Synthesis and self-assembly of oligomers containing cruciform 9,10-bis(arylethynyl)anthracene unit: Formation of supramolecular nanostructures based on rod-length-dependent organization

Article abstract of DOI:10.1016/j.tet.2013.12.072

Conjugated rod-coil molecules, incorporating flexible and rigid blocks, have a strong affinity to self-organize into various supramolecular nanostructures in the bulk state.In this study, we report synthesized oligomers containing cruciform 9,10-bis(aryle

Full text of DOI:10.1016/j.tet.2013.12.072

Tetrahedron 70 (2014) 1230e1235
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis and self-assembly of oligomers containing cruciform
9,10-bis(arylethynyl)anthracene unit: formation of supramolecular
nanostructures based on rod-length-dependent organization
,
,
,
a,
Jikai Zhu a y, Keli Zhong b y, Yongri Liang c, Zhuoshi Wang a, Tie Chen a , Long Yi Jin
*
*
a Key Laboratory for Organism Resources of the Changbai Mountain and Functional Molecules, Ministry of Education, and Department of Chemistry,
College of Science, Yanbian University, No. 977 Gongyuan Road, Yanji 133002, China
b College of Chemistry, Chemical Engineering and Food Safety, Bohai University, Jinzhou 121013, China
c Beijing National Laboratory for Molecular Sciences, Joint Laboratory of Polymer Science and Materials, Institute of Chemistry, Chinese Academy of
Sciences, Beijing 100190, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Conjugated rod-coil molecules, incorporating flexible and rigid blocks, have a strong affinity to self-
organize into various supramolecular nanostructures in the bulk state.In this study, we report synthe-
sized oligomers containing cruciform 9,10-bis(arylethynyl)anthracene units and characterized their self-
assembly behavior. The molecular structures were characterized with 1H, 13C NMR, and matrix-assisted
laser desorption ionization time-of-flight (MALDI-TOF) mass spectroscopy. An investigation of the su-
pramolecular nanostructures of these molecules using differential scanning calorimetry, thermal po-
larized optical microscopy, and small-angle X-ray scattering revealed that the rod length of coil-rod-coil
molecules with identical rod to coil volume ratios dramatically influences self-assembly behavior in the
bulk state. Molecules 2 and 3 with relatively longer rod lengths self-assemble into lamellar structures in
the solid state, whereas, molecules 1 and 4 self-assemble into two-dimensional (2-D) oblique columnar
structures in the liquid crystalline phase, in addition, on heating, molecule 1 transforms from the oblique
columnar phase to the nematic phase.
Received 14 September 2013
Received in revised form 13 December 2013
Accepted 24 December 2013
Available online 31 December 2013
Keywords:
Anthracene
Self-assembly
Cruciform molecule
Coil-rod-coil
Supramolecular structure
Ó 2013 Elsevier Ltd. All rights reserved.
1. Introduction
and coil cross-sectional area.9 Anthracene-centered cruciform
compounds have been studied widely, with a focus on their two-
Synthesis of supramolecular units through self-assembly is one
of the most exciting interdisciplinary researches areas involving
chemistry, biology, and material science.1 Among self-assembling
molecular systems, rod-coil block molecules consisting of an
elongated rigid rod and a flexible coil have attracted attention as
interesting self-assembling soft materials given the possibility of
synthesizing novel functional materials by combining their self-
assembling capability and functional uniqueness.2 Self-assembly
studies concerning supramolecular structures and their intriguing
properties have been reported, with a focus on the various shapes
of the rigid conjugated rod segment, such as Y-,3 T-,4 O-,5 K-,6
propeller-,7 and dumbbell-shaped8 rod-coil molecules. Precise
control over a supramolecular nanostructure with a well-defined
shape and size is of critical importance for their application in
photoelectronic self-organizing materials. This control is achieved
by adjusting the cooperative effects of various molecular parame-
ters such as volume fraction of rod to coil segment, rod anisotropy,
photon absorption (TPA) properties;2b,10 however, there are few
studies on the self-assembling behavior of anthracene-centered
cruciform derivates that explore the relationship between molec-
ular aggregates and their unique physical properties. Therefore, it is
interesting to design and synthesize new types of cruciform com-
pounds possessing excellent TPA properties and study their self-
assembling behavior for improving molecular photoelectronic
properties.
