Materials Chemistry and Physics 112 (2008) 853–857

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

Synthesis and characterization of hybrid molecular material prepared

by ionic liquid and silicotungstic acid
T. Rajkumar, G. Ranga Rao ∗
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India

a r t i c l e i n f o a b s t r a c t

Article history: A white colour IL-SiWA hybrid molecular material has been synthesized using 1-butyl 3-methyl imida-
Received 5 December 2007 zolium bromide ionic liquid and silicotungstic acid. The material is found to dissolve in polar organic
Received in revised form 4 June 2008 solvent such as DMSO, but not in water. It is characterized by CHN analysis, FTIR, XRD, UV–vis DRS, TGA
Accepted 21 June 2008
and SEM. The FTIR spectra indicate the formation of a hybrid compound showing fingerprint vibrational
bands of both Keggin ions of silicotungstic acid and imidazolium ions. There is a strong evidence of inter-
Keywords:
action between the Keggin anions and imidazolium cations from the UV–vis DR spectra and the splitting
Ionic liquid
of imidazolium C–H bands in the IR spectrum of the IL-SiWA. The near IR shows loss of crystallization
Silicotungstic acid
Keggin unit
water from heteropoly acid when it reacts with ionic liquid forming the hybrid molecular material.
Near IR © 2008 Elsevier B.V. All rights reserved.
Hybrid molecular material

1. Introduction
Synthesis of hybrid materials using polyoxometalates has been
a subject of immense interest in solid-state materials chemistry
[1–10]. The new polyoxometalate composite materials offer rich
structural chemistry and physicochemical properties of interest in
catalysis [7], photochromism [3,8,9], proton conductors [10,11]. The
pairing of polyoxometalate (POM) anions with organic cations and
ionic liquids (ILs) continue to yield interesting materials, including
a recent report on the synthesis of ambient temperature POM-
based ionic liquids [12]. The POM-based materials may retain
Keggin anion structure and show hybrid properties of both poly-
oxometalates and the organic part. Inorganic polyoxometalates are
solid acid materials having Brønsted acidity and contain Keggin
anions such as [XM12 O40 ]ı−8 (X = P5+ or Si4+ and M = W6+ , Mo6+ ),
which are interconnected by hydrogen-bonded water molecules
(maximum 29). These large metal oxide framework anions (size
∼1 nm) can react with room temperature ionic liquids forming
new organic–inorganic hybrid composite materials [12,13]. The
purpose of synthesizing the POM-based hybrid molecular salt is
to explore the potential applications in POM-based catalysis and
catalytic materials chemistry [14–16]. It is also important to under-
stand the nature of interactions between the Keggin anions and
organic cations and their stability in the molecular material [17].
Here we report for the fist time the synthesis and characterization
of a molecular compound based on 1-butyl 3-methyl imidazolium
(BmIm) cation and silicotungstic Keggin anion (SiWA). Near IR, IR
and UV–vis DR spectroscopy methods show that the molecular
compound contains Keggin anions paired with BmIm cations. The
split in the C–H stretching region (3050–3200 cm−1 ) and the red-
shift of the 332 nm transition to 305 nm in the UV–vis DR spectra
show strong electrostatic interactions between Keggin anions and
BmIm cations.
2. Experimental
2.1. Synthesis of ionic liquid
1-Butyl 3-methyl imidazolium bromide ionic liquid was synthesized using
materials as received (Fluka) and following procedure reported [18]. The IL was
prepared by taking 1:1 mole ratio of 1-methyl imidazole and 1-bromobutane. In a
typical preparation, 33.29 g of liquid 1-bromobutane was added to 20 g of liquid 1-
methyl imidazole in a round bottom flask fitted with reflux condenser under stirring
conditions at 80 ◦ C for 24 h. The top phase of the two phases formed contains unre-
acted starting material which can be removed by washing twice with ethyl acetate.
This also ensures the removal of the unreacted material in the bottom phase contain-
ing IL product. The yellowish IL product of 1-butyl 3-methyl imidazolium bromide
(BmImBr) liquid was further heated to 50 ◦ C to eliminate any dissolved ethyl acetate
solvent and its formation was confirmed by FTIR, 1 H and 13 C NMR [18,19].
2.2. Synthesis of 1-butyl 3-methyl imidazolium silicotungstic hybrid

