Calix[4]resorcinarene-cholesterol columnar liquid crystals: Synthesis, mesomorphism and the influence of spacers on liquid crystalline behaviors

Article abstract of DOI:10.1016/j.molliq.2017.01.111

Novel calix[4]resorcinarene derivatives with four cholesterol units bridging by soft spacers or rigid Schiff-base spacers were prepared in yields of 63–76%. The hexagonal columnar liquid crystalline behaviors were firstly observed for calix[4]resorcinarene derivatives. The mesomorphic properties were influenced greatly by the structures of spacers. The rigid spacers were favorable for enhancing the phase transition temperatures and enlarging the temperature scopes of mesophase.

Full text of DOI:10.1016/j.molliq.2017.01.111

Accepted Manuscript
Calix[4]resorcinarene-cholesterol columnar liquid crystals:
Synthesis, mesomorphism and the influence of spacers on liquid
crystalline behaviors
Chenyang Han, Hongyu Guo, Jianbin Lai, Fafu Yang
PII:
DOI:
Reference:
S0167-7322(16)33638-8
doi: 10.1016/j.molliq.2017.01.111
MOLLIQ 6916
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
16 November 2016
12 January 2017
31 January 2017
Please cite this article as: Chenyang Han, Hongyu Guo, Jianbin Lai, Fafu Yang ,
Calix[4]resorcinarene-cholesterol columnar liquid crystals: Synthesis, mesomorphism and
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Molliq(2017), doi: 10.1016/j.molliq.2017.01.111
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ACCEPTED MANUSCRIPT
Calix[4]resorcinarene-cholesterol columnar liquid
crystals: Synthesis, mesomorphism and the
influence of spacers on liquid crystalline behaviors
Chenyang Han,1 Hongyu Guo,*1 Jianbin Lai,1 and Fafu Yang*1,2
Address: 1 College of Chemistry and Chemical Engineering, Fujian Normal University,
Fuzhou 350007, P. R. China and 2Fujian Key Laboratory of Polymer Materials,
Fuzhou 350007, P. R. China
Email: Fafu Yang - yangfafu@fjnu.edu.cn
* Corresponding author
Abstract
Novel calix[4]resorcinarene derivatives with four cholesterol units bridging by soft
spacers or rigid Schiff-base spacers were prepared in yields of 63-76%. The
hexagonal columnar liquid crystalline behaviours were firstly observed for
calix[4]resorcinarene derivatives. The mesomorphic properties were influenced
greatly by the structures of spacers. The rigid spacers were favorable for enhancing
the phase transition temperatures and enlarging the temperature scopes of
mesophase.
Keywords
calix[4]resorcinarene; cholesterol; synthesis; mesophase
1

