Hydrazide-based organogels and liquid crystals with columnar order

Article abstract of DOI:10.1039/b614444f

We report on the synthesis and self-assembly of a new series of compounds containing a hydrazide unit in the rigid core and three alkoxy chains with varying lengths. The compounds N-(3,4,5-cetyloxybenzoyl)-N′-(4′- nitrobenzoyl) hydrazine (C16) and N-(3,4,

Full text of DOI:10.1039/b614444f

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www.rsc.org/njc | New Journal of Chemistry
Hydrazide-based organogels and liquid crystals with columnar order
Binglian Bai, Haitao Wang, Hong Xin, Fenglong Zhang, Beihong Long,
Xiaobing Zhang, Songnan Qu and Min Li*
Received (in Montpellier, France) 4th October 2006, Accepted 5th January 2007
First published as an Advance Article on the web 2nd February 2007
DOI: 10.1039/b614444f
We report on the synthesis and self-assembly of a new series of compounds containing a
hydrazide unit in the rigid core and three alkoxy chains with varying lengths. The compounds
N-(3,4,5-cetyloxybenzoyl)-N0-(40-nitrobenzoyl) hydrazine (C16) and N-(3,4,5-dodecyloxybenzoyl)-
N0-(40-nitrobenzoyl) hydrazine (C12) exhibited stable columnar phase and strong gelation ability
in several apolar organic solvents. The columnar structure was found both in the liquid crystalline
state and in the xerogels by wide-angle X-ray diffraction analysis. SEM and TEM images revealed
that the molecules self-assembled into twist fibrous aggregates in the xerogels. FT-IR and
1H NMR studies confirmed that the intermolecular hydrogen bonding and van der Waals
interactions were the major driving force for the formation of self-assembling both the liquid
crystals and gels processes. Further detailed analysis of their aggregation modes were conducted
by FT-IR spectroscopy and X-ray diffraction measurement.
derivatives; for example, linear N,N0-bis(4-alkoxybenzoyl)
hydrazines exhibit a cubic phase,13,14 while monomeric,
Introduction
Self-assembling processes are common throughout nature and
technology.1 Self-assembled materials, such as liquid crystals
dimeric and polymeric N,N0-bis[3,4,5-tris(alkoxybenzoyl)] hy-
drazines formed a columnar phase,14,15 little attention has
and organogels, formed by non-covalent bonding have
been paid to organogels based on dihydrazide derivatives.
attracted much attention because they are good candidates
Recently, our groups have demonstrated that intermolecular
for the next generation of materials, for which dynamic
hydrogen bonding was still interacting in the SmA phase and
function, environmental benignity, and low energy processing
played important roles in stabilizing the mesophase and
organogels of dihydrazide derivatives.16–18
are required.
The liquid crystalline state represents fascinating states of
In this context, a series of low molecular compounds con-
soft matter combining order and mobility on a molecular and
taining of dihydrazide groups were designed. Notably, the
supra-molecular level.2,3 The organogels are a class of nano-
compounds showed thermotropic mesophase and strong gela-
structured materials composed of a self-assembled superstruc-
tion ability in organic solvents, and the twist fibers were
ture of the low molecular weight organogelators through
observed, which was due to the steric hindrance and hydrogen
specific intermolecular interactions and a large volume of
bonding interactions between the dihydrazide groups co-
organic liquid immobilized therein.4 In order for these self-
operating with the packing of the alkoxy chains instead of
assemblies to form, it is important to control the intermole-
any chiral groups. Both the length of the alkyl chains and the
cular interactions in such a way that they enable the formation
existence of hydrogen bonding can strongly influence the
of liquid crystals and organogels, but avoid transformation to
properties of the mesophase and organogels.
a crystalline state. It is relatively rare to find low molecular
rod-like compounds capable of both gelling solvents and
Results and discussion
exhibiting thermotropic mesomorphic behaviors, whereas this
is the usual case for some wedge-shape or disk-like molecules.5
Synthesis of compounds
Among those non-covalent interactions, hydrogen bonding
The compounds were synthesized according to the route
was most commonly used to direct the self-assembling process.