With this in mind, we synthesized coil-rod-coil molecules 1e4
(Scheme 1) with conjugated rod building blocks and investigated
their self-assembly behaviors in the bulk state with differential
scanning calorimetry (DSC), thermal polarized optical microscopy
(POM), and small-angle X-ray scattering (SAXS).
2. Results and discussion
2.1. Synthesis and characterization of molecules 1e4
* Corresponding authors. E-mail addresses: tchen@ybu.edu.cn (T. Chen), lyjin@
The synthetic route of cruciform 9,10-bis(arylethynyl)anthra-
cene derivatives consisting of 9,10-bis(arylethynyl)anthracene as
ybu.edu.cn (L.Y. Jin).
y
These authors contributed equally to this work.
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.12.072

J. Zhu et al. / Tetrahedron 70 (2014) 1230e1235
1231
Scheme 1. Chemical structures of the molecules 1e4 based on anthracene aromatic rod building block.
a rigid rod segment connecting poly(ethylene oxide) (PEO)
chains of different lengths is outlined in Scheme 2. Target mol-
ecules were obtained through successive reaction steps including
tosylation, substitution reaction, methylation, demethylation re-
action, and Sonogashira coupling reaction. Target molecules 1e4
were characterized with 1H, 13C NMR and matrix-assisted laser
desorption ionization time-of-flight (MALDI-TOF) mass spec-
troscopy and were shown to be in full agreement with the
structures presented in Scheme 1. A representative 1H NMR
spectrum analysis of molecule 1 is shown in Fig. 1 (three other
molecular 1H, 13C NMR spectra are shown in Figs. S1e7, and
1He1H COSY and NOESY spectra of molecule 1 are shown in Figs.
S8 and 9, see Supplementary data). As confirmed by 1H NMR
spectroscopy, the ratio of the aromatic protons of the rod block to
the alkoxyl protons is consistent with the calculated value, and
the MALDI-TOF mass spectra of the molecules show three signals
that can be assigned to Hþ, Naþ, and Kþ labeled molecular ions
(Fig. S10, see Supplementary data). The experimental mass based
on peak positions in the spectrum is well matched with the
theoretical molecular weight of each molecule.
Scheme 2. Synthetic route of molecules 1e4.

1232
J. Zhu et al. / Tetrahedron 70 (2014) 1230e1235
On heating, molecule 1 melts into a liquid crystalline phase at
56.1 ꢀC and then into a second liquid crystalline phase, which in
turn undergoes isotropization at 132.2 ꢀC (Fig. 2A). On the slow
cooling of molecule 1 from the isotropic liquid to liquid crystalline
mesophase, a schlieren-like texture is observed in the POM ex-
periment. This corresponds to a nematic liquid crystalline phase
(Fig. 3A). A schematic diagram of the nematic phase of molecule 1 is
shown in Fig. 5A. As the temperature decreases further, a focal,
conical, fan-shaped spherulitic texture is observed, which pre-
liminarily confirms the presence of a 2-D ordered columnar phase
(Fig. 3B). As the sample is cooled to room temperature, the liquid
crystalline phase transforms into a crystalline phase (Fig. 3C). To
corroborate the detailed liquid crystalline structure of molecule 1,
we performed SAXS experiments at various temperatures during
cooling from the isotropic phase to the solid state. Fig. 4A shows the
X-ray diffraction patterns of molecule 1 at 80 ꢀC; the SAXS profile of
molecule 1 shows a number of Bragg reflections, which can be
assigned to a 2-D oblique columnar structure with lattice param-
Fig. 1. 1H NMR spectrum of molecule 1 (solvent: CDCl3).
2.2. Structural analysis in bulk state
eters a¼4.7 nm, b¼2.9 nm, and
g
¼63ꢀ (Table 2). For obtaining de-
The self-assembly behavior of 1e4 was investigated with DSC,
POM, and XRD in the bulk state. Fig. 2 shows the DSC heating and
cooling traces of molecules 1e4. The transition temperatures of
molecules 1e4 obtained from the DSC heating and cooling scans are
summarized in Table 1.
