You are on page 1of 6

Mesomorphic Structures of Protonated Surfactant-Encapsulated Polyoxometalate

Complexes
Shengyan Yin, Wen Li, Jinfeng Wang, and Lixin Wu*
State Key Laboratory of Supramolecular Structure and Materials, Jilin UniVersity, Changchun 130012,
People’s Republic of China
ReceiVed: NoVember 16, 2007; In Final Form: December 28, 2007
Keggin-type heteropolyanions, H
3
PW
12
O
40
(HPW), Na
3
PW
12
O
40
(NaPW), H
4
SiW
12
O
40
(HSiW) and K
4
SiW
12
O
40
(KSiW), were encapsulated by a cationic surfactant, di[12-(4′-octyloxy-4-azophenyl)dodecyloxy]dimethylam
monium bromide (L), through the replacement of counterions. The resulting surfactant-encapsulated
polyoxometalate complexes were characterized by UV-vis, Raman, and NMR spectra in detail. The
measurement results indicated that some azobenzene groups of the surfactant were protonated in the complexes
HL/HPW (HL is the abbreviation of the protonated surfactant), HL/NaPW, and HL/HSiW during the process
of encapsulation, whereas the protonation was not observed in L/KSiW. The thermotropic liquid crystal
properties of these complexes were investigated by differential scanning calorimetry, polarized optical
microscopy and variable-temperature X-ray diffraction. Interestingly, different smectic mesophases were
observed between the protonated HL/HSiW and the non-protonated L/KSiW, which suggests that the
protonation of azobenzene groups in HL/HSiW plays a key role in the liquid crystalline organization. However,
protonated HL/HPW and HL/NaPW exhibit a similar smectic B phase to that of the de-protonated one, L/HPW.
A competitive balance between the phase separation and the volume minimization of surfactants was proposed
to explain the self-organized liquid crystal structures of these protonated and non-protonated complexes. To
the best of our knowledge, the present investigation provides a specific example for protonated hybrid materials
with stable liquid crystal properties.
Introduction
Design and synthesis of organic/inorganic hybrid liquid
crystals (LCs) have been one of the most active research areas
in both chemistry and material science over recent years because
the rich physical properties of inorganic components could be
properly introduced into LC systems.
1
The resulting hybrids
open up a new possibility to exploit promising functional LCs
with optical,
2
electronic,
3
and magnetic
4
properties. To date,
most studies have focused on metallomesogens, in which metal
ions are chemically integrated into organic ligands, presenting
a tunable fluidity of the whole complex in mesophase.
5
Very
recently, the fabrication of self-assembled organic/inorganic
nanohybrids, through combining the unique magnetic, electronic,
and optical properties of inorganic nanoparticles or clusters with
the soft nature of organic LCs, has given rise to a new
perspective in the area of hybrid LCs.
1b,6
The ordered liquid
crystalline assemblies are expected to possess synergistic
properties of the hybrids. For example, a gold nanoparticle
6c
and ferric oxide nanorod
6d
have previously been prepared with
a large length to diameter ratio, chemically modified with
mesomorphic organic molecules. These hybrids exhibit typical
LC properties. However, the reported instances are rare, and it
is desirable to design and prepare novel organic/inorganic hybrid
LCs using different strategies.
Polyoxometalates (PMs) are a kind of nanoscale polyanion
cluster possessing potential applications in electrochemistry,
proton conduction, magnetism, and optics.
7
The realization of
these various properties strongly depends on their molecular
properties including size, shape, charge number, chemical
structure, acidity and solubility, etc.
7a,8
To utilize these functions
in a processable way, many interesting methods have recently
been exploited,
9
and among them, the enwrapping PMs with
organic molecules through electrostatic interaction has proven
to be a highly effective route.
9c,10
The surfactant encapsulated
PM complexes (SECs) can be well-organized into various
matrices such as Langmuir-Blodgett film,
10a
casting film,
10b
multilayer vesicles,
10c
and polymers.
10d
However, more stable
and applicable matrices that can be further functionalized are
also in demand, especially those with precisely designed
nanostructures. Therefore, it is expected that the introduction
of PMs into organic LC systems could lead to novel hybrid LC
materials. In previous reports,
11a
we applied a mesomorphic
cationic surfactant to enwrap an elliptical PM and found that
the resulting SEC exhibits interesting thermotropic LC behavior.
The effects of the shape, charge number, and charge density of
the PM, as well as alkyl chain length and rigid group of
surfactants on the mesophase transitions have been studied in
detail.
11b,11c
Because PMs are common strong acids,
7
it is of
interest to know whether the intrinsic properties of PMs such
as acidity can also affect the LC behavior of the complexes.
On the basis of this motivation, we chose an acid-sensitive
surfactant and studied the thermal properties of the resulting
complexes in detail. It is expected that the mesophases could
be adjusted by the acidity of PMs, as in some cases, the tuning
of liquid crystalline structures by acid stimulation is important
for the functionalization of LCs.