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Introduction
As the first liquid crystal was reported by Friedrich Reinitzer in 1888 [1], liquid
crystalline materials have attracted much research interest due to their optical
applications [2-5]. Among all kinds of liquid crystals, columnar liquid crystal was paid
much attention in the past decades [6,7]. This kind of subclass of mesophase
possesses π-π stacking arrangement in one direction, resulting in 1D conduction of
charge and/or energy and potential application such organic light-emitting diodes,
organic photovoltaic cells and organic field-effect transistors [8-11]. In general,
columnar liquid crystal had the high symmetric structure, which was prepared by
modifying a conjugated aromatic core or large rigid aromatic core with several soft
and long alkyl chains. For examples, the columnar liquid crystals based on the
triphenylene, phthalocyanine and hexabenzocoronene derivatives with 3~6 aliphatic
chains were extensively studied up to now [12-16]. In recent years, the calixarene
skeleton was also successfully used as rigid core to construct columnar liquid crystal.
Series of columnar calix[4]arene-based liquid crystals were prepared by introducing
several soft chains on calixarene sketelons [17-25]. These researches suggested that
the structures of both calixarene skeletons and the soft chains influenced greatly on
the mesomorphic properties of obtained liquid srystals. Calix[4]resorcinarene is one
of the important building blocks in calixarene chemistry, however, no columnar liquid
crystal based on calix[4]resorcinarene was studied so far, although two smectic and
nematic liquid crystals based on calix[4]resorcinarene derivatives with long alkyl
chains were presented [26,27].
On the other hand, cholesteric liquid crystals have attracted great interest
because of their application prospects on optical switching, soft actuators, information
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storage, and molecular motor applications [28-33]. Popularly, the nematic or smectic
cholesteric liquid crystal was easily prepared by introducing one or two cholesterols
on a rigid unit. For instance, Yeap and co-workers reported the nematic or smectic
mesophases comprising a cholesterol unit as one of the side arms connected to a
1,2,3-triazole ring [34]. Tandel and Patel synthesized some chiral nematic cholesterol
liquid crystals with hydrogen bonding [35]. Yelamaggad’s group prepared the nematic
liquid crystals based on non-symmetric cholesterol trimers and tetramers [36]. Kumar
Pal and Gupta obtained room temperature cholesterol liquid crystal dimers with
pentaalkylnylbenzene [37]. Baumgartner’s group observed the mesophase transition
between nematic and smectic phase of cholesteric click-phospholes [38]. However,
as to columnar cholesteric liquid crystal, only few examples were studied by
modifying the large aromatic core with four cholesteric units. Yin and his co-workers
reported the mesophase transition from smectic to columnar phase of the
tetrathiafulvalene/1,3-dithiol-2-thione derivatives with four cholesterol units [39].
Bhattacharya and Datta also presented the hexagonal columnar mesophase of
triazole derivative with four cholesteric units in the presence of alkali metal ions lately
[40]. Besides these several examples, the cholesteric columnar liquid crystal was still
known little so far. In this paper, we wish to report the design and synthesis of novel
calix[4]resorcinarene derivatives with four cholesteric units in highly symmetric
structures. Moreover, the columnar liquid crystal based on calix[4]resorcinarene was
observed for the first time. The influence of different spacers between
calix[4]resorcinarene and four cholesterols was also investigated.
Results and Discussion
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O
Cl
H
HO
CHO
H
H
OH
n
H
H
H
H
DCC, DMAP, DCM
O
K2CO3, MeCN
H
H
O
2a ( n = 1 )
2b ( n = 3 )
O
1
O
HO
Cl
3a ( n = 1 )
3b ( n = 3 )
n
O
n
OHC
H3CO
OH
HO
H3CO
OH
OCH3
BF3-Et2O
CH2Cl2
+ CH3CH2CH2CHO
H3CO
OH
HO
OCH3
OCh
4
O
n
O
H3CO
OCH3
OCh
O
O
n
O
n
K2CO3, KI, MeCN
O
4 + 2a(b)
ChO
H3CO
OCH3
O
O
5a ( n = 1 )
5b ( n = 3 )
n
OCh
O
3a(b)
K2CO3, KI, MeCN
N2H4
4 +
6
7
8a(b)
Cl
OCH3
OR
H3CO
6 (R = -CH2COOCH3)
7 (R = -CH2CONHNH2)
RO
O
8a (n = 1)
8b (n = 3)
OCH3
n
-CH2CONHN
C
O
OCh
8 (R =
)
H
H3CO
H
OR
Ch =
H
RO
OCH3
H
Scheme 1: The synthetic routes of compounds 5a, 5b 8a and 8b
4