tailed information on the packing arrangement, we calculated the
number (n) of molecules in a single slice of the column. From the
experimental values of the unit cell parameters (a, b, c, and
g) and
density ( ), the average number of molecules per cross-sectional
r
slice of the column can be calculated using Eq. 1, where M is the
molecular mass and NA is Avogadro’s number. The number of
molecules in a single slice of the column, calculated based on the
lattice constants and measured densities of molecule 1, is about 4
(implying an equal number of molecules per columnar cross section
irrespective of the PEO chain length). On the basis of this data,
a schematic representation of the oblique columnar structure of
molecule 1 is shown in Fig. 5B.
abc
r
sin NA
g
M
n ¼
(1)
To further evaluate the influence of rod length on the self-
assembly behaviors of coil-rod-coil molecules, we synthesized
coil-rod-coil molecules 2 and 3, and investigated their self-
assembly behaviors in the bulk state. In sharp contrast to mole-
cule 1, molecules 2 and 3 show the solid phase and transform into
an isotropic liquid at 240.5 ꢀC and 269.4 ꢀC, respectively (Fig. 2B and
C). Upon slow cooling from the isotropic liquid temperature to
room temperature, these two molecules exhibit a wide range of
crystallization phenomena in the field of vision. Notably, the
melting point of molecules 1e3 with different rod lengths but
identical rod to coil volume ratios, as shown in Fig. 2, increases as
the length of the conjugated rod segment increases. This can be
ascribed to the fact that the extended conjugated rod segment
enhances intermolecular
pep interaction, thereby increasing the
melting points of those coil-rod-coil molecules. The small-angle
XRD patterns of molecules 2 and 3 contain several sharp re-
flections. These reflections correspond to equidistant q-spacing
(Fig. 4B and C) and can be indexed to a lamellar lattice with the
layer spacing of 4.6 nm and 5.1 nm, respectively. Considering the
estimated molecular lengths (9.8 nm and 11.4 nm using the CPK
model for molecules 2 and 3, respectively), the PEO coil segments of
molecules 2 and 3 are fully interdigitated and the rod segments are
packed in a monolayer arrangement (Fig. 5C).
To investigate the effect of molecules with the same building
block rod length but different PEO coil chain lengths on the self-
assembly behavior of this molecular architecture, we synthesized
coil segments of the coil-rod-coil molecule 4 consisting of poly(-
ethylene oxide) with a degree of polymerization of 3. Similar to
molecule 1, molecule 4 also displays a columnar mesophase in the
liquid crystalline phase. The DSC results show that the crystal
melting transition involves a birefringent liquid crystalline phase at
Fig. 2. DSC traces (10 ꢀC/min) recorded during the second heating and the first cooling
scans of molecules 1e4.
Table 1
Thermodynamic transformation of molecules 1e4 (data are from the second heating
and the first cooling scans)
Molecule
fcoil
Phase transition temperature (ꢀC)
Heating
Cooling
1
2
3
4
0.48
0.48
0.48
0.38
k 56.1 Colo 95.9 N 132.2 i
L 240.5 i
L 269.4 i
i 123.7 N 76.1 Colo
i 272.7 L
i 262.3 L
k 95.9 Colo 146.6 i
i 126.3 Colo
k: crystalline phase; L: lamellar; Colo: oblique columnar; N: nematic phase; i: iso-
tropic phase. fcoil: coil volume fraction.

J. Zhu et al. / Tetrahedron 70 (2014) 1230e1235
1233
Fig. 3. Representative optical polarized micrographs of the texture exhibited by (A) nematic phase of 1 at the transition from the isotropic liquid, (B) oblique columnar structure of 1
in the liquid crystalline phase, (C) the crystalline phase of 1, (D) oblique columnar structure of 4 in the liquid crystalline phase.
Table 2
Small-angle X-ray diffraction data for oblique columnar structure for molecule 1
(measured at 80 ꢀC)
h
k
l
qobsd (nmꢁ1
)
qcalcd (nmꢁ1
)
1
1
0
2
2
0
1
1
1
0
0
0
0
0
0
1.520
2.220
2.461
2.923
3.050
1.523
2.219
2.461
2.937
3.042
qobsd and qcalcd are the scattering vectors of the observed and calculated reflections
for the oblique columnar structure with lattice parameters a¼4.7 nm, b¼2.9 nm,
g
¼63ꢀ
(
l¼0.154 nm).
planes of a 2D oblique columnar structure with lattice parameters
a¼4.5 nm, b¼2.8 nm, and
g
¼63ꢀ (Table 3). The number of mole-
cules in a single slice of the column, calculated according to Eq. 1, is
about 4. Compared with molecule 1, the nematic liquid crystalline
phase is not observed for molecule 4, which is due to the reduction
in rod to coil volume fraction from 0.48 to 0.38.