For the synthesis of 1-butyl 3-methyl imidazolium silicotungstic hybrid molec-

ular material, 1-butyl 3-methyl imidazolium bromide and silicotungstic acid
(H4 SiW12 O40 ·nH2 O) were taken in 4:1 mole ratio in order to prepare one mole of
∗ Corresponding author. Tel.: +91 44 2257 4226; fax: +91 44 2257 4202. 1-butyl 3-methyl imidazolium silicotungstate. Ionic liquid was added drop wise to
E-mail address: grrao@iitm.ac.in (G. Ranga Rao). the solution containing silicotungstic acid (SiWA) under constant stirring at room

0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.06.046
854 T. Rajkumar, G. Ranga Rao / Materials Chemistry and Physics 112 (2008) 853–857

temperature. The white precipitate obtained was washed with distilled water and
dried at 80 ◦ C for overnight. It was characterized by CHN analysis which shows that
one mole of Keggin anions of [SiW12 O40 ]4− consume four moles of 1-butyl 3-methyl
imidazolium cations to form the molecular material. The formula estimated from
the C–H–N elemental analysis of the sample is C32.13 H55.85 N8.08 SiW12 O40 which gives
an empirical structure of [BmIm]4 [SiW12 O40 ]. This is consistent with 4:1 mole ratio
of BmIm cation to [SiW12 O40 ]4− used. The white colour hybrid material has sur-
face area of 0.7 m2 g−1 and has no porous structure. The hybrid material can be
dissolved readily in dimethyl sulphoxide (DMSO) and re-crystallized. However, it
scarcely dissolves in other standard organic solvents and water.

2.3. Characterization

The samples were analysed by X-ray diffraction employing Shimadzu XD-D1

diffractometer using Cu K␣ radiation ( = 1.5418 Å). The IR spectra of samples as KBr
pellets were recorded using PerkinElmer infrared spectrometer with a resolution
of 4 cm−1 and in the range of 400–4000 cm−1 . Thermogravimetric analysis (TGA) of
IL-SiWA hybrid molecular material was conducted in pure N2 gas (30 ml min−1 ) at
a heating rate of 20 ◦ C per min on a PerkinElmer TGA-7 instrument.
The UV–vis NIR spectra were recorded in diffuse reflectance mode on Jasco
V-570 UV-vis NIR spectrophotometer equipped with an integrating sphere in the
spectral range of 200–2500 nm. The spectra are presented as F(R), Kubelka–Munk
function versus incident photon wavelength. Scanning electron microscopy (SEM)
images were taken using a FEI Quanta 200 microscope operating at 30 kV. The sample
powders were deposited on a carbon tape before mounting on a sample holder.
Fig. 1. FTIR spectra of (a) 1-butyl 3-methyl imidazolium bromide (BmImBr) ionic
liquid, (b) H4 SiW12 O40 ·nH2 O and (c) [MmIm]4 [SiW12 O40 ] hybrid molecular material.
3. Results and discussion

3.1. FTIR analysis
The FTIR spectra are useful to study the skeletal modes appear-
ing between 700 and 1100 cm−1 of Keggin anions present in the
IL-SiWA hybrid molecular material. The parent [SiW12 O40 ]4− Keg-
gin structure shows characteristic bands due to W–O–W vibrations
of edge- and corner-sharing WO6 octahedra linked to the central
SiO4 tetrahedra [1,20]. Accordingly, the stretching modes of edge
sharing (W–Oe –W) and corner sharing (W–Oc –W) units appear
between 790 and 890 cm−1 , whereas the Si–O stretching mode
appears at 926 and 1014 cm−1 (Fig. 1). The IR spectrum of BmImBr
ionic liquid is also presented in Fig. 1, which is consistent with
the IR spectrum reported by Wu et al. [19]. It shows the char-
acteristic IR modes at 590–690, 1080–1600 and 2800–3200 cm−1
(alkyl and imidazole ring C–H stretch). In addition to these char-
acteristic bands, both the parent compounds (BmImBr and SiWA)
are hydrophilic and show the presence of large amount of water
at ∼3450 cm−1 (Table 1) [14,15,19]. However, the water content is
reduced significantly in the IL-SiWA hybrid molecular compound,
which is discussed in the near IR study in Section 3.5. The IL-SiWA
hybrid molecular material is hydrophobic and insoluble in water.
The main characteristic vibrations of various modes of organic
and inorganic moieties in the IL-SiWA molecular salt are given in
Table 1.
The basic structure and geometry of Keggin anions entrapped
in the BmIm cations are preserved in the hybrid molecular mate-
rial. However, a closer examination of IR spectra in the imidazolium
ring C–H stretch (3000–3250 cm−1 ) and imidazolium ring stretch
(1500–1620 cm−1 ) in Fig. 2 reveals that there is a strong electro-
static interaction between BmIm cation and large Keggin anion
[21–23]. Due to this interaction, the two C–H stretching peaks of the
imidazolium ring in BmImBr are split into five vibrational peaks in
the [MmIm]4 [SiW12 O40 ] molecular salt Fig. 2(A). The imidazolium
ring vibration is also split with intensity variations Fig. 2(B). The
origin of such C–H split is clearly attributed to specific interaction
of BmIm+ ion with bulky Keggin anion. This type of interaction is
demonstrated by Jerman and co-workers in the case of MPIm+ I− x
compounds [23]. The SEM picture of the [BmIm]4 [SiW12 O40 ] hybrid
molecular material is given in Fig. 3 which shows powdery mor-
phology with small clusters of adhered IL-SiWA particles.
3.2. Powder XRD
In this work, the bulky anion [SiW12 O40 ]4− , is substituted in
place of Br− in the imidazolium-based ionic liquid template. This
has lead to the formation of organic–inorganic hybrid solid mate-
rial. Fig. 4 shows the powder X-ray diffraction (PXRD) pattern of
pure silicotungstic acid and IL-SiWA hybrid molecular material.