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The synthetic routes for calix[4]resorcinarene derivatives with four cholesteric
units were exhibited in Scheme 1. In order to evaluate the influence of different
structures of spacers on mesomorphic properties, the soft alkyl chains and rigid
Schiff-base chains with different lengths were designed as the spacers between
calix[4]resorcinarene and cholesterols. According to the published literature [23], the
cholesterol derivatives 2a and 2b was synthesized by condesation of cholesterol 1
and corresponding carboxylic acid. Further reacting compounds 2a or 2b with p-
hydroxybenzaldehyde gave compounds 3a and 3b in yields of 80% and 75%,
respectively. On the other hand, according to the reported procedure [41],
calix[4]resorcinarene 4 was prepared in 74% yield by treating m-methoxyphenol with
n-butyl aldehyde under the catalysis of BF3.Et2O. Subsequently, the
calix[4]resorcinarene derivative 7 was obtained by etherification of compound 4 with
methyl chloroacetate and then hydrazinolysis with hydrazine hydrate in yield of 80%.
As reactants were prepared, target calix[4]resorcinarene-cholesteric derivatives 5a
and 5b with soft spacers were conveniently synthesized by reacting compound 4 with
2a (or 2b) in K2CO3/MeCN system in yields of 72% and 63%, respectively. Also, the
target calix[4]resorcinarene-cholesteric derivatives 8a and 8b with rigid spacers were
easily prepared by the Schiff-base condensation of compound 7 with 3a (or 3b) in
yields of 76% and 72%, respectively.
The structures of novel calix[4]resorcinarene-cholesteric derivatives 5a, 5b, 8a
and 8b were characterized by MS and NMR spectra. In their HR-MS spectra, the
strong peaks at 2441.7892, 2575.8964, 3125.0448 and 3259.1519 exactly agreed
with molecular weight of compounds 4a, 4b, 5a and 5b, and no other substituted
model (such as mono-, bi- or tri-substituted derivatives) were observed in MS spectra.
1
As to their H NMR spectra, the proton signals were well in accordance with the
structures. For example, two signals for ArH of calix[4]resorcinarene certainly
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supported the tetra-substituted structures. Only one singlet for proton of CH=N
suggested that all Schiff-base bonds adopted one kind of structure. Due to the strong
steric hindrance of cis-structure, it was reasonable to deduce compounds 8a and 8b
possessed the trans-structure for Schiff-base bonds. The 13C NMR spectra were also
in agreement with the structures of compounds 5a, 5b, 8a and 8b.
Cr
Col
8b
Iso
Cr
cooling
heating
Col
Col
8a
Cr
Iso
Iso
Cr
cooling
heating
Col
cooling
Iso
Col
Col
Iso
Cr
5b
5a
heating
cooling
Iso
Col
Iso
Cr
Cr
heating
Iso
0
50
100
150
200
250
Temperature (oC)
Figure 1 The DSC traces of compounds 5a, 5b, 8a and 8b on second heating and
cooling (scan rate 10oC min-1)
The mesomorphic behaviors of compounds 5a, 5b, 8a and 8b were firstly
investigated by differential scanning calorimetry (DSC). The DSC traces were shown
in Figure 1 and the thermodynamic parameters were collected in Table 1. All of them
exhibited two obvious thermic peaks during cooling and second heating, indicating
that they might have mesophase upon cooling and heating. Two broad endothermic
o
peaks at 68.1 oC and 123.1 C were observed upon heating for compound 5a. The
o
o
corresponding broad exothermic peaks were at 55.7 C and 87.5 C for 5a.
Compound 5b also exhibited two broad thermic peaks on heating (79.9 oC and 118.2
6

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o
o
oC) and cooling (78.8 C and 106.3 C). As to compound 8a, the endothermic peaks
o
appeared at 159.2 C and 224.9 oC upon heating, and the exothermic peaks were at
134.9 oC and 212.6 oC upon cooling, respectively. Compound 8b also showed similar
phase transition behaviors. Upon heating, it displayed two endothermic peaks at
139.2 oC and 200.1 oC. The corresponding exothermic peaks were observed at 126.3
o
oC and 180.8 C, respectively. Based on these DSC traces, the phase transitions of
solid state-mesophase-isotropic phase could be deduced for the four novel
calix[4]resorcinarene-cholesteric derivatives, which were further confirmed by the
studies of polarizing optical microscopy (POM) and X-ray diffraction (XRD) analysis.
On the other hand, the obvious hysteresis of exothermic peaks could be attributed to
super-cooling phenomena, which was common for such highly viscous materials.
Moreover, by comparing with the broad DSC peaks of compounds 5a and 5b, the
peaks of compounds 8a and 8b became narrow. The phase transition temperatures
of compounds 8a and 8b were also remarkably higher than that of compounds 5a
and 5b. These results could be explained by their structures. The spacers between
calix[4]resorcinarene and cholesterol units were soft alkyl chains for compounds 5a
and 5b and rigid Schiff-base chains for compounds 8a and 8b, respectively. The rigid
spacers were favorable for enhancing the crystallinity and reducing the viscosity at
melting, which leaded to high phase transition temperatures and narrow thermic
peaks. After calculation, the temperature scopes of two phase transition of
o
compounds 8a and 8b were 60 C approximately, which was wider than that of 5a
o
and 5b (about 40 C). These results suggested that all novel calix[4]resorcinarene-
cholesteric derivatives 5a, 5b, 8a and 8b possessed good mesomorphic properties.
The phase transition behaviors were influenced greatly by the structures of spacers.
The rigid spacers were favorable for enhancing the phase transition temperatures
and enlarging the temperature scopes of mesophase.
7