12
Therefore, herein we introduce a representative investigation
concerning PM-containing hybrid LCs. Strong acidic Keggin- * To whom correspondence should be addressed. E-mail: wulx@jlu.edu.cn.
3983 J. Phys. Chem. B 2008, 112, 3983-3988
10.1021/jp710940y CCC: $40.75 © 2008 American Chemical Society
Published on Web 03/08/2008
type PMs, H
3
PW
12
O
40
(HPW) and H
4
SiW
12
O
40
(HSiW), and
their corresponding salts, Na
3
PW
12
O
40
(NaPW) and K
4
SiW
12
O
40
(KSiW), were encapsulated by surfactant L (Figure 1), giving
the SECs, HL/HPW (HL means the surfactant L is protonated),
HL/HSiW, HL/NaPW and L/KSiW, respectively. The structural
characterization confirmed the protonation of azobenzene groups
of surfactant L in HL/HPW, HL/HSiW, HL/NaPW, rather than
L/KSiW. From the study of the LC properties of these
complexes, we obtained a series of stable protonated LC
complexes, some of which displayed different LC characteristics
when compared to the neutral ones. To the best of our
knowledge, these stable and reversible mesomorphic transitions
based on protonated hybrid LC materials have not yet been
reported.
Experimental Section
Materials. HPW and HSiW were purchased from Sinopharm
Chemical Reagent Co., Ltd and used without further purification.
NaPW and KSiW were freshly prepared according to the
literature procedure.
13
Surfactant L, di[12-(4′-octyloxy-4-
azophenyl)dodecyloxy]dimethylammonium bromide (see Figure
1) was synthesized as reported previously.
11a
Preparation of Complexes. All SECs were synthesized
according to a modified procedure previously reported.
9c,10
Typically, a yellow chloroform solution of L was added
dropwise with stirring to the HPW aqueous solution under a
pH of 1.2. The initial molar ratio of L to HPW was controlled
at 2.8:1. Notably, the color of the organic phase turned red in
several minutes. After stirring continuously for 4 h at 35 °C,
the organic phase was separated and the red powder was
obtained by the evaporation of chloroform to dryness. The
product HL/HPW was further dried under vacuum until its
weight remained constant. According to a similar procedure,
other complexes were obtained from a mixture of L with other
PMs, corresponding to HL/NaPW, HL/HSiW, and L/KSiW. The
molar ratio of L to PMs was controlled at 3.6:1 for HSiW and
KSiW, and 2.8:1 for NaPW, approaching the charge ratio in
each of them. It is noted that PMs are sensitive to the pH value
of the solution, and the chemical structure of these PMs can
only be maintained under the definite pH region.
13b
The
preliminary pH values of the aqueous solutions in our case are
1.5, 1.1, and 4.3 for NaPW, HSiW, and KSiW, respectively, in
the definite pH region.
13b
With the exception of L/KSiW, whose
color is the same as L (yellow), the colors of the obtained
complexes are red for HL/HPW and HL/NaPW, and brown for
HL/HSiW. The de-protonated complex (L/HPW) of HL/HPW,
used in the control experiment, was obtained with HL/HPW as
follows: aqueous ammonia was added to the hot HL/HPW
chloroform solution (pH value of aqueous ammonia was
adjusted to ∼8) stepwise with stirring until the Raman spectrum
of the residue from the solution was the same as that of L, and
yellow solid was obtained by removing the solvent under
reduced pressure. All five complexes were characterized by IR
spectrum, elemental analysis, and TGA as follows.
HL/HPW: IR (KBr, cm
-1
) for HL/HPW: ν ) 3415, 2953,
2919, 2852, 1602, 1581, 1500, 1469, 1247, 1078, 975, 896, 809.
Anal. Calcd for HL/HPW (C
198
H
321
N
15
O
55
PBr
3
W
12
, 6268.50):
C, 37.94; H, 5.16; N, 3.35. Found: C, 37.71; H, 5.04; N, 3.25.
TGA suggests a mass loss of 0.833% in the range of 30-
150 °C arising from crystal water in HL/HPW, which matches
the formula: (L)
3
(HBr)
3
(PW
12
O
40
)(H
2
O)
3
(6268.50).
HL/NaPW: IR (KBr, cm
-1
) for HL/NaPW: ν ) 3452, 2952,
2921, 2850, 1602, 1581, 1500, 1467, 1247, 1079, 975, 894, 840,
809. Anal. Calcd for HL/NaPW (C
198
H
319
N
15
O
54
W
12
Br
3
P,
6250.49): C, 38.05; H, 5.14; N, 3.36. Found: C, 38.50; H, 5.19;
N, 3.03. TGA suggests a mass loss of 0.749% in the range of
30-150 °C arising from crystal water in HL/NaPW, which
matches the formula: (L)
3
(HBr)
3
(PW
12
O
40
)(H
2
O)
2
(6250.49).