shown in Scheme 1. 4-Nitrobenzoyl chloride was reacted with
Many low molecular weight organogels, containing, for
example, amide,6–10 urea,9–11 and hydrazide12 groups have
3,4,5-alkoxy-benzoylhydrazine in THF, yielding the products
of compounds Cn. The molecular structure of Cn was con-
been reported to show strong gelation ability in organic
firmed by the disappearance of the protons of the –NH2 group
solvents, and where the intermolecular hydrogen bonding
at about 4.4 ppm from 3,4,5-alkoxy-benzoylhydrazine and the
was considered to be the driving force. Although it has been
appearance of two different ones from the –NH groups at
known that intermolecular hydrogen bonding played an
upwards of 9.0 ppm. In order to investigate the hydrogen
important role in mesophase formation in the dihydrazide
bonding effect on the behaviour of liquid crystals and gel
ability, compound Me–C16 was prepared in which the hydro-
Key Laboratory for Automobile Materials(JLU), Ministry of
gens of dihydrazide group of C16 were substituented by
Education, Institute of Materials Science and Engineering, Jilin
methyl. The disappearance of N–H stretching vibrations
(n(N–H)) of C16 at 3187 cmꢀ1 clearly indicated the proposed
University, Changchun, 130012, P. R. China. E-mail:
minli@mail.jlu.edu.cn
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Scheme 1 The synthesis of compound Cn and Me–C16.
molecular structure of Me–C16. Detailed characterization
data for Cn and Me–C16 were given in experimental section.
Table 1 presented the assignments of infrared frequencies for
C12.16,21 The presence of –N–H stretching vibrations at
3193 cmꢀ1 (the absence of free n(N–H), which exhibits a
relatively sharp band at around 3400 cmꢀ1), intense absorp-
tion of amide I at 1662, 1594 cmꢀ1 clearly indicated that
almost all the –NH groups are associated with –CQO groups
via –CQOꢂ ꢂ ꢂH–N– hydrogen bonding.16,22
Intermolecular hydrogen bonding in Cn
In order to explore the hydrogen bonding motif, temperature
dependent FT-IR and concentration dependent 1H NMR
spectroscopic experiments were performed. In the 1H NMR
dilution studies, the amide protons of compounds Cn showed
a strong concentration dependence, for example, reducing the
concentration of C3 in CDCl3 from 104 to 0.033 mM causes
both NH-1 (near to nitro phenyl, Dd = 1.405 ppm) and NH-2
(near to alkoxy phenyl, Dd = 0.841 ppm) to shift upfield
remarkably (Fig. 1), which strongly indicates that both the two
amide protons in C3 participate in forming supramolecules via
cooperative double intermolecular hydrogen bonds.19 The
data from the diluting experiment fit well with the calculated
curves using the simplest (isodesmic) model (i.e., Kn = K, for
n Z 2),20 giving association constants (K) of 81.3 Mꢀ1 and
62.1 Mꢀ1 based on NH-1 and NH-2, respectively.
Moreover, these conclusions were supported by the fact that
the n(N–H) became weaker and shifted to higher frequencies
as well as the hydrogen bonding length23,24 of –CQOꢂ ꢂ ꢂH–N–
increasing upon heating, as shown in Fig. 2. The wavenumbers
of n(N–H) of C12 are at around 3193, 3216 and 3277 cmꢀ1 in
the crystalline state, Col phase and isotropic phase, respec-
tively, and apart from the main band at 3277 cmꢀ1, a shoulder
peak appeared at 3395 cmꢀ1 (free n(N–H)) in isotropic phase.
