pure state can be obtained only through mixing
the two components together mechanically. Second, in eutectic mixture
many inorganic and organic chemicals perform better solubility than in
water. Even some insoluble metal oxides were found to have signicant
solubility in eutectic mixture. Third, it doesn't react with water and it is
biodegradable. Since choline chloride is vitamin B4 as an addictive for
Corresponding authors. Tel./fax: +86 431 85098787.
E-mail addresses: wangeb889@nenu.edu.cn (E.-B. Wang), liyg658@nenu.edu.cn
(Y.-G. Li).
1387-7003/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2010.05.010

feeding chicken and urea is a kind of common fertilizer, the choline

chloride/urea eutectic mixture we used in this paper possesses very low
toxicity [15,18]. Zeolite and coordinaton polymer were synthesized
using this eutectic mixture as a solvent at high temperature [1822]. We
reported two POM-based hybrids not long ago. That was the rst time
POM-based hybrids were obtained from choline chloride/urea eutectic
mixture. [23] The work reported in this paper is the continuation. The
work in this communication is deeper than the work we reported last
time. This choline chloride/urea eutectic mixture is not very stable at
higher temperature, for the urea can be decomposed into ammonium
ion. Large liquid phase temperature scale is one of the choline chloride/
urea eutectic mixture's features, for its eutectic temperature is 12 C
[15,19]. Therefore, all the experiments were performed at room
temperature to avoid the decomposition of urea. We successfully
synthesized three POM-based hybrids, {[(CH3)3N(CH2)2OH]2(H3O)}
[Na2(H2O)6][IMo6O24]H2O 1, {Na2[(CH3)3N(CH2)2OH]4}[Al(OH)6Mo6
O18]28NH2CONH24H2O 2 and {Na6(H2O)18[(CH3)3N(CH2)2OH]2
(CON2H5)2}[NaMo7O24]24NH2CONH2H2O 3. Compounds 1 and 2
perform a chain-like structure, whereas compound 3 performs a 3-D
structure on the basis of the different linkers. The reactant quantities of
water presented in the eutectic mixture may inuence the structures of
the linkers. According to the PXRD results, they all show high phase
purity. The successful synthesis of the three compounds also indicates
the choline chloride/urea eutectic mixture performs good solvent
characteristic and good stability at room temperature.
Compounds 1, 2 and 3 were synthesized at room temperature [24].
The details of the synthesis procedure of 2 and 3 are listed in the
Supplementary material. We successfully avoided the decomposition
of urea during the synthesis procedure. The urea molecules maintain
their structures in compounds 2 and 3. Moreover the choline cations

S.-M. Wang et al. / Inorganic Chemistry Communications 13 (2010) 972975

973

Fig. 1. Polyhedral and ball-and-stick representation of structure unit and 3-D hydrogen-bonded supramolecular framework of compound 1.

not only act as the counter cation, but also bond to the Na+ through
their OH groups in compound 3. The choline chloride/urea eutectic
mixture can be used at room temperature due to its good solvent
properties. Through trials and errors, the proper amount of reactants
was found. In the synthesis process, small amount of water was added
into this nonaqueous system, which takes an important role during
the formation of the linkers. The water in the eutectic mixture is apt to
form small cluster with Na+. In compound 1, the linker is only
composed of water molecules and Na+ cations (Fig. S1a); in
compound 2, there exists two kinds of linkers Na[H2O]+
2 and Na
[NH2CONH2]+
2 (Fig. S1b); in compound 3, the protonated urea and
choline cations all come into the linker (Fig. S1c). The structures of the
linkers can be inuenced by adding different amounts of water.
Single-crystal X-ray diffraction analysis of compound 1 [25]
reveals that there is one A-type Anderson anion cluster [IMo6O24]5
which links to a [Na2(H2O)6]2+ cluster, two choline cations, one
protonated water molecule and one lattice water molecule in the
basic structure unit.(see Fig. 1) The [IMo6O24]5 cluster retains the
well-known A-type Anderson structure and exhibits a centrosymmetric arrangement, that is, six slightly distorted {MoO6} octahedral
edge-sharing units surrounding the central {IO6} octahedron [26,27].
An innite 1-D chain is formed along c-axis bases on this connection
(Fig. S3). Considering the hydrogen bonding interactions between the
terminal oxygen atoms of the Anderson cluster and the choline