L/HPW: IR (KBr, cm
-1
) for L/HPW: ν )3352, 2952, 2921,
2852, 1602, 1581, 1500, 1465, 1249, 1078, 975, 896, 838, 809.
Anal. Calcd for L/HPW (C
198
H
320
N
15
O
56
W
12
P, 6043.78): C,
39.35; H, 5.34; N, 3.48. Found: C, 39.66; H, 5.09; N, 3.11.
TGA suggests a mass loss of 1.13% in the range of 30-150 °C
arising from crystal water in L/HPW, which matches the
formula: (L)
3
(PW
12
O
40
)(H
2
O)
4
(6043.78).
Figure 1. Chemical structure of surfactant, coordination polyhedral representations of PMs and schematic drawings of complexes.
3984 J. Phys. Chem. B, Vol. 112, No. 13, 2008 Yin et al.
HL/HSiW: IR (KBr, cm
-1
) for HL/HSiW: ν ) 3352, 2952,
2921, 2852, 1602, 1581, 1498, 1471, 1317, 1247, 1106, 973,
919, 844, 794. Anal. Calcd for HL/HSiW (C
264
H
422
N
20
O
58
W
12
-
SiBr
2
, 7198.25): C, 44.05; H, 5.91; N, 3.89. Found: C, 44.25;
H, 5.99; N, 3.62. TGA suggests a mass loss of 0.506% in the
range of 30-150 °C arising from crystal water in HL/HSiW,
which matches the formula: (L)
4
(HBr)
2
(SiW
12
O
40
)(H
2
O)
2
(7198.25).
L/KSiW: IR (KBr, cm
-1
) for L/KSiW: ν ) 3450, 2952,
2921, 2852, 1602, 1581, 1500, 1471, 1247, 974, 920, 842, 792.
Anal. Calcd for L/KSiW (C
264
H
420
N
20
O
58
W
12
Si, 7036.42): C,
45.06; H, 6.02; N, 3.98. Found: C, 44.63; H, 6.44; N, 3.57.
TGA suggests a mass loss of 0.493% in the range of 30-
150 °C arising from crystal water in L/KSiW, just matching
the formula: (L)
4
(SiW
12
O
40
)(H
2
O)
2
(7036.42).
Measurements. Elemental analysis (C, H, N) was performed
on a Flash EA1112 from ThermoQuest Italia S.P.A. Infrared
spectra, from pressed KBr pellets, were carried out on a Bruker
IFS-66V Fourier transform infrared spectrometer equipped a
DTGS detector with a resolution of 4 cm
-1
.
1
H NMR spectra
were recorded on a Bruker UltraShield 500 MHz spectrometer
instrument using CDCl
3
as solvent and TMS as internal
reference. UV-visible spectra were recorded on a Shimadzu
UV-3100 spectrophotometer. Raman spectra were recorded on
a Renishaw Model 1000 or Jobin-Yvon T6400 spectrometer and
the 514.5-nm and 488-nm lines of argon ion laser were used as
excitation source, respectively. TGA was conducted with a
Perkin-Elmer TG/DTA-7 instrument and the heating rate was
10 K/min. The phase behaviors were measured using a polarized
optical microscope (POM) of Leica DMLP equipped with a
Mettler FP82HT hot stage and a Mettler FP90 central processor.
Differential scanning calorimetry (DSC) measurements were
completed on a Netzsch DSC 204 at a scanning rate of 5 K/min.
The samples were sealed in aluminum capsules in air, and the
holder atmosphere was dry nitrogen. Variable-temperature X-ray
diffraction (XRD) experiments were carried out on a Philips
PW 1700 X-ray diffractometer (using Cu KR
1
radiation of a
wavelength of 1.54 Å) with a TTK-HC temperature controller.
Results and Discussion
Characterization of Complexes. In this study, we employed
azobenzene-containing surfactant L to encapsulate Keggin-type
strong acids HPW and HSiW. Their corresponding salts, NaPW
and KSiW, were also encapsulated as a comparison. The
synthetic procedure was described in detail in the Experimental
Section. All of the as-prepared complexes were no longer soluble
in water, but were soluble in hot organic media such as
chloroform, suggesting that the surface of PMs had been
effectively modified by surfactant L. However, it should be
mentioned that the solubility of complexes in chloroform
solution is considerably poor, and their colors are different from
that of the surfactant L, with the exception of L/KSiW, which
evidently differs from those in our previous reports.
11a,11b
All
of the complexes are thermally stable in air according to the
identical IR spectra before and after the heating cycles.
Considering the color darkening of surfactant L in the com-
plexes, we propose some change having taken place during the
encapsulation process, as the color is unchangeable when we
perform the same procedure under the neutral conditions.
Spectroscopic measurements were used to examine the color
change from L to the complexes, and as a representative
example, UV-vis absorption spectra of L and HL/HPW are
shown in Figure 2. Both pure surfactant L and the de-protonated
complex L/HPW in their chloroform solution show a typical
absorption band at 360 nm, indicating that L and L/HPW exist
in their molecularly dispersed states.