The calculated hydrogen bonding length of –CQOꢂ ꢂ ꢂH–N–
was 2.00 A at 30 1C, which is in the range of moderate
hydrogen bonds.24 It increased slowly with temperature within
the crystalline and columnar phase, while jumped to 2.18 A,
which indicated a weak hydrogen bonding in the isotropic
state.24 The integral intensity of n(N–H) increases strongly
upon formation of a hydrogen bond, and this is often taken as
Intermolecular hydrogen bonding in Cn was further
confirmed by temperature dependent FT-IR spectroscopy.
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transitional temperatures and associated enthalpies were sum-
marized in Table 2. No mesophase was observed in C3,
whereas the compounds C12 and C16 showed enantiotropic
columnar liquid crystalline phases. The melting points
decreases and the mesophase appears with the elongating
terminal chains. This may be explained as the elongation of
the terminal chains increased the micro-segregation effect by
enhancing the incompatibility between the hydrogen bonded
rigid aromatic rings and flexible alkoxy chains. On the other
hand, melting point of Me–C16 decreased nearly 15 1C
compared to that of C16 and no mesomorphic phase was
observed in Me–C16.
Compound C12 exhibits a ribbon-like texture coexistence
with a spherulitic one, while no characteristic texture was
observed for C16 under POM. X-ray diffraction measurements
of Cn have been performed across a wide temperature range in
their mesophases. The X-ray diffraction pattern of C12, as
shown in Fig. 4a, taken at 130 1C revealed a hexagonal
columnar structure with the column diameters of 31.45
(100), 18.17 (110), 15.62 A (200) in the low angle region with
a reciprocal spacing ratio of 1 : 1/O3 : 1/2. Table 3 lists the
d-spacings (A) and the corresponding Miller indices shown in
the graph in Fig. 4a. The estimated all-trans molecular length
of the most extended conformation of C12 is 28.83 A,
obtained by the MM2 method, and the diameter of a column
of the columnar phase is 36.32 A. The number of molecules
within one disk was calculated to be four,4b,25 assuming that
the density of C12 is 1 g cmꢀ3. Thus, the alkoxy chains can
effectively surround the polar (nitro) part and a circular shape
of the columns can be assumed and the four molecules
distribute the disk averagely. Likewise, X-ray diffraction
measurements of C16 was performed and displayed in
Fig. 4b and Table 3. The calculated spacings, shown in
Table 3, were obtained after fitting the experimentally ob-
served spacings to a monoclinic unit cell, where the best fit for
the data was obtained for a rectangular cell with dimensions
a = 110.62 A and b = 45.05 A. Thus, the compound C16
shows a rectangular columnar cell. The calculated molecular
length of C16 is 34.75 A, obtained by the MM2 method, and
the value of a, b of a column of the columnar phase is in
reasonable agreement with the calculated molecular length.
The number of molecules within a slice was calculated to be
six,4b,25 assuming that the density of C16 is 1 g cmꢀ3, the
packing model for the rectangular column is shown in Fig. 4c.
Fig. 1 The chemical shifts of amide protons for C3 vs. concentrations
in CDCl3 (NH-1: near to nitro phenyl, NH-2: near to alkoxy phenyl).
a more reliable indicator of hydrogen bond formation.24 The
integral intensity of the n(N–H) (Fig. 2b) of C12 decreased
slowly near the melting temperature, and it decreased drasti-
cally upon isotropic transition (Ti) and remained more or less
constant above Ti. The reason for this decrease in the intensity
of n(N–H) can be ascribed to the increased mobility of the
system. In a word, changes of both the intensity and wave-
number of n(N–H) and the increase of hydrogen bonding
length of –CQOꢂ ꢂ ꢂH–N– with temperature strongly indicated
that the presence of the intermolecular hydrogen bonding in
the Col phase of C12.14 Furthermore, this conclusion was also
supported by the fact that the –CQO stretching vibrations
shifted from 1662, 1594 cmꢀ1 to 1691, 1646 cmꢀ1, and a sharp
decrease of the absorption intensity at columnar–isotropic
transition (Fig. 3). All these demonstrated that there were
moderate hydrogen bonding between –CQO and –N–H in the
liquid crystalline state of Cn, and the intermolecular hydrogen
bonding was very important for the stabilization of the
columnar phase.