Table 1
IR bands of BmImBr, H4 SiW12 O40 ·nH2 O and [BmIm]4 [SiW12 O40 ] hybrid molecular material

Wavenumber (cm−1 ) Vibration

BmImBr SiWA [BmIm]4 [SiW12 O40 ]

3450 3450 – Water in the material

3147, 3090 – 3086, 3104, 3112, 3141, 3157 Imidazole ring (C–H)
2959, 2936, 2873 – 2958, 2933, 2871 Aliphatic (C–H)
1630 1630 – O–H bending
1573, 1562 – 1562, 1570, 1573 Imidazole (ring stretching)
1168 – 1164 Imidazole H–C–C & H–C–N bending
– 1018, 926 1014, 926 (Si–O)
– 980 976 (W O)
– 878 883 (W–Oc –W)
– 781 795 (W–Oe –W)
840 – – In-plane imidazole ring bending
752 – – Out-of-plane C–H bending of imidazole ring
620 – 621 Imidazole C2 –N1 –C5 bending
 T. Rajkumar, G. Ranga Rao / Materials Chemistry and Physics 112 (2008) 853–857 855

Fig. 2. Imidazole ring C–H stretch (panel A) and imidazole ring stretch (panel B) regions of (a) 1-butyl 3-methyl imidazolium bromide (BmImBr) ionic liquid and (b)
[MmIm]4 [SiW12 O40 ] hybrid molecular material.

Using Scherrer’s formula, the average size of the IL-SiWA clus-
ter is estimated to be 18.5 nm. The silicotungstic acid undergoes
structural transformation where the four acidic protons and H2 O
molecules are replaced by 1-butyl 3-methyl imidazolium cations.
The PXRD pattern of IL-SiWA hybrid material reveals different
structure compared to pure SiWA salt. The PXRD pattern suggests
the existence of host–guest interactions between silicotungstic acid
and 1-butyl 3-methyl imidazolium cations in the absence of sand-
wiched water molecules, which are normally present in the bulk
polyoxometalates.
weight loss at 400–580 ◦ C and a minor loss at 580–700 ◦ C. Ther-
mal analysis of polyoxometalates generally shows water loss below
300 ◦ C and the Keggin anion decomposition in the temperature
range of 350–600 ◦ C [24,25]. Pure silicotungstic acid decomposes
to the constituent oxides around 500 ◦ C which falls in the major
decomposition region of IL-SiWA at 400–580 ◦ C. This region is

3.3. TG analysis

The thermogravimetric behaviour of IL-SiWA hybrid molecu-

lar material is shown in Fig. 5. The TGA curve shows a major

Fig. 4. Powder XRD pattern of (a) H4 SiW12 O40 ·nH2 O, and (b) [MmIm]4 [SiW12 O40 ]
Fig. 3. SEM image of [MmIm]4 [SiW12 O40 ] hybrid molecular material. hybrid molecular material.
856 T. Rajkumar, G. Ranga Rao / Materials Chemistry and Physics 112 (2008) 853–857

Fig. 5. TGA of [MmIm]4 [SiW12 O40 ] hybrid molecular material.