14
In contrast, HL/HPW in
chloroform solution shows multiple absorption bands at 260,
360 nm and a broad absorption band in the range of 470-570
nm. On the basis of the pH dependence of UV-vis spectra of
azobenzene derivatives,
15
the broad band at 535 nm can be
clearly ascribed to the absorption of a protonated azobenzene
group, which is consistent with the color of the complex. Even
in this case, we still observed the normal band of the azobenzene
group appearing at 360 nm, suggesting the coexistence of neutral
and protonated species in the chloroform solution of HL/HPW.
Protonation of Azobenzene Groups. To further confirm the
protonation of azobenzene groups in the complex, Raman
spectra were employed to investigate the protonation of the
complexes (see Supporting Information), and the results show
that the protonation of azobenzene is present in HL/HPW, HL/
NaPW, and HL/HSiW, but not in L/KSiW and L/HPW.
Furthermore, elemental analysis and TGA measurements were
applied to quantitatively calculate the degree of protonation.
TGA curves in the range of 30-150 °C show the presence of
2-4 crystal water molecules in all of the complexes. The results
of elemental analysis and the TGA suggest that half of the
azobenzene groups have been protonated in HL/HPW and HL/
NaPW, and one-fourth in HL/HSiW, but none in L/KSiW and
L/HPW, as indicated in the molecular formula of these
complexes in the experimental section. Thus, the azobenzene
groups are not protonated completely in the complexes, which
is consistent with the observation of UV-vis and Raman
spectra.
As the encapsulation process is driven by electrostatic force
between L and PMs, there are two possible binding positions
of L: one is the cationic ammonium and the other is the
protonated azobenzene group. To identify the exact binding
position of protonated L with PMs, the complexes were
characterized by
1
H NMR spectra. As shown in Figure 3, the
proton chemical shift of surfactant L in the complex HL/HPW,
Figure 2. UV-vis spectra of HL/HPW (red), L/HPW (green) and L
(black) in chloroform solution.
Figure 3.
1
H NMR spectra of (a) surfactant L and (b) HL/HPW in
CDCl3, respectively.
Protonated Polyoxometalate Complexes J. Phys. Chem. B, Vol. 112, No. 13, 2008 3985
in contrast to that of surfactant L alone, shows the following
characteristic: (1) the proton peak of N-methyl (N
+
-CH
3
) has
significantly broadened and shifted to high field by 0.12 ppm;
(2) the proton signal of N-methylene (N
+
-CH
2
), which is a
triplet in pure L, becomes a considerably broadened singlet and
has shifted toward high field by 0.24 ppm; and (3) other peaks
maintain the same positions as pure L. The peak broadening
should result from the strong electrostatic interaction between
the L and PW cluster, which restricts the mobility of the
ammonium head group, as reported in the literature.
16
Consider-
ing that the chemical shift and peak width of the proton signal
are related to the local physical and chemical environment, we
suggest that it is the cationic ammonium headgroup of surfactant
L that binds to the negative charged cluster electrostatically,
even if some azobenzene groups of surfactant L are protonated.
Thus, to balance the charge on the protonated azobenzene group,
the corresponding counterion should be Br
-
, which comes from
L. To verify this assumption, an aqueous solution of AgNO
3
was added to the chloroform solution of HL/HPW, HL/NaPW,
and HL/HSiW. Upon addition, the color of the complexes
changed to yellow, as pure L, and was immediately accompanied
by a white precipitate, while a similar phenomenon was not
observed for the non-protonated L/KSiW, suggesting the pres-
ence of Br
-
as the counterion in the protonated samples.
Furthermore, we tried to remove hydrogen bromide from the
protonated azobenzene groups by carefully treating HL/HPW
with aqueous ammonia. Raman spectra confirmed that the
deprotonation of the azobenzene groups was successful (see
Supporting Information). IR spectra proved that the chemical
structure of the heteropolyanion cluster PW
12
O
40
3-
in the
protonated complex L/HPW was well-maintained and elemental
analysis of L/HPW shows that the molar ratio of surfactant L
to PW still retained 3:1. Those results suggest that the
PW
12
O
40
3-
cluster was not lost during the deprotonation process,
confirming the corresponding counterion around the protonated
azobenzene group is Br
-
, which comes from the surfactant.
Therefore, we propose that the hydrogen bromide, resulting from
counterions of both L and PMs, protonates the azobenzene
groups during the encapsulation process, as presented schemati-
cally in Figure 1.
Mesomorphic Behavior of Complexes. The thermal proper-
ties of the obtained complexes are investigated by DSC, POM,
and variable-temperature XRD. The phase transition tempera-
tures, enthalpies and assignments of the phase transitions for
all the complexes are summarized in Table 1.