Thermotropic mesomorphic behaviour of the Cn and Me–C16
The thermotropic properties of Cn and Me–C16 were investi-
gated by a combination of DSC, POM and XRD. Their
Table 1 Assignments of infrared frequencies for C12 at room
temperature
Gelation
Interestingly, only C12 and C16 with long alkyl chains and
intermolecular hydrogen bonding showed strong gelation
ability in organic solvents such as benzene, 1,2-dichloroethane
et al. No gelation is observed for compounds C3 and Me–C16
in which the hydrogen of dihydrazide group of C16 were
replaced by methyl groups. Table 4 lists the minimum gelation
concentrations (MGC) of C12 and C16 in organic solvents. It
can be seen that C16 gelator is more efficient than C12. Fig. 5
shows the melting temperature (Tm) of benzene gel based on
C12 as a function of concentration. Tms were determined by
the ‘‘falling drop’’ method.26 The Tm increases from 27 1C to
41 1C as the concentration of C12 increase from 1.02 wt% to
4.90 wt%.
IR frequencies (cmꢀ1
)
Assignments
3193
2956
2922
2871
2851
1662, 1594
1610, 1581, 1566
1492
1525, 1342
1466, 1456
1229
n(N–H)
n
n
as(CH3)
as(CH2)
ns(CH3)
ns(CH2)
Amide I, n(CQO)
n(CQC) of phenyl ring
Amide II, III, nC–N + dN–H
nas, ns(NO2)
d(CH2)
n(Ar–O)
n(C–O)
(CH2)n rocking modes, n Z 4
1123
719
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Fig. 2 (a) The temperature dependent FT-IR spectra of C12 at an interval of 10 1C in the range of 3500–2800 cmꢀ1, the plot of (b) n(N–H)
wavenumbers and hydrogen bond length of –CQOꢂ ꢂ ꢂH–N– of C12 vs. temperature and (c) integral intensity of n(N–H) of C12 vs. temperature.
Self-assembled behaviours of the organogels
from toluene and 1,2-dichloroethane exhibited the similar
SEM images to that from benzene. The self-assembled twisted
fibers with the diameter of ca. 100 nm of C16 were also clearly
observed by the TEM even in the homogeneous fluid benzene
solution (0.13 wt%) (Fig. 6c and d), but the twist can only be
seen on a few fibers, many straight fibers were observed. It is
possible that the steric hindrance decreases and the free energy
increases in the homogeneous fluid solution.
In order to investigate the aggregation morphology of these
organogels, the xerogels were prepared and subjected to the
SEM observation. Fig. 6a showed the SEM image of C12
xerogels from benzene that revealed a network structure
composed of twist bundles of fibers. The diameter of each
bundle was found to be 300–400 nm, juxtaposed and inter-
twined by several long slender aggregations with the diameter
of ca. 150–200 nm. While the SEM image of a benzene gel of
C16 reveals a number of bundles of fibers, similar to that of
C12 with the diameter of ca. 100 nm. Xerogels of C12 and C16
To reveal the packing conformations of the molecules in gel
phase, X-ray diffraction was measured. The XRD pattern (as
seen in Fig. 7a) of benzene xerogels (2.802 wt%) of C12
consists of seven peaks at 55.85 (200), 30.32 (110), 14.28
(420), 9.46 (530), 7.22 (440), 5.71 (550), 4.20 (001) A, which
correspond to a rectangular columnar packing (a = 111.70 A,
b = 31.50 A). Based on these observations, we propose that
columns assemblies with rectangular lattice parameters to
Table 2 Phase behaviour of compounds of Cn and Me–C16a
Compound
T/1C(DH/kJ molꢀ1
)
C3
Cr 177.9 (37.23) I
C12
C16
Me–C16
a
Cr 109.0 (13.70) Colh 142.0 (37.19) I
Cr 111.2 (40.61) Colr 135.2 (45.21) I
Cr 95.8 (99.11) I
The transitional temperatures and enthalpies (in parentheses) were
determined by DSC (10 1C/min). Cr indicates a crystalline phase, Colh
indicates a hexagonal columnar phase, Colr indicates a rectangular
columnar phase and I indicates an isotropic phase.