cations, the polyoxoanions and the choline cations are well-arranged

into a 3-D supramolecular assembly (as shown in Fig. 1).
Single-crystal X-ray diffraction analysis of compound 2 [28]
reveals that there are two B-type Anderson anion clusters
[AlMo6O24]5 which are linked by a sodium cation, four choline
cations, eight urea molecules, four lattice water molecules in the basic
structural unit (as shown in Fig. 2). The [AlMo6O24]5 cluster retains
the well-known B-type Anderson structure and exhibits a centrosymmetric arrangement [29,30], that is, six slightly distorted {MoO6}
octahedral edge-sharing units surrounding the central {AlO6} octahedron. The Anderson polyanions [Al(OH)6Mo6O18]3 assemble into
1-D chain through the co-ordination of the terminal oxygen atoms
and the sodium cations (see Fig. S5). According to the literature, the
linker usually performs the same coordination environment [3135].
But the linker with different coordination environments is really rare.
Considering the hydrogen bonding interactions between the neighbor
chains, it is well-arranged into a 3-D supramolecular assembly (see
Fig. 2).
Single-crystal X-ray diffraction analysis of compound 3 [36] reveals that there are two heptamolybdate anion clusters [Na2Mo7O24]4
which link to a frog-like linker {Na6(H2O)18(NH2CONH2)2[(CH3)3 N
(CH2)2OH]2}, four dissociated neutral urea molecules and lattice water
molecules in the basic structural unit of 3 (as shown in Fig. 3). The
[Mo7O24]6 cluster in 1 consists of seven slightly distorted edge-sharing

Fig. 2. Polyhedral and ball-and-stick representation of structure unit and 3-D hydrogen-bonded supramolecular framework of compound 2.

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S.-M. Wang et al. / Inorganic Chemistry Communications 13 (2010) 972975

Fig. 3. Polyhedral and ball-and-stick representation of structure unit and 3-D hydrogen-bonded supramolecular framework of compound 3.

{MoO6} octahedral [37,38]. And the heptamolybdate clusters are also

interconnected through Na+ to form an innite 1-D chain. (see Fig. S7)
Base on the above-mentioned connections, compound 3 exhibits a
unique 3-D frame. (as shown in Fig. 3) Interestingly, the adjacent layers
in bc plane are enantiomorphous (as shown in Fig. S8, Fig. S9).
The photocatalytic property of 1 is shown in Fig. 4. The
photocatalytic performance of compounds 1 and 2 were investigated
with photodegradation of RhB.[39] From the results, it can be
concluded that compound 1 (see Fig. 4a) has good catalytic activity
compared with compound 2 (see Fig. S10a). The degradation rate of
RhB with 1 in it is nearly two times over that with 2 in it. In the four
runs of photocatalytic tests the photoactivity of compounds 1 and 2
did not display signicant loss when RhB was re-added in the system
(see Fig. 4b, Fig S10b). This indicates that compounds 1 and 2 were
stable under the condition used.
In order to check the phase purity of 13, the powder X-ray
diffraction (PXRD) patterns of 13 were recorded at room temperature. As shown in Fig. 5, the peak positions of simulated (Fig. 5a) and
experimental (Fig. 5b) patterns of compound 1, the simulated (Fig.
S14a) and experimental (Fig. S14b) patterns of compound 2, as well as
the simulated (Fig. S14c) and experimental (Fig. S14d) patterns of
compound 3 are in good agreement with each other respectively,
indicating the good phase purity of 13. The differences in intensity

may be due to the preferred orientations of the crystalline powder

samples. This result indicates that the compounds which formed in
eutectic mixture also have good phase purity.
In summary, using choline chloride/urea eutectic mixture at room
temperature as the solvent is a good choice for the synthesis of
polyoxometalate-based multi-dimentional hybrids. The successful
synthesis of the three new POM-based hybrids indicates that using
eutectic mixture is feasible, convenient and safe in POM synthesis
area. And this synthesis route successfully avoids the decomposing of
urea. Different reactant quantities of water in the eutectic mixture
could inuence the nal structures of the products. The phase quality
of the compounds was high according to the PXRD analysis data. Some
other novel POM-based hybrid materials will be obtained using this
route. In our group, further research is continuing in this area.

Acknowledgements
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 Testing Foundation of
Northeast Normal University and Science Foundation for Young
Teachers of Northeast Normal University (No. 20070312/20070302).

Fig. 4. (a) Changes in UVvisible absorption spectra of RhB solutions (2 105 mol L1): in the presence of 0.005 g compound 1. (b) The comparison of four cycles' decomposition
rate of RhB with 1 in the system.

S.-M. Wang et al. / Inorganic Chemistry Communications 13 (2010) 972975

Fig. 5. Simulated (a) and experimental (b) PXRD patterns of compound 1.

Appendix A. Supplementary data

Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallgraphic Data Center, CCDC
reference number 752873 for compound 1, 752872 for compound 2
and 763141 for compound 3. These data can be obtained free of charge
at www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK;
fax: +44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk). Supplementary data contains the experimental section, synthesis of 2 and 3.
IR, TG, UV, PXRD and more structural gures of compound 13
associated with this article, as well as selected bond lengths and
angles of 13. Table of the BVS of the protonated oxygen atoms of
compound 2 is also included, at doi:10.1016/j.inoche.2010.05.010.
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5 cm between the liquid surface and the lamp. The solution was kept stirring
during irradiation. Every 30 minutes intervals, 3 mL of samples were taken out
from the beaker and subsequently analyzed by UVvisible spectroscopy. After the
initial amount of RhB had degraded, the same amount of RhB was added into the
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