From the DSC curves shown in Figure 4, protonated
complexes HL/HPW and HL/NaPW exhibit two phase transi-
tions similar to that of the deprotonated L/HPW, which can be
assigned to the changes from solid state to liquid crystal phase
and then to isotropic liquid, respectively. In the cases of HL/
HSiW and L/KSiW, both display rich transitions, especially for
the former, presenting more phase changes during the cooling
cycle from isotropic liquid.
The POM images of the complexes are shown in Figure 5.
A smectic B (SmB) phase is affirmed in the case of HL/HPW
and HL/NaPW (see Figure 5, parts a and b) because the observed
mosaic texture is a common characteristic of SmB phase,
particularly when it is obtained through directly decreasing
temperature from isotropic liquid.
17
The texture of L/HPW is
also indicative of SmB phase during the cooling process, which
is consistent with that of HL/HPW and HL/NaPW (see Figure
5c). In the case of HL/HSiW, the focal conic fan-shaped texture
at 201 °C (Figure 5d) and broken fan-shaped texture at 185 °C
(Figure 5e) are observed and can be attributed to Smectic A
(SmA) and Smectic C (SmC) phase, respectively. For L/KSiW,
the lancet texture, which appeared at 210 °C (Figure 5f),
suggests the formation of SmB phase. The different liquid
crystalline structures and phase transitions between HL/HSiW
and L/KSiW reveal that the protonation of azobenzene groups
plays a key role in the mesomorphic characterization of
complexes.
The LC behaviors of all the complexes were further inves-
tigated by a variable-temperature XRD measurement. The XRD
data supports the assignments of mesophases. As shown in
Figure 6, when HL/HPW and HL/NaPW slowly cool down from
their isotropic state, strong equidistant diffractions in the small-
angle region emerge along with a single sharp diffraction at 2θ
≈ 20° (Figure 6, parts a and b). The equidistant diffractions
correspond to a layered structure with the d-spacing of 4.01
and 4.06 nm calculated from the Bragg equation, respectively.
The appearance of a single sharp diffraction at the wide-angle
region for HL/HPW and HL/NaPW indicates the existence of
SmB phase.
18
Meanwhile, L/HPW shows an order smectic
layered structure with a layer spacing of 4.11 nm. On the basis
of our present results, we believe that the LC structure of the
protonated HL/HPW and HL/NaPW is the same as the de-
protonated L/HPW.
HL/HSiW features a disordered smectic phase corresponding
to a periodicity of 4.26 nm during its cooling run from the
isotropic state, as demonstrated by the presence of equidistant
diffractions in the small-angle region (Figure 6c) and a broad
and unconspicuous halo centered at 2θ ≈ 20° (Figure 6c, inset).
Considering the fan-shaped texture (Figure 5d), this phase is
identified as SmA phase. When the temperature decreases to
197 °C, another lamellar structure appears (Figure 6c). Com-
bining the unchanged diffusion peak in the wide-angle region
TABLE 1: Phase Transition Temperatures (°C), Enthalpies
(kJ/mol), and Assignments of the Phase Transitions for All
of the Complexes
a
first cooling second heating
sample transition T (°C) ∆H (kJ/mol) T (°C) ∆H (kJ/mol)
HL/HPW S-SmB 110 39.85 123 41.59
SmB-Iso 198 9.26 207 8.18
HL/NaPW S-SmB 110 34.94 121 34.50
SmB-Iso 196 9.85 206 6.47
L/HPW S-SmB 109 42.75 121 45.23
SmB-Iso 188 8.45 191 6.04
HL/HSiW S1-S2 109 29.87 111 41.55
S2-SmC 164 38.81 170 43.25
SmC-SmA 197 31.96
SmA-Iso 205 22.49 218 75.01
L/KSiW S1-S2 109 13.30 113 11.61
S2-S3 128 4.90 133 6.37
S3-SmB 169 47.12 175 49.46
SmB-Iso 210 58.24 220 75.29
a
(S, SmC, SmB, SmA, and Iso indicate solid, smectic C, smectic
B, smectic A, and isotropic phase, respectively.)
Figure 4. DSC curves of HL/HPW, HL/NaPW, L/HPW, HL/HSiW,
and L/KSiW on their (a) second heating and (b) first cooling cycles,
respectively.
3986 J. Phys. Chem. B, Vol. 112, No. 13, 2008 Yin et al.
(Figure 6c, inset) and the broken fan-shaped texture (Figure 5e),
the mesophase appearing at 185 °C is identified as SmC phase.
With decreasing temperature, the phase transition from SmC
to a solid state occurs at 164 °C, and the further cooling leads
to a solid-solid transition. Hence, the sequence of mesophases
for HL/HSiW in the cooling run can be ascribed to the process
of Iso-SmA-SmC-(Solid-2)-(Solid-1). In contrast to HL/HSiW,
L/KSiW displays a different mesophase sequence. When cooled
from isotropic liquid, the first lamellar LC phase with a layer
thickness of 5.04 nm forms, as illustrated in Figure 6d.