Fig. 3 The temperature dependent FT-IR spectra of C12 at an
interval of 10 1C in the range of 1750–1450 cmꢀ1
.
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Fig. 4 XRD of (a) C12 at 130 1C, (b) C16 at 125 1C and (c) the packing model for the rectangular column of C16.
make elementary fibers. Each bundle with the diameter of
300–400 nm can be thought to consist of 30–40 elementary
fibers, which are visible by SEM. When the length of the
alkoxy chains increased (C16), the self-assembled structures
changed from rectangular to hexagonal packing with the
spacings of 56.56 (100), 32.32 (110), 28.01 A (200) in the
small-angle regions, with a reciprocal spacing ratio of 1 : 1/
O3 : 1/2 (Fig. 7b). The diameter of a column of the hexagonal
packing is 65.31 A, namely the diameter of elementary fibers.
Each bundle with the diameter of 100 nm can be thought to
consist of ca. 15 elementary fibers, as shown in Fig. 6b.
The formation of elongated fiber-like aggregates indicates
that the self-assembly of Cn is driven by strong directional
intermolecular interactions. To ascertain whether hydrogen
bonding plays a role in the gelation process, infrared spectrum
of the C12 organogel was examined. The presence of –N–H
stretching vibrations at 3184 cmꢀ1 and –CQO stretching
vibrations at 1665 cmꢀ1 and 1593 cmꢀ1 for C12 in the gel
state unambiguously suggested that the hydrogen bonding
through –N–Hꢂ ꢂ ꢂOQC– exists in the gelation process. The
hydrogen bonding was confirmed to be the intermolecular one
through the 1H NMR studies (vide supra), and it is confirmed
that the compound Me–C16 did not gel organic solvent. These
results strongly indicated that –N–H groups were exclusively
involved in intermolecular hydrogen bonding19,27 and play an
important role in the gelation process. Furthermore, the
absorption bands of the antisymmetric (nas) and symmetric
(ns) –CH2– stretching vibrational modes of C12 are observed
Table 3 XRD data for the liquid crystalline phases of C12 and C16
d,
(obsd)/A (calcd)/A index
d,
Miller
Compound T/1C Phase
C12
130
Colh a = 36.32 31.45
31.45
18.16
15.73
—
10.48
9.08
8.72
7.86
6.29
4.54
—
55.31
41.72
27.56
20.85
18.37
13.90
12.41
—
100
110
200
—
18.17
15.62
14.53
10.72
8.97
8.30
7.79
6.23
4.66
300
220
310
400
500
440
001
200
110
400
220
600
330
530
001
Table 4 Minimum gel concentrations (MGC) of C12 and C16
4.35
C16
125
Colr
a = 110.62
b = 45.05
55.31
41.72
27.76
20.68
18.17
13.64
12.58
4.03
MGC (wt%)
C16
C12
Solvent
Benzene
Toluene
0.280
0.305
0.686
0.590
1,2-dichloroethane
Chloroform
0.105
Solution
0.173
Solution
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of the alkyl chains due to the strong organization of the alkyl
groups via a van der Waals interaction.28 Consequently, the
driving forces for organogelation followed by entanglement of
the self-assembled nanofibers are mainly hydrogen bonding
and van der Waals interactions.
Combining the above results from the FT-IR and XRD
data, the reason for the generation of the twisted fibers from
achiral molecules could be deduced. In the process of gelation,
the hydrogen bonding, p–p and the van der Waals interactions
arranged the molecules to aggregate into fibrous structure.