On the basis of the above discussion, we draw the interesting
conclusion that molecules 1e3 have different rod lengths but equal
rod to coil volume ratios. Molecule 1 self-assembles into oblique
columnar and nematic aggregates in the liquid crystalline phase.
However, molecules 2 and 3 with longer rod segments self-
assemble into lamellar structures in the solid state (Table 4), al-
though these molecules have equal rod to coil segment volume
fractions. As mentioned in the Introduction, generally, the volume
fraction of rod to coil segment, rod anisotropy, and coil cross-
sectional area influence the self-assembly behaviors of supramo-
lecular nanostructures. For the rod-coil molecule system, rod to coil
volume ratio is a major parameter for constructing various supra-
molecular nanostructures. Hence, we can attribute the self-
assembly behavior of molecules 1e3, which have different rod
lengths but identical rod to coil volume ratios, to microphase sep-
aration between the rod and coil domains of the molecules due to
Fig. 4. Small-angle X-ray diffraction patterns of (A) oblique columnar structure on
cooling to 80 ꢀC for molecule 1, (B) lamellar structure at 100 ꢀC for molecule 2, (C)
lamellar structure at 90 ꢀC for molecule 3, (D) oblique columnar structure on cooling to
110 ꢀC for molecule 4.
95.9 ꢀC, followed by an isotropic phase at 146.6 ꢀC (Fig. 2D). In
addition, upon cooling from the isotropic liquid temperature, a fan-
shaped spherulitic texture can be observed. This indicates the
presence of a two-dimensional (2D) ordered columnar phase
(Fig. 3D). As shown in Fig. 4D, in the liquid crystalline phase, the
corresponding small-angle XRD patterns show several reflections,
which can be indexed as the (100), (110), (010), (210), and (200)
different driving forces of the
with molecule 1, which has a relatively short conjugated rod length,
the driving force of the stacking interactions of molecules 2
pep stacking interaction. Compared
pep
and 3 is slightly stronger. Subsequently, this affects the construction
of supramolecular nanostructures. The DSC results of molecules

1234
J. Zhu et al. / Tetrahedron 70 (2014) 1230e1235
Fig. 5. Schematic representation of self-assembly of (A) nematic phase and (B) oblique columnar structure of molecule 1, and (C) lamellar structure of molecule 2.
Table 3
the melt state. Therefore, the coil to rod volume fraction, presence
of lateral alkyl or benzene groups in the middle of rod segment, and
rod segment length collaboratively contribute to the construction
of supramolecular nanostructures with a well-defined size and
shape for rod-coil molecular systems.
Small-angle X-ray diffraction data for oblique columnar structure for molecule 4
(measured at 110 ꢀC)
h
k
l
qobsd (nmꢁ1
)
qcalcd (nmꢁ1
)
1
1
0
2
2
0
1
1
1
0
0
0
0
0
0
1.556
2.259
2.491
2.969
3.104
1.552
2.260
2.491
2.971
3.118
3. Conclusions
Cruciform molecules 1e4 consisting of 9,10-bis(arylethynyl)
anthracene as a rigid rod segment connecting PEO chains of various
lengths were synthesized, characterized, and their self-assembly
behavior was investigated in the bulk state. The experimental re-
sults reveal that the rod length of coil-rod-coil molecules with
equal rod to coil volume ratios dramatically influences their self-
assembly behavior in the bulk state. Furthermore, the benzene
units of cruciform 9,10-bis(arylethynyl)anthracene in the center of
rod building block have the same effect. Molecules 2 and 3 with
relatively longer PEO coil chains self-assemble into a lamellar
structure in the solid state, whereas molecules 1 and 4 with rela-
tively short PEO chains self-assemble into 2D oblique columnar
structures in the liquid crystalline phase. In addition, on heating,
molecule 1 transforms from an oblique columnar structure to the
nematic phase.
qobsd and qcalcd are the scattering vectors of the observed and calculated reflections
for the oblique columnar structure with lattice parameters a¼4.5 nm, b¼2.8 nm,
g
¼63ꢀ
(
l¼0.154 nm).