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Table 1: Transition temperatures (oC) and enthalpies (kJ·mol-1) of compounds 5a, 5b,
8a and 8b
Comp.
T(ΔH)
T(ΔH)
Phase transition[a]
Cr-Col(Col-Cr)
Col-Iso(Iso-Col)
Cr-Col(Col-Cr)
Col-Iso(Iso-Col)
Cr-Col(Col-Cr)
Col-Iso(Iso-Col)
Cr-Col(Col-Cr)
Col-Iso(Iso-Col)
Heating scan
68.1(12.2)
123.1(11.2)
79.9(13.5)
118.2(15.7)
159.2(15.5)
224.9(18.6)
139.2(18.5)
200.1(16.4)
Cooling scan
55.7(7.9)
5a
87.5(6.8)
5b
78.8(6.2)
106.3(7.2)
134.9(11.4)
212.6(12.4)
126.3(17.2)
180.8(16.9)
8a
8b
[a] Cr=crystalline, Col=columnar phase, Iso=isotropic
Figure 2: Mesomorphic textures obtained under POM on cooling for compounds 5a,
5b, 8a and 8b at 75 oC, 90 oC, 170 oC, and 160 oC (×500), respectively.
8

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Further, the mesophase textures were studied by POM. The two phase
transitions of corresponding solid state-mesophase-isotropic phase were obviously
observed upon heating and cooling for compounds 5a, 5b, 8a and 8b. The phase
temperatures under POM were approximately in accordance with the thermic peaks
of DSC traces. By cooling slowly from their isotropic phase to mesophase, the orderly
mesomorphic textures appeared gradually. The typical textures of compounds 5a, 5b,
8a and 8b were illustrated in Figure 2. One can see that the textures were the focal-
conic and band ones, indicating compounds 5a, 5b, 8a and 8b were columnar liquid
crystals.
2.78
4.83
5.56
2.90
22.52
5.00
5.82
3.03
22.18
8b
5.19
6.05
23.57
8a
3.18
5.49
5b
6.36
23.00
5a
10
20
30
40
Scattering angle 2θ (degree)
o
o
Figure 3: XRD traces of compounds 5a, 5b, 8a and 8b measured at 75 C, 90 C,
170 oC, and 160 oC, respectively.
The XRD analysis was also used to obtain the information about the possible
molecular packing patterns for the mesophase of compounds 5a, 5b, 8a and 8b.
9