Combination the steric hindrance and hydrogen bonding
interactions between the dihydrazide groups effects some
degree rotation of the phenyl. Therefore the disks would be
aggregated in a propeller-like conformation, which might
provide an induction for the formation of twist. And the
slightly disordered packing of the alkoxy chains (the absence
of sharp peaks in the wide-angle region for XRD data)
induced the formation of twist propeller-like conformations
and gave macroscopic twisted structures. All of above results
indicate that both the steric hindrance and hydrogen bonding
interactions between the dihydrazide groups as well as the
packing of the alkoxy chains are critically important to form
the twist fibers in this series of compounds.
Fig. 5 Concentration-dependent melting temperature of gels based
on C12 in benzene.
at 2924 cmꢀ1 (nas –CH), 2854 cmꢀ1 (ns –CH) in CHCl3
solution, while they shift to 2921 and 2850 cmꢀ1 in the benzene
gel, respectively. The red-shift reveals a decrease in the fluidity
Fig. 6 (a) SEM image of xerogel from C12 in benzene (2.802 wt%), (b) SEM image of xerogel from C16 in benzene (0.607 wt%), (c, d) TEM
image of the benzene solution of C16 (0.13 wt%).
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Fig. 7 X-Ray diffraction pattern of the benzene xerogels of (a) C12 (2.802 wt%) and (b) C16 (0.607 wt%).
Experimental technique
Conclusion
1H NMR spectra were recorded with a Bruker Avance 500
MHz spectrometer, using chloroform-d as solvent and tetra-
methylsilane (TMS) as an internal standard. FT-IR spectra
were recorded with a Perkin–Elmer spectrometer (Spectrum
One B). The sample was pressed tablet with KBr. The thermal
properties of the compounds were investigated with a Mettler-
Toled. DSC821e instrument. The rate of heating and cooling
was 10 1C minꢀ1; the weight of the sample was about 2 mg,
and indium and zinc were used for calibration. The peak
maximum was taken as the phase transition temperature.
Optical textures were observed by polarizing optical micro-
scopy (POM) using a Leica DMLP microscope equipped with
a Leitz 350 heating stage. X-Ray diffraction was carried out
with a Bruker Avance D8 X-ray diffractometer. Tms were
determined by the ‘‘falling drop’’ method. An inverted gel was
immersed in a water bath initially at or below the room
temperature. The water was heated slowly until Tm, the
temperature at which the gel fell due to the force of gravity.
SEM observations were taken with a SSX-550 apparatus.
Samples for SEM study were xerogels. Transmission electron
microscopy (TEM) morphology was obtained with JEM 2010
apparatus. Samples for TEM study were prepared by drop-
ping small amount of solution onto a 400-mesh copper grid
following by natural evaporating the solvent.
In conclusion, a new series of achiral compounds containing a
dihydrazide unit in the rigid core was designed. We demon-
strated the unique self-assembling ability of the compounds
C12 and C16, which showed stable thermotropic Col phase
and strong gelation abilities. The columns assemblies were
found both in the liquid crystalline state and in the xerogels.
Intermolecular hydrogen bonding between the dihydrazide
groups and van der Waals interactions between the alkyl
chains were demonstrated to be the major driving force for
both self-assembling processes. The formation of the twist
fibers was due to the steric hindrance and hydrogen bonding
interactions between the dihydrazide groups cooperating with
the packing of the alkoxy chains.
Experimental
Synthesis
All commercially available chemicals were of reagent grade
and were used without further purification. 3,4,5-trihydroxy
benzoic acid ethyl ester and 1-bromide alkyl were purchased.
3,4,5-Trialkoxy-benzoyl hydrazine was prepared according to
literature procedures.29 Alcohol used for recrystallization is
anhydrous and alcohol content is more than 99.7%. The
compounds were synthesized according to the route shown
in Scheme 1.