Table 4
Summary of small-angle X-ray diffraction data for molecules 1e4
Molecule
Crystalline phase
Liquid crystalline phase
Lamellar (L) d (nm)
Oblique columnar structure (Colo)
a (nm)
b (nm)
g
n
1
2
3
4
4.7
2.9
63
4
4.6
5.1
4.5
2.8
63
4
d, the layer spacing; a, b, lattice constant (nm); g, characteristic angle; n, the average
number of molecules per cross-sectional slice of the column.
4. Experimental
4.1. Materials
1e3 indirectly demonstrate the point that the extended conjugated
rod segment enhances intermolecular
pep interaction, thereby
All reagents were obtained from SigmaeAldrich, Acros, and TCI
leading to an increase in the melting points of those coil-rod-coil
molecules. It should be pointed out that we have reported the
synthesis and self-assembly behavior of coil-rod-coil molecules
with lateral methyl and ethyl groups in the center of the rod seg-
ment. The experimental results reveal that the lateral alkyl group in
the middle of the rod segment dramatically influences self-
assembly behavior in the liquid crystalline phase. Compared with
rod-coil molecules without side chains, rod-coil molecules with
lateral alkyl groups in the middle of rod segments lead to 2D or 3D
self-assembly. Generally, linear rod-coil molecules without lateral
rod groups and a rod to coil volume fraction of approximately 0.5
self-assemble into lamellar structures or isotropic liquid in the solid
state and melt state, respectively,11 whereas molecules 1 and 4 self-
organize into 2D columnar nanostructures in the liquid crystalline
phase. This behavior is reasonable considering the influence of the
two benzene groups of cruciform 9,10-bis(arylethynyl)anthracene
outside the linear rod segment. Compared with rod-coil molecules
without a lateral alkyl group in the center of the rod segment and
equal rod to coil volume fractions, the driving force of the in-
Chemical Co. and used as received. Trimethylsilyl-acetylene, tet-
rakis(triphenyl-phosphine)
palladium(0),
iodomethane,
4-
hydroxy-40-iodobiphenyl, cuprous iodide, 2-methyl-3-butyn-2-ol,
4-iodophenol, toluene-p-sulfonyl chloride (TsCl, 98%), 9,10-
dibromoanthracene, 2-methoxyethanol, tetraethylene glycol, tri-
ethylene glycol-monomethyl ether, 4,40-diiodobiphenyl, and con-
ventional reagents were used as received. Tetrahydrofuran (THF)
was distilled from sodium metal at the presence of benzophenone
and degassed prior to use. All manipulations involving air-sensitive
reagents were performed under an atmosphere of dry N2.
4.2. Techniques
Flash column chromatography was performed using silica gel
(200e300 mesh). 1H NMR (300 MHz) and 13C NMR (75 MHz)
spectra were recorded in CDCl3 on Bruker AM-300 instruments.
Chemical shifts were described in parts per million (ppm) (d units)
downfield of tetramethylsilane (TMS) as an internal standard and
the coupling constants (J values) were reported in hertz (Hz). Ref-
termolecular pep interaction of molecules 1 and 4 decreases due to
the two benzene groups that are outside the linear rod building
block. This leads to the formation of the 2D columnar mesophase in
erence values for residual solvent were taken as
d
¼7.27 (CDCl3) for
1H NMR;
d
¼77.1 (CDCl3) for 13C NMR. Multiplicities for coupled

J. Zhu et al. / Tetrahedron 70 (2014) 1230e1235
1235
signals are designated using the following abbreviations: s¼singlet,
d¼doublet, t¼triplet, m¼multiplet. Two-dimensional 1He1H COSY
and 1He1H NOESY techniques were measured using standard
micro-programs provided by Bruker. A PerkineElmer Pyris Di-
amond differential scanning calorimeter was used to determine the
thermal transitions, which were reported as the maxima and
minima of their endothermic or exothermic peaks; the heating and
cooling rates were controlled to 10 ꢀC/min under N2 atmosphere.
The SAXS measurements were performed in transmission mode
with synchrotron radiation at the 1W2A X-ray beam line at Beijing
Accelerator Laboratory. A Nikon Optiphot 2-pol optical polarized
microscope, equipped with a Mettler FP 82 hot-stage and a Mettler
FP90 central processor, was used to observe the thermal transitions
and to analyze the anisotropic texture. MALDI-TOF-MS was per-
formed on a percaptive Biosystems Voyager-DESTR using a 2-
cyano-3-(4-hydroxyphenyl) acrylic acid (CHCA) as matrix.