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Their XRD traces at the corresponding temperatures were presented in Figure 3.
One can see that three reflections at small-angle region were observed obviously for
compound 5a at 3.18o, 5.49o and 6.36o, compound 5b at 3.03o, 5.19o and 6.05o,
compound 8a at 2.90o, 5.0o and 5.82o, and compound 8b at 2.78o, 4.83o and 5.56o,
respectively. According to Bragg’s formula d = λ/(2Sinθ), the corresponding d-
spacings were calculated as 27.8, 16.1 and 13.9 Å for compound 5a, 29.1, 17.0 and
14.6 Å for compound 5b, 30.4, 17.7 and 15.2 Å for compound 8a, 31.8, 18.3 and
15.8 Å for compound 8b, respectively. The ratios of these reflections agreed with 1:
1/√3:1/2, indicating the [100], [110] and [200] planes of hexagonal columnar
mesophase, respectively. At the wide-angle regions, the broad halos at 2θ = 13~25o
suggested the mean distance of 4.7 Å and the very short correlation length of the
molten cholesterol and alkyl chains. Moreover, a small reflection peaks appeared at
23.00o, 23.57o, 22.18o and 22.52o for compounds 5a, 5b, 8a and 8b, respectively.
The corresponding spacings for these angels were 3.86 Å, 3.77 Å, 3.99 Å and 3.94 Å,
respectively, which were in accordance with the typical intracolumnar distance of π-π
interactions of ordered hexagonal columnar liquid crystals. All these XRD analysis
suggested the hexagonal columnar liquid crystals for these novel
calix[4]resorcinarene-cholesteric derivatives. On the other hand, the lattice parameter
ɑ for compounds 5a, 5b, 8a and 8b was approximately 32~37 Å after calculation.
These data were 30% less than the diameters of compounds 5a, 5b, 8a and 8b
estimated by CPK molecular model (45~55 Å). These results might imply that the
folding or the possible interdigitation of cholesteric chains in the neighbouring
columns. Thus, the possible schematic representation of the hexagonal mesophase
of compounds 5a, 5b, 8a and 8b were proposed in Figure 4. Based on all the data of
DSC, POM and XRD analyses, it could be summarized that these novel
calix[4]resorcinarene-cholesteric derivatives 5a, 5b, 8a and 8b possess the
10

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hexagonal columnar liquid crystalline phases, which could be attributed to the
influences of their high symmetrical structures. The spacers between
calix[4]resorcinarene and cholesterol units influenced greatly on the mesomorphic
properties. The soft spacers showed the mesophase at 55-123oC but the rigid
spacers enhanced the mesomorphic temperatures to 126-224oC. The rigid spacers
were favorable for enhancing the phase transition temperatures and enlarging the
temperature scopes of mesophase.
H
H
H
H
d100
H
H
d110
§Ñ
H3CO
O
O
d001
OCH3
H3CO
O
OCH3
O
H
H
H
H
H
H
Figure 4: The proposed schematic representation of the hexagonal mesophase of
compounds 5a, 5b, 8a and 8b.
Conclusion
In conclusion, by reacting calix[4]resorcinarene with cholesterol terminal-chloric
derivatives, the calix[4]resorcinarene derivatives with four cholesterol units bridging
by soft spacers 5a and 5b were prepared in yields of 72% and 63%, respectively.
The similar calix[4]resorcinarene derivatives with four cholesterol units bridging by
rigid Schiff-base spacers 8a and 8b were prepared in yields of 76% and 72%,
respectively. Their structures were confirmed by NMR and MS. Their liquid crystalline
11