Combining the lancet texture (Figure 5f) at the same temperature
region and the single sharp diffraction at 2θ ≈ 20° (Figure 6d
inset), the mesophase can be attributed to SmB phase, and its
structure keeps until the temperature goes down to 169 °C, then
the phase changes to solid. The solid state can be definitely
assigned from the feature of multiple diffractions in the small-
angle region and a number of sharp peaks in the wide-angle
region in the diffraction pattern. The calculated layer spacings
for all the complexes are listed in Table 2. It is noted that the
layer spacing of L/KSiW is around 5 nm, whereas those of the
other complexes are around 4 nm. Combining the radius (0.52
nm) of Keggin-type PMs, and the ideal length of L with all
trans-conformation (3.45 nm, calculated by MM2 force field
method), the total thickness of a single complex should be
around 7.9 nm. The simulated molecular length is much larger
than the measured layer distance of all the complexes in their
mesophases, indicating the presence of a partially interdigitated
lamellar structure in L/KSiW and deeply interdigitated lamellar
structures in other complexes.
It is interesting to discuss the reason that HL/HSiW exhibits
two mesophases, SmA and SmC, whereas L/KSiW forms only
SmB phase. From a quick comparison of the chemical formulas,
we can find that the only difference between L/KSiW and HL/
HSiW is the presence of protonated azobenzene groups in HL/
HSiW. Therefore, it is reasonable that the protonation of
azobenzene groups leads to the different mesomorphic behaviors
in HL/HSiW when compared to with that of L/KSiW. Figure 1
shows that all the complexes possess a hydrophobic organic
shell and a hydrophilic inorganic core. These complexes are
likely to form lamellar structures due to the phase separation
of incompatible molecular components, the aggregation of
compatible units and the volume minimization of the surfactants.
Combining the present results and the crystal structures of some
similar complexes reported in the literature,
19
we propose that
the mesomorphic structures of the complexes correlate with the
matching extent of the volume between the hydrophilic PM
cluster and hydrophobic alkyl chains. When the volume ratio
of two components in the complex is well-proportioned, an
ordered smectic phase would be the predominant structure.
Otherwise a disordered smectic phase should be the preferential
structure. In our case, SmB phase of L/KSiW suggests that the
volume of the SiW cluster is well-proportioned to that of the
alkyl chains. And in HL/HSiW, as the presence of protonated
azobenzene group increases the incompatibility between the
surfactants, the volume of alkyl chains increases. The enlarged
volume of hydrophobic part makes the volume of SiW cluster
mismatch with that of alkyl chains, leading to disordered SmA
and SmC phases. The explanation can be supported by the
results of XRD. For L/KSiW with a tight packing of alkylchains,
Figure 5. POM images of (a) HL/HPW at 172 °C, (b) HL/NaPW at 164 °C, (c) L/HPW at 150 °C, (d) HL/HSiW at 201 °C, (e) HL/HSiW at 185
°C, and (f) L/KSiW at 194 °C, respectively, during the cooling process (magnification: ×400).
Figure 6. Variable-temperature X-ray diffraction patterns of (a) HL/
HPW, (b) HL/NaPW, (c) HL/HSiW, and (d) L/KSiW, respectively.
(Inset: diffractions in wide-angle region).
TABLE 2: Summary of Layer Spacings (d) for All of the
Complexes Calculated from X-ray Diffractions
layer spacing d (nm)
sample SmA SmB SmC solid 3 solid 2 solid 1
HL/HPW 4.01 3.69
HL/NaPW 4.06 3.64
L/HPW 4.11 3.72
HL/HSiW 4.26 4.27 4.17 4.04
L/KSiW 5.04 4.81 4.45 4.29
Protonated Polyoxometalate Complexes J. Phys. Chem. B, Vol. 112, No. 13, 2008 3987
it shows a bit larger layer thickness due to the partially
interdigitated layer structure, whereas for HL/HSiW with relaxed
alkyl chains, it exhibits a deeply interdigitated structure. This
implies that the volume of alkyl chains in HL/HSiW is larger
than that of L/KSiW. As for HL/HPW, in spite of the presence
of protonated azobenzene groups, the complex still exhibits SmB
phase. Comparing HL/HPW with HL/HSiW, the following
characteristics are obvious: (1) SiW and PW are both Keggin
type clusters and have the same size and shape; (2) both HL/
HPW and HL/HSiW show deeply interdigitated layers and the
layer spacings of HL/HPW and HL/HSiW are almost the same;
(3) the unique difference is in the amount of surfactant molecules
in HL/HPW and HL/HSiW. According to the results of
elemental analysis and TGA, the surfactants around PW are less
than those covered on SiW, providing more space for the
interdigitation of alkyl chains. Though the deeply interdigitated
lamellar structures are present in HL/HPW, the volume of the
PW cluster is still well-proportioned to that of the alkyl chains,
thus the SmB phase is well maintained. The current result
implies that the protonation of azobenzene groups can be used
to tune the LC mesophase of the complexes by the appropriate
choice of PMs.