therefore attributed to the total decomposition of both organic

part and the inorganic Keggin anions in the hybrid molecular
material. There is no water loss seen below 300 ◦ C indicating that Fig. 6. UV–vis DR spectra of (a) BmImBr ionic liquid, (b) H4 SiW12 O40 ·nH2 O and (c)
[MmIm]4 [SiW12 O40 ] hybrid molecular material.
the bonding between BmIm and [SiW12 O40 ]4− eliminates water
and four acidic protons associated with bulk silicotungstic acid.
3.5. Near IR analysis
The minor loss around 640 ◦ C is attributed to the formation of
defective WO3 [25].
Near IR spectroscopy can be used to detect water content in
polyoxometalates and the hybrid molecular material by studying
3.4. UV–vis DRS analysis

UV–vis diffuse reflectance method is often employed to study

solids such as dispersed metal oxides, polyoxometalates, lay-
ered clays and hybrid materials by measuring d–d, f–d and
oxygen–metal ion charge transfer transitions [8,14,15,26,27]. The
polyoxometalates in their non-reduced form are generally char-
acterized by ligand to metal charge transfer (LMCT) bands which
appear in the UV region between 200 and 400 nm [8,26,27]. When
hybrid materials based on polyoxometalates are irradiated with UV
light, electrons are excited from the low-energy electronic states (O
2p orbitals) to the high-energy states (metal d orbitals). The energy
of the electronic transitions in polyoxometalates depends on the
size of the cluster and counter-cation [26]. The UV–vis DR spec-
tra of IL-SiWA hybrid material recorded using integrating sphere
are shown in Fig. 6. The electronic spectrum of silicotungstic acid
shows three absorption bands at 217, 259 and 330 nm due to LMCT
transitions in the Keggin units and there is no electronic transition
related to BmImBr ionic liquid in this region. The diffuse reflectance
spectrum of the IL-SiWA salt shows the same three transitions in
spectrum (c) in Fig. 6. However the position of the bands at 217
and 259 nm remains unchanged while the lowest energy absorp-
tion band at 330 nm has become sharp and blue shifted to lower
wavelength at 304 nm. This indicates again that there is an inter-
action between Keggin ions and BmIm cations. The blue shift is
attributed to large size of the BmIm cations substituted in place
of Br− ions. Due to the reaction with BmImBr, the Keggin anions
are also isolated and their polarizing power decreased causing the
blue shift (from 330 to 304 nm) in the hybrid molecular material Fig. 7. Near IR spectra of (a) H4 SiW12 O40 ·nH2 O, and (b) [MmIm]4 [SiW12 O40 ] hybrid
[26,27]. molecular material.
 T. Rajkumar, G. Ranga Rao / Materials Chemistry and Physics 112 (2008) 853–857
overtones and combination bands in the absorption region between
1100 and 2500 nm of water and structural hydroxyl groups [15,28].
Thus the near IR spectra of parent polyoxometalate and the IL-SiWA
hybrid materials are recorded by diffuse reflectance mode in the
range of 1200–2500 nm, which are shown in Fig. 7. The two promi-
nent bands observed at 1460 and 1961 nm in the near IR spectrum
show the presence of crystallization water in H4 SiW12 O40 ·nH2 O.
These bands are attributable to the first overtone of hydroxyl groups
(2O–H ), and combination bands corresponding to hydroxyl stretch-
ing and bending (2O–H + ıH2 O) vibrational modes, respectively, of
the water present in silicotungstic acid. The characteristic overtones
and combination bands due to H2 O are absent in the IL-SiWA hybrid
material (Fig. 7b). The IR peak at 1630 cm−1 due to water is also neg-
ligible in the IR spectrum of the hybrid molecular material (Fig. 1c).