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properties were studied by DSC, POM and XRD. They possessed good hexagonal
columnar liquid crystalline behaviors based on the high symmetrical structures. The
spacers played important roles on mesomorphic properties. The soft spacers were
favorable for the mesophase at low temperature. The rigid spacers enhanced the
phase transition temperatures and enlarged the temperature scopes of mesophase
obviously. The paper suggested that calix[4]resorcinarene could be used as a good
building block to construct the columnar liquid crystals. The design and synthesis of
the other calix[4]resorcinarene columnar liquid crystals will be further investigated in
following work.
Experimental
General Methods: All chemical reagents were obtained from commercial
suppliers and used without further purification. The other organic solvents and
inorganic reagents were purified according to standard anhydrous methods before
use. TLC analysis was performed using pre-coated glass plates. Column
chromatography was performed using silica gel (200-300 mesh). NMR spectra were
recorded in CDCl3 on a Bruker-ARX 400 instrument at 25oC. Chemical shifts are
reported in ppm, using tetramethylsilane (TMS) as internal standard. MS spectra
were obtained from Bruker MALDI-TOF mass spectrometer. POM (Leica DMRX) was
used along with a hot stage (Linkam THMSE 600) to examine phase transitions.
Thermal analysis of the materials was carried out using DSC (Thermal Analysis
Q100) at a scanning rate of 10oC/min under N2 atmosphere. XRD experiments were
performed on SEIFERT-FPM (XRD7), using Cu Kα 1.5406Å as the radiation source
with 40 kV, 30 mA power. Compounds 2a and 2b were synthesized by the literature
[23]. Compound 4, 6 and 7 were prepared according to the literature [41].
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The synthetic procedure of compounds 5a and 5b: Under N2 atmosphere, a
mixture of compound 4 (0.324 g, 0.5 mmol), compound 2a or 2b (2.5 mmol), K2CO3
(0.83g, 6mmol) and KI (0.6 g, 3.6 mmol) was stirred and refluxed in 50 mL of dry
acetonitrile for 24h. TLC detection indicated the disappearance of starting materials.
Then the solvent was evaporated under reduced pressure. The residue was treated
with 50 mL distilled water and subsequently was extracted with 3×20 mL of CHCl3.
The CHCl3 solution was concentrated and was further purified by column
chromatography on silica gel using a mixture of hexane:CH2Cl2 (3:1) as eluant.
Compounds 5a and 5b were obtained as white solid in yields of 72% and 63%,
1
respectively. Compound 5a: H NMR (400 MHz, CDCl3) δppm: 6.61(s, 4H, ArH),
6.29(s, 4H, ArH), 5.38(m, 4H, CH=C on cholesterol), 5.04(bs, 8H, OCH2CO), 4.69(bs,
4H, OCH), 4.54(t, J = 8.0Hz, 4H, CH), 3.63(s, 12H, OCH3), 2.34-0.68(m, 200H, CH,
13
CH2 and CH3); C NMR (100 MHz, CDCl3) δppm: 168.96, 155.54, 140.79, 139.35,
128.08, 127.44, 126.15, 122.95, 121.69, 74.60, 71.79, 56.79, 56.27, 50.07, 42.34,
39.78, 39.29, 38.07, 37.29, 36.79, 36.65, 36.21, 35.79, 35.07, 31.93, 31.68, 28.23,
28.01, 24.30, 23.73, 22.96, 22.56, 21.10, 19.29, 18.73, 14.33, 11.87; MALDI-TOF-
MS Calcd.for m/z = 2418.8, found: m/z = 2458.3 (MK+); HR-MS(ESI) (C160H240O16)
1
[MNa]+: Calcd.: 2441.7892. found:2441.7949. Compound 5b: H NMR (400 MHz,
CDCl3) δppm: 6.61(s, 4H, ArH), 6.34(s, 4H, ArH), 5.38(m, 4H, CH=C on cholesterol),
4.69(bs, 4H, OCH), 4.54(t, J = 8.0Hz, 8H, OCH2), 4.30(t, J = 8.0Hz, 4H, CH), 3.83(s,
12H, OCH3), 2.34-0.68(m, 216H, CH, CH2 and CH3);13C NMR (100 MHz, CDCl3)
δppm: 172.79, 155.41, 154.96, 139.65, 125.93, 123.27, 122.79, 121.37, 97.18, 73.91,
71.80, 56.78, 56.07, 55.59, 50.05, 42.33, 39.80, 39.53, 38.21, 37.02, 36.61, 36.20,
35.67, 35.28, 31.92, 30.90, 28.24, 28.02, 27.61, 24.89, 24.42, 23.96, 22.98, 22.49,
21.31, 19.33, 18.73, 14.29, 11.73; MALDI-TOF-MS Calcd.for m/z = 2531.7, found:
13