7.58e7.70 (m, 12H, Ar), 7.04 (d, J¼8.8 Hz, 4H, Ar), 4.20 (t, J¼4.6 Hz,
4H, 2phenylOCH2CH2O), 3.92 (t, J¼4.6 Hz, 4H, 2phenylOCH2CH2O),
3.51e3.81 (m, 15H, 2phenylOCH2CH2O(CH2CH2O)2CH3), 3.34 (s, 6H,
2OCH3). 13C NMR (75 MHz, CDCl3,
d, ppm): 158.7, 132.0,130.3, 128.6,
128.2, 127.4, 126.5, 121.5, 119.5, 115.2, 102.4, 72.1, 71.2, 70.7, 70.2,
67.3, 58.9. MALDI-TOF-MS m/z [M]þ 854.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (grant numbers: 21164013, 21304009) and the
Jilin Provincial Science and Technology Department (grant number:
201115225). We are grateful to Beijing Synchrotron Radiation Fa-
cility (BSRF), Institute of High Energy Physics, Chinese Academy of
Sciences for help with the X-ray scattering measurements of mo-
lecular structures.
4.3. Synthesis of molecules 1e4
Supplementary data
Molecules 1e4 were synthesized using the same procedure. A
representative example is described for molecule 1.
Procedure of the synthetic reaction, and spectroscopic data di-
agrams of all products 5e14. Supplementary data associated with
this article can be found in the online version, at http://dx.doi.org/
10.1016/j.tet.2013.12.072.
Compound 6 (150 mg, 0.66 mmol) and compound 9 (725 mg,
1.98 mmol) were added to tetrahydrofuran (40 mL). Triethylamine
(20 mL) was added and then tetrakis(triphenyl-phosphine)palla-
dium(0) (23 mg, 19.8 mmol) and copper iodide (5 mg, 26.4 mmol)
were added. The mixture was degassed and then heated at reflux
for 48 h with vigorous stirring under nitrogen. The solvent was
removed in a rotary evaporator and the resulting mixture was
poured into water and extracted with dichloromethane, dried over
anhydrous magnesium sulfate, and filtered. The solvent was
evaporated to dryness. The crude product was purified by column
chromatography (silica gel) using methylene dichloride/ethyl ace-
tate (1:3 v/v) as eluant to yield a red solid (0.19 g, 35%).
References and notes
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1H NMR (300 MHz, CDCl3,
d
, ppm): 8.72 (dd, J¼6.6 and 3.2 Hz,
4H, Ar), 7.82 (d, J¼8.4 Hz, 4H, Ar), 7.57e7.67 (m, 12H, Ar), 7.03 (d,
J¼8.8 Hz, 4H, Ar), 4.18 (t, J¼4.6 Hz, 4H, 2phenylOCH2CH2O), 3.91 (t,
J¼4.6 Hz, 4H, 2phenylOCH2CH2O), 3.54e3.75 (m, 32H, 2phenyl-
OCH2CH2O(CH2CH2O)4CH3), 3.38 (s, 6H, 2OCH3). 13C NMR (75 MHz,
CDCl3, d, ppm): 158.5, 140.7, 133.1, 131.9, 128.1, 127.1, 126.7, 121.6,
118.3, 115.1, 102.4, 71.9, 70.7, 69.7, 67.6, 58.9. MALDI-TOF-MS m/z
[M]þ 1031.
Molecule 2: red solid, 32%. 1H NMR (300 MHz, CDCl3,
d, ppm):
8.75 (dd, J¼6.6 and 3.2 Hz, 4H, Ar), 7.88 (d, J¼8.2 Hz, 4H, Ar),
7.60e7.75 (m, 16H, Ar), 7.51 (d, J¼8.5 Hz, 4H, Ar), 6.93 (d, J¼8.5 Hz,
4H, Ar), 4.18 (t, J¼4.3 Hz, 4H, 2phenylOCH2CH2O), 3.89 (t, J¼4.3 Hz,
4H, 2phenylOCH2CH2O), 3.52e3.82 (m, 46H, 2phenyl-
OCH2CH2O(CH2CH2O)6CH3), 3.39 (s, 6H, 2OCH3). 13C NMR (75 MHz,
3. (a) Olsen, B. D.; Segalman, R. A. Mat. Sci. Eng., R 2008, 62, 37; (b) Rubatat, L.;
Kong, X.; Jenekhe, S. A.; Ruokolainen, J.; Hojeij, M.; Mezzenga, R. Macromole-
cules 2008, 41, 1846.