N-(3,4,5-Propyloxybenzoyl)-N0-(40-nitrobenzoyl) hydrazine
(C3)
3,4,5-tripropyloxy-benzoylhydrazine (1.96 g, 4.26 mM) and
4-nitrobenzoyl chloride (0.79 g, 4.26 mM) were dissolved in
tetrahydrofuran (100 ml), pyridine (2 ml) was added, and the
resulting mixture was stirred at room temperature for 8 h. The
reaction mixture was poured into an excess of ice water, and
the precipitate recrystallized from anhydrous alcohol; yield
64.5%. Compounds C12 and C16 were synthesized according
to the same procedure.
Gelation experiments
The weighted powder compound and solvent were sealed in a
little glass tube, and were then gently heated to make the
gelator completely dissolved. The resulting solution was
cooled in air or ice–water bath (in the low concentration case)
for several minutes, and then the gelation was checked
visually. When upon inversion of the test tube no fluid
ran down the walls of the tube, we judge it ‘‘gelation’’.
The xerogels were obtained through slowly evaporating
the solvents from organogels, which were kept in the air at
about 4 1C.
dH (500 MHz; CDCl3; Me4Si): 10.50 (s, 1H), 9.69 (s, 1H),
8.19 (d, 2H, J = 8.4 Hz), 8.00 (d, 2H, J = 8.3 Hz), 7.04 (s,
2H), 3.98–3.89 (m, 6H), 1.78 (m, 6H), 1.02 (td, 9H, J = 7.3
Hz, J = 14.8 Hz); FTIR (KBr disc, umax/cmꢀ1): 3182, 2966,
2938, 2878, 1661, 1643, 1575, 1522, 1494, 1460, 1428, 1390,
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1347, 1228, 1125, 1060, 957, 842, 719. Elem. Anal: Found: C
60.23, N 8.95, H 6.41%. Calcd for C23H29N3O7: C60.12, N
9.14, H 6.36%.
20050183057) and Project 985-Automotive Engineering of
Jilin University for their financial support of this work.
References
N-(3,4,5-Cetyloxybenzoyl)-N0-(40-nitrobenzoyl) hydrazine
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2 T. Kato, N. Mizoshita and K. Kanie, Macromol. Rapid Commun.,
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(C16)
yield 59.5%. dH(ppm) (500 MHz; CDCl3; Me4Si): 9.48 (s, 1H),
9.12 (s, 1H), 8.33 (d, 2H, J = 8.4 Hz), 8.05 (d, 2H, J = 8.4
Hz), 7.04 (s, 2H), 4.01 (dd, 6H, J = 6.1 Hz, J = 12.4 Hz), 1.78
(m, 6H), 1.47 (m, 6H), 1.26 (s, 72H), 0.88 (d, 9H, J = 13.2 Hz);
FTIR (KBr disc, umax/cmꢀ1): 3193, 2922, 2852, 1663, 1593,
1610, 1579, 1494, 1542, 1341, 1467, 1456, 1257, 1232, 1123,
1100, 868, 863, 719. Elem. Anal: Found: C 73.89, N 4.36, H
10.75%. Calcd for C62H107N3O7: C 73.98, N 4.17, H 10.72%.
3 D. Demus, J. W. Goodby, G. W. Gray and H. W. Spiess, Hand-
book of Liquid Crystals, Wiley-VCH: Weinheim, 1998.
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N-(3,4,5-Dodecyloxybenzoyl)-N0-(40-nitrobenzoyl) hydrazine
(C12)
yield 58.9%. dH(ppm) (500 MHz; CDCl3; Me4Si): 9.69 (s, 1H),
9.22 (s, 1H), 8.30 (d, 2H, J = 8.3 Hz), 8.03 (d, 2H, J = 8.4
Hz), 7.04 (s, 2H), 4.00 (m, 6H), 1.78 (m, 6H), 1.45 (dd, 6H,
J = 7.8 Hz, J = 14.2 Hz), 1.26 (s, 24H), 0.88 (t, 9H, J = 6.7
Hz); FTIR (KBr disc, umax/cmꢀ1): 3193, 2922, 2851, 1662,
1594, 1566, 1610, 1581, 1492, 1525, 1342, 1466, 1456, 1255,
1229, 1123, 1011, 869, 852, 719. Elem. Anal: Found: C 71.35,
N 5.17, H 9.89%. Calcd for C50H83N3O7: C 71.64, N 5.01, H
9.98%.