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m/z = 2571.8 (MK+); HR-MS(ESI) (C168H256O16) [M+2Na-H]+: Calcd.: 2575.8964.
found: 2575.8682.
The synthetic procedure of compounds 8a and 8b: Under N2 atmosphere, a
mixture of compound 7 (0.20 g, 0.2 mmol) and 3a or 3b (0.8 mmol) was stirred and
refluxed in 50 mL of EtOH/CHCl3 (1:1, V/V) for 18 h. TLC detection indicated the
disappearance of starting materials. Then the solvent was evaporated under reduced
pressure. The residue was treated with 30 mL of MeOH and the white precipitation
was purified by recrystallization in CH2Cl2/EtOH. Compounds 8a and 8b were
obtained in yields of 76% and 72%, respectively. Compound 8a: 1H NMR (400 MHz,
CDCl3) δppm: 9.53 (s, 4H, NH), 8.25 (s, 4H, N=CH), 7.68 (d, 8H, J = 8.0Hz, ArH),
6.90 (d, 8H, J = 8.0Hz, ArH), 6.80(s, 4H, ArH), 6.32(s, 4H, ArH), 5.38(s, 4H, CH=C on
cholesterol), 4.45-4.75(m, 24H, OCH, OCH2 and CH), 3.65(s, 12H, OCH3), 2.37-
0.68(m, 200H, CH, CH2 and CH3); 13C NMR (100 MHz, CDCl3) δppm: 167.88, 164.36,
163.38, 159.78, 154.41, 153.57, 140.13, 139.27, 129.36, 127.58, 127.00, 125.42,
122.96, 118.78, 114.87, 75.42, 68.38, 65.25, 56.77, 56.02, 53.45, 49.79, 42.32,
39.71, 39.53, 37.97, 36.89, 36.56, 36.19, 35.81, 31.83, 28.25, 27.90, 27.69, 24.29,
23.70, 22.85, 22.54, 21.04, 19.32, 18.58, 14.30, 11.72; MALDI-TOF-MS Calcd.for
m/z = 3124.0, found: m/z = 3163.6 (MK+); HR-MS(ESI) (C196H272N8O24) [MH]+: Calcd.:
3125.0448. found:3125.0435. Compound 8b: 1H NMR (400 MHz, CDCl3) δppm: 9.54
(s, 4H, NH), 8.21 (s, 4H, N=CH), 7.65 (d, 8H, J = 8.0Hz, ArH), 6.99 (d, 8H, J = 8.0Hz,
ArH), 6.87(s, 4H, ArH), 6.33(s, 4H, ArH), 5.38(s, 4H, CH=C on cholesterol), 4.60 (bs,
12H, OCH and OCH2), 4.10 (t, J = 7.2Hz, 4H, CH), 4.01 (bs, 8H, OCH2), 3.71(s, 12H,
OCH3), 2.52-0.68(m, 216H, CH, CH2 and CH3); 13C NMR (100 MHz, CDCl3) δppm:
167.99, 160.97, 155.30, 154.75, 144.08, 143.07, 141.55, 139.16, 131.96, 130.17,
129.38, 128.61, 127.29, 123.13, 114.93, 75.45, 65.96, 65.26, 56.68, 56.05, 55.06,
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49.99, 42.32, 39.71, 39.35, 37.98, 36.89, 36.56, 36.20, 35.81, 31.83, 28.23, 28.03,
27.63, 24.29, 23.87, 22.83, 22.58, 21.03, 19.13, 18.73, 14.25, 11.94; MALDI-TOF-
MS Calcd.for m/z = 3236.1, found: m/z = 3260.9 (MNa+); HR-MS(ESI) (C204H288N8O24)
[MNa]+: Calcd.: 3259.1519. found:3259.1589.
Supporting Information
The experimental procedure for the synthesis of compounds 5a, 5b, 8a and 8b
with the intermediate steps involved and the spectral characterization were given in
Supporting Information.
Acknowledgements
Financial support from the National Natural Science Foundation of China (No:
21406036), Fujian Natural Science Foundation of China (No. 2014J01034) and the
Program for Innovative Research Team in Science and Technology in Fujian
Province University were greatly acknowledged.
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Highlights
Novel calix[4]resorcinarene-cholesterol derivatives were synthesized.
The calix[4]resorcinarene columnar liquid crystals were firstly observed.
The mesomorphic properties were influenced by the structures of spacers.
The rigid spacers enhanced the phase transition temperatures.
19