Conclusions
In this paper, we report mesomorphic structures of a kind of
novel hybrid LC material with protonated mesogenic groups.
Azobenzene-containing surfactant encapsulated polyoxometalate
complexes, HL/HPW, HL/HSiW, HL/NaPW, and L/KSiW, have
been prepared. Among them, HL/HPW, HL/HSiW, and HL/
NaPW are protonated while L/KSiW is non-protonated. The
intrinsic acidity of the applied PMs is considered to be the main
reason for the protonation of these complexes. Although the
protonation creates additional positively charged sites in the
surfactant molecule, the bonding position between L and PMs
is still at the ammonium head group definitely. The bromic anion
derived from ion replacement binds to the azobenzene group
as a counterion in these protonated complexes. The protonated
complex HL/HSiW reveals SmA and SmC phases, while the
corresponding non-protonated complex L/KSiW exhibits only
SmB phase. The protonated complexes HL/HPW and HL/NaPW
self-organize into SmB phase, similar to that of non-protonated
L/HPW. The competitive balance between the phase separation
and the volume minimization of surfactants is supposed to play
an important role and could be employed to explain the different
self-organized LC structures of these protonated and non-
protonated complexes. Both the number of surfactants on the
surface of PMs and the protonation of the azobenzene group
make the LC phase of SECs become diversified. This allows
potential applications in developing acidity stimulation-response
hybrid LC materials.
Acknowledgment. The authors acknowledge the financial
support from National Basic Research Program (2007CB808003),
National Natural Science Foundation of China (20473032,
20574030), PCSIRT of Ministry of Education of China
(IRT0422), and Open Project of State Key Laboratory of
Polymer Physics and Chemistry of CAS.
Supporting Information Available: Raman spectra of the
complexes, assignments of characteristic Raman shift, and
additional references. This material is available free of charge
via the Internet at http://pubs.acs.org.
References and Notes
(1) (a) Tschierske, C. J. Mater. Chem. 2001, 11, 2647. (b) Saez, I. M.;
Goodby, J. W. J. Mater. Chem. 2005, 15, 26. (c) Gin, D. L.; Lu, X.; Nemade,
P. R.; Pecinovsky, C. S.; Xu, Y.; Zhou, M. AdV. Funct. Mater. 2006, 16,
865.
(2) (a) Guillet, E.; Imbert, D.; Scopelliti, R.; Bu¨nzli, J.-C. G. Chem.
Mater. 2004, 16, 4063. (b) Bayon, R.; Coco, S.; Espinet, P. Chem. Eur. J.
2005, 11, 1079. (c) Pucci, D.; Barberio, G.; Bellusci, A.; Crispini, A.;
Donnio, B.; Giorgini, L.; Ghedini, M.; Deda, M. L.; Szerb, E. I. Chem.
Eur. J. 2006, 12, 6738.
(3) Matsuo, Y.; Muramatsu, A.; Kamikawa, Y.; Kato, T.; Nakamura,
E. J. Am. Chem. Soc. 2006, 128, 9586.
(4) Barbera´, J.; Gime´nez, R.; Marcos, M.; Serrano, J. L.; Alonso, P.
J.; Martı ´nez, J. I. Chem. Mater. 2003, 15, 958.
(5) (a) Hudson, S. A.; Maitilis, P. M. Chem. ReV. 1993, 93, 861. (b)
Metallomesogens: Synthesis and Applications; Serrano, J. L., Ed.; VCH:
Weinheim 1996. (c) Binnemans, K.; Go¨rller-Walrand, C. Chem. ReV. 2002,
102, 2303. (d) Donnio, B.; Guillon, D.; Deschenaux, R.; Bruce, D. W. In
ComprehensiVe Coordination Chemistry; McCleverty, J. A., Meyer, T. J.,
Eds.; Elsevier: Oxford, 2003; Vol. 7, pp 357-627.
(6) (a) Kanayama, N.; Tsutsumi, O.; Kanazawa, A.; Ikeda, T. Chem.
Commun. 2001, 2640. (b) Kanie, K.; Sugimoto, T. J. Am. Chem. Soc. 2003,
125, 10518. (c) Cseh, L.; Mehl, G. H. J. Am. Chem. Soc. 2006, 128, 13376.
(d) Kanie, K.; Muramatsu, A. J. Am. Chem. Soc. 2005, 127, 11578. (e)
Cseh, L.; Mehl, G. H.; J. Mater. Chem. 2007, 311.
(7) (a) Pope, M. T.; Mu¨ller, A. Angew. Chem., Int. Ed. 1991, 30, 34.
(b) Hill, C. L. Chem. ReV. 1998, 98, 1. The entire issue is devoted to
polyoxometalates. (c) Pope, M. T.; Mu¨ller, A. Polyoxometalate Chemistry
from Topology Via Self-Assembly to Application; Kluwer Academic Publish-
ers: Dordrecht, The Netherlands, 2001.