CDCl3, d, ppm): 159.0, 140.6, 139.7, 133.1, 132.2, 132.0, 127.2, 127.0,
126.9, 123.2, 118.6, 115.5, 114.7, 102.3, 90.4, 88.0, 87.6, 71.9, 70.9,
70.6, 69.6, 58.9. MALDI-TOF-MS m/z [M]þ 1406, [MþNa]þ 1429,
[MþK]þ1445.
4. (a) Chen, X. L.; Jenekhe, S. A. Macromolecules 2000, 33, 4610; (b) Rahman, M. S.;
Samal, S.; Lee, J. S. Macromolecules 2006, 39, 5009.
5. Gao, L.; Yao, J.; Shen, Z.; Wu, Y.; Chen, X.; Fan, X.; Zhou, Q. Macromolecules 2009,
42, 1047.
6. Lim, Y. B.; Lee, E.; Lee, M. Macromol. Rapid Commun. 2011, 32, 191.
7. Ryu, J.; Cho, B.; Lee, M. Bull. Korean Chem. Soc. 2006, 27, 1270.
8. Prehm, M.; Liu, F.; Baumeister, U.; Zeng, X.; Ungar, G.; Tschierske, C. Angew.
Chem., Int. Ed. 2007, 46, 7972.
Molecule 3: red solid, 40%. 1H NMR (300 MHz, CDCl3,
d, ppm):
8.71 (dd, J¼6.6 and 3.2 Hz, 4H, Ar), 7.84 (d, J¼8.0 Hz, 4H, Ar),
7.52e7.71 (m, 28H, Ar), 6.99 (d, J¼8.6 Hz, 4H, Ar), 4.17 (t, J¼4.4 Hz,
4H, 2phenylOCH2CH2O), 3.88 (t, J¼4.4 Hz, 4H, 2phenylOCH2CH2O),
3.50e3.81 (m, 56H, 2phenylOCH2CH2O(CH2CH2O)7CH3), 3.38 (s, 6H,
9. (a) Liu, J.; Pang, Y.; Huang, W.; Huang, X.; Meng, L.; Zhu, X.; Zhou, Y.; Yan, D.
Biomacromolecules 2011, 12, 1567; (b) Liu, J.; Huang, W.; Pang, Y.; Zhu, X.; Zhou,
€
2OCH3). 13C NMR (65 MHz, CDCl3,
d, ppm): 159.3, 140.7, 132.9, 132.2,
Y.; Yan, D. Langmuir 2010, 26, 10585; (c) Antonietti, M.; Forster, S. Adv. Mater.
2003, 15, 1323; (d) Chiu, Y. C.; Chen, Y.; Kuo, C. C.; Tung, S. H.; Kakuchi, T.; Chen,
W. C. ACS Appl. Mater. Interfaces 2012, 4, 3387.
132.1, 131.9, 127.9, 127.0, 126.9, 126.5, 120.0, 115.0, 102.4, 90.9, 88.1,
87.7, 71.9, 70.9, 70.6, 69.7, 67.6, 59.1. MALDI-TOF-MS m/z [M]þ 1648,
[MþNa]þ 1671.
10. (a) Lian, S. L.; Liu, C. L.; Chen, W. C. ACS Appl. Mater. Interfaces 2011, 3, 4504; (b)
Hoeben, F. J. M.; Jonkheijm, P.; Meijer, E. W.; Schenning, A. P. H. J. Chem. Rev.
2005, 105, 1491; (c) Chen, B.; Baumeister, U.; Pelzl, G.; Das, M. K.; Zeng, X.;
Ungar, G.; Tschierske, C. J. Am. Chem. Soc. 2005, 127, 16578.
Molecule 4: red solid, 42%. 1H NMR (300 MHz, CDCl3,
d, ppm):
8.73 (dd, J¼6.6 and 3.2 Hz, 4H, Ar), 7.86 (d, J¼8.4 Hz, 4H, Ar),
11. Lee, M.; Cho, B. K.; Zin, W. C. Chem. Rev. 2001, 101, 3869.