8 U. Beginn, S. Keinath and M. Moller, Macromol. Chem. Phys.,
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¨
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Chem. Soc., 2003, 125, 15128.
3,4,5-tris(Hexadecyloxy)-N,N0-dimethyl-N0-(4-nitrobenzoyl)
benzohydrazide (Me–C16)
C16 (2.52 g, 2.50 mM) was dissolved in N,N0-dimethylforma-
mide (100 ml), anhydrous potassium carbonate (6.92 g, 50
mM) and CH3I (3.55 g, 25 mM) were added. The mixture was
stirred under reflux for 3 h. After cooling to room tempera-
ture, the reaction mixture was poured into an excess of ice
water, and the precipitate recrystallized from anhydrous alco-
hol; yield 91.5%.
20 R. B. Martin, Chem. Rev., 1996, 96, 3043.
21 The assignments of IR absorption bands were based on ref., (a) H.
Gunzler and H. Gremlich, IR Spectroscopy, Wiley-VCH, New
York, 2002; (b) L. J. Bellamy, in The Infra-Red Spectra of Complex
Molecules, vol. 1, 3rd ed. Chapman and Hall, London, 1975; (c) H.
H. Zhang, Y. Q. Wu, B. L. Bai and M. Li, Spectrochim. Acta, Part
A, 2006, 63, 117.
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23 M. Rozenberg, A. Loewenschuss and Y. Marcus, Phys. Chem.
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24 T. Steiner, Angew. Chem., Int. Ed., 2002, 41, 48.
dH(ppm) (500 MHz; CDCl3; Me4Si): 8.26 (d, 2H, J = 7.2
Hz), 7.67 (s, 2H), 6.72 (s, 0.5H), 6.02 (s, 1.5H), 3.84 (m, 6H),
3.37 (d, 3H, J = 10.3 Hz), 3.04 (d, 3H, J = 51.0 Hz), 1.72 (m,
6H), 1.33 (d, 78H, J = 73.3 Hz), 0.88 (t, 9H, J = 6.8 Hz);
FTIR (KBr disc, umax/cmꢀ1): 2956, 2918, 2850, 1677, 1666,
1585, 1529, 1522, 1468, 1427, 1354, 1232, 1124. Elem. Anal:
Found: C 74.44, N 3.88, H 11.11%. Calcd for C64H111N3O7: C
74.30, N 4.06, H 10.81%.
25 K. Borisch, S. Diele, P. Goring, H. Kresse and C. Tschierske,
¨
J. Mater. Chem., 1998, 8, 529.
Acknowledgements
26 D. J. Abdallah and R. G. Weiss, Langmuir, 2000, 16, 352.
27 Y. Hamuro, S. J. Geib and A. D. Hamilton, J. Am. Chem. Soc.,
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28 M. Suzuki, Y. Nakajima, M. Yumoto, M. Kimura, H. Shirai and
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The authors are grateful to the National Science Foundation
Committee of China (project No. 50373016), Program for
New Century Excellent Talents in University of China Min-
istry of Education, Special Foundation for PhD Program in
Universities of China Ministry of Education (Project No.
29 Y. D. Zhang, K. G. Jespersen, M. Kempe, J. A. Kornfield, S.
Barlow, B. Kippelen and S. R. Marder, Langmuir, 2003, 19, 6534.
ꢁc
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408 | New J. Chem., 2007, 31, 401–408