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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
1557
2. Experimental
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.
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).
1558
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
.
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
1559
1560
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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