(8) (a) Pope, M. T. Heteropoly and Isopoly Oxometalates; Springer-
Verlag: Berlin, 1983. (b) Pope, M. T.; Mu¨ller, A. Polyoxometalates: from
PlatonicSolids to Anti-retroViral ActiVity; KluwerAcademic Publishers:
Norwell, MA, 1994.
(9) (a) Volkmer, D.; Du Chesne, A.; Kurth, D. G.; Schnablegger, H.;
Lehmann, P.; Koop, M. J.; Mu¨ller, A. J. Am. Chem. Soc. 2000, 122, 1995.
(b) Liu, S.; Kurth, D. G.; Bredenko¨tter, B.; Volkmer, D. J. Am. Chem. Soc.
2002, 124, 12279. (c) Errington, R. J.; Petkar, S. S.; Horrocks, B. R.;
Houlton, A.; Lie, L. H.; Patole, S. N. Angew. Chem., Int. Ed. 2005, 44,
1254.
(10) (a) Kurth, D. G.; Lehmann, P.; Volkmer, D.; Mu¨ller, A.; Schwahn,
D. J. Chem. Soc. Dalton Trans. 2000, 3989 (b) Bu, W.; Fan, H.; Wu, L.;
Hou, X.; Hu, C.; Zhang, G.; Zhang, X. Langmuir 2002, 18, 6398. (c) Li,
H.; Sun, H.; Qi, W.; Xu, M.; Wu, L. Angew. Chem., Int. Ed. 2007, 46,
1300. (d) Li, H.; Qi, W.; Li, W.; Sun, H.; Bu, W.; Wu, L. AdV. Mater.
2005, 17, 2688.
(11) (a) Li, W.; Bu, W.; Li, H.; Wu, L.; Li, M. Chem. Comm. 2005,
3785. (b) Li, W.; Yin, S.; Wu, Y.; Wu, L. J. Phys. Chem. B 2006, 110,
16961. (c) Li, W.; Yin, S.; Wang, J.; Wu, L. Chem. Mater. 2008, 20,
514.
(12) (a) Pecinovsky, C. S.; Nicodemus, G. D.; Gin, D. L. Chem. Mater.
2005, 17, 4889. (b) Tan, B.; Yoshio, M.; Ichikawa, T.; Mukai, T.; Ohno,
H.; Kato, T. Chem. Comm. 2006, 4703.
(13) (a) Cao, H. Handbook of Inorganic Chemistry Synthesis: Beijing
Science Press: Beijing, 1988; Vol. 3, pp 409, 565. (b) Moffat, J. B. Metal-
Oxygen Clusters: The Surface and Catalytic Properties of Heteropoly
Oxometalates; Kluwer Academic/Plenum Publishers: New York, 2001; pp
62-68.
(14) (a) Kuiper, J. M.; Engberts, J. B. F. N. Langmuir 2004, 20, 1152.
(b) Shimomura, M.; Kunitake, T. J. Am. Chem. Soc. 1987, 109,
5175.
(15) (a) Tian, Y.; Isono, N.; Kawai, T.; Umemura, J.; Takenaka, T.
Langmuir 1988, 4, 693. (b) Tian, Y.; Umemura, J.; Takenaka, T. Langmuir
1988, 4, 1064. (c) Nihei, M.; Kurihara, M.; Mizutani, J.; Nishihara, H. J.
Am. Chem. Soc. 2003, 125, 2964.
(16) (a) Kurth, D. G.; Lehmann, P.; Volkmer, D.; Mu¨ller, A.; Schwahn,
D. J. Chem. Soc. Dalton Trans. 2000, 3989. (b) Polarz, S.; Smarsly, B.;
Antonietti, M. Chem. Phys. Chem. 2001, 2, 457.
(17) (a) Xu, J.; Toh, C. L.; Liu, X.; Wang, S.; He, C.; Lu, X.
Macromolecules 2005, 38, 1684. (b) Dierking, I. Textrue of Liquid Crystals;
Wiley-VCH: Weinheim, Germany, 2003; p 135, and references
therein.
(18) (a) de Vries, A. Chem. Phys. Lett. 1974, 28, 252. (b) Krigbaum,
W. R.; Watanabe, J.; Ishikawa, T. Macromolecules 1983, 16, 1271. (c) Hsu,
C.; Lin, J.; Chou, L.; Hsiue, G. Macromolecules 1992, 25, 7126. (d) Xu,
J.; Toh, C. L.; Liu, X.; Wang, S.; He, C.; Lu, X. Macromolecules 2005,
38, 1684.
(19) Nyman, M.; Ingersoll, D.; Singh, S.; Bonhomme, F.; Alam, T.;
Brinker, C.; Rodriguez, M. Chem. Mater. 2005, 17, 2885.
3988 J. Phys. Chem. B, Vol. 112, No. 13, 2008 Yin et al.