This corroborates the elimination of water molecules associated
with SiWA when reacted with the BmIm counter cations forming
the molecular material.
4. Conclusions
The hybrid molecular material formed between 1-butyl 3-
methyl imidazolium bromide ionic liquid and silicotungstic acid
has been studied. IR spectrum shows the presence of both 1-butyl
3-methyl imidazolium cations and Keggin anions. The substitution
of bulky BmIm cation in place of Br− ion blue shifts the elec-
tronic transition from 330 to 304 nm and splits the imidazolium
ring C–H stretching modes which confirms the interaction between
the organic cations and inorganic Keggin anions in the material.
Near IR shows no water present in the hybrid molecular material
[BmIm]4 [SiW12 O40 ].
Acknowledgment
The DRDO research grant No. ERIP/ER/0300231/M/01/791 is
gratefully acknowledged.
857
References
[1] U.L. Štangar, N. Grošelj, B. Orel, Ph. Colomban, Chem. Mater. 12 (2000) 3745.
[2] C. Sanchez, G.J. de, A.A. Soler-Illia, F. Ribot, T. Lalot, C.R. Mayer, V. Cabuil, Chem.
Mater. 13 (2001) 3061.
[3] J.A.F. Gamelas, A.M.V. Cavaleiro, E. De, M. Gomes, M. Belsley, E. Herdtweck,
Polyhedron 21 (2002) 2537.
[4] L. Yang, H. Naruke, T. Yamase, Inorg. Chem. Commun. 6 (2003) 1020.
[5] M. Vasylyev, R. Popovitz-Biro, L.J.W. Shimon, R. Neumann, J. Mol. Struct. 656
(2003) 27.
[6] P. Gómez-Romero, K. Cuentas-Gallegos, M. Lira-Cantu, N. Casań-Pastor, J. Mater.
Sci. 40 (2005) 1423.
[7] M. Vazylyev, D. Sloboda-Rozner, A. Haimov, G. Maayan, R. Neumann, Top. Catal.
34 (2005) 93.
[8] T. He, J. Yao, Prog. Mater. Sci. 51 (2006) 810.
[9] Y. Huang, Q.Y. Pan, X.W. Dong, Z.X. Cheng, Mater. Chem. Phys. 97 (2006) 431.
[10] U.L. Štangar, N. Grošelj, B. Orel, A. Schmitz, Ph. Colomban, Solid State Ionics 145
(2001) 109.
[11] U.B. Mioč, M.R. Todorović, M. Davidović, Ph. Colomban, I. Holclajtner-Antunović,
Solid State Ionics 176 (2005) 3005.
[12] P.G. Rickert, M.R. Antonio, M.A. Firestone, K. Kubatko, T. Szreder, J.F. Wishart,
M.L. Dietz, Dalton Trans. (2007) 529.
[13] J. Kim, S. Hayashi, T. Mori, I. Honma, Electrochim. Acta 53 (2007) 963.
[14] G. Ranga Rao, T. Rajkumar, Catal. Lett. 120 (2008) 261.
[15] G. Ranga Rao, T. Rajkumar, J. Colloid Interface Sci. 324 (2008) 134.
[16] C.L. Hill, J. Mol. Catal. A: Chem. 262 (2007) 2.
[17] S. Liu, Z. Tang, Z. Wang, Z. Peng, E. Wang, S. Dong, J. Mater. Chem. 10 (2000)
2727.
[18] J.G. Huddleston, A.E. Visser, W.M. Reichert, H.D. Willauer, G.A. Broker, R.D.
Rogers, Green Chem. 3 (2001) 156.
[19] W. Wu, W. Li, B. Han, Z. Zhang, T. Jiang, Z. Liu, Green Chem. 7 (2005) 701.
[20] C.R. Deltcheff, M. Fournier, R. Franck, R. Thouvenot, Inorg. Chem. 22 (1983) 207.
[21] Y. Jeon, J. Sung, C. Seo, H. Lim, H. Cheong, M. Kang, B. Moon, Y. Ouchi, D. Kim, J.
Phys. Chem. B 112 (2008) 4735.
[22] A. Yokozeki, D.J. Kasprzak, M.B. Shiflett, Phys. Chem. Chem. Phys. 9 (2007) 5018.
[23] I. Jerman, V. Jovanovski, A. Šurca Vuk, S.B. Hočevar, M. Gaberšček, A. Jesih, B.
Orel, Electrochim. Acta 53 (2008) 2281.
[24] J.B. Moffat, Metal–Oxygen Clusters: The Surface and Catalystic Properties of
Heteropoly Oxometalates, Kluwer Academic/Plenum, New York, 2001.
[25] U.B. Mioč, R.Ž. Dimitrijević, M. Davidović, Z.P. Nedić, M.M. Mitrović, Ph. Colom-
ban, J. Mater. Sci. 29 (1994) 3705.
[26] M. Fournier, C. Louis, M. Che, P. Chaquin, D. Masure, J. Catal. 119 (1989) 400.
[27] G. Ranga Rao, T. Rajkumar, B. Varghese, Solid State Sci., Solid State Sci. (2008),
doi:10.1016/j.solidstatesciences.2008.05.017.
[28] J. Luypaert, D.L. Massart, Y.V. Heyden, Talanta 72 (2007) 865.