Coordinative nanoporous polymers synthesized with hydrogen-bonded columnar liquid crystals

Article abstract of DOI:10.1166/jnn.2012.6600

In this paper, we report the development of nanoporous polymer which demonstrates the coordination property toward zinc porphyrin. A hydrogen-bonded columnar liquid crystalline precursor composed of a triphenylene template and three equivalent of the surr

Full text of DOI:10.1166/jnn.2012.6600

Copyright © 2012 American Scientific Publishers
All rights reserved
Printed in the United States of America
Journal of
Nanoscience and Nanotechnology
Vol. 12, 7885–7895, 2012
Coordinative Nanoporous Polymers
Synthesized with Hydrogen-Bonded
Columnar Liquid Crystals
Shinsuke Ishihara1
ꢀ2ꢀ3ꢀ∗
, Yusuke Furuki , Jonathan P. Hill ,
1
2ꢀ3
2
ꢀ3
4ꢀ∗
Katsuhiko Ariga , and Shinji Takeoka
1Department of Applied Chemistry, Graduate School of Advanced Science and Engineering, Waseda University,
3
-4-1 Okubo, Shinjyuku-ku, Tokyo 169-8555, Japan
2
World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA),
National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
Japan Science and Technology Agency (JST), Core Research for Evolutional Science and Technology (CREST),
Go-bancho, Chiyoda-ku, Tokyo 102-0076, Japan
3
4
Department of Life Science and Medical Bioscience, Graduate School of Advanced Science and Engineering,
Waseda University (TWIns), 2-2 Wakamatsucho, Tokyo 162-8480, Japan
In this paper, we report the development of nanoporous polymer which demonstrates the coor-
dination property toward zinc porphyrin. A hydrogen-bonded columnar liquid crystalline precursor
composed of a triphenylene template and three equivalent of the surrounding dendric amphiphile
bearing a pyridyl head group and a polymerizable aliphatic chain, was covalently fixed by photo-
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polymerization, and then the subsequent selective removal of the template successively resulted
IP: 193.0.129.51 On: Thu, 26 May 2016 02:08:47
in a nanoporous polymer in which the pore wall is modified with pyridyl groups. The nanoporous
Copyright: American Scientific Publishers
polymer reflected the conformation of template, and displayed considerable coordination ability of
the pyridyl groups towards zinc porphyrin. The coordinative nanoporous polymer is promising as a
nano-scaled scaffold for the organization of dyes into functional supramolecular architectures.
Keywords: Nanoporous Polymer, Coordination, Supramolecular Chemistry, Coordination, Liquid
Crystal.
3
2–34
1
. INTRODUCTION
strategies using surfactant templates,
coordination
and nano-segregated
have been developed.
3
5ꢀ36
37–39
polymers,
supramolecular assemblies
Of these, template polymerization
ular columnar liquid crystals, including lyotropic liq-
block copolymers,
Development of nanoscience and nanotechnology1–3
depends strongly on creation of nano-sized structures and
nanospaces as can be found in the various excellent inves-
40–43
44ꢀ45
of supramolec-
4
ꢀ5
6–10
tigations of nanotubes,
nanoparticles,
and nanoporous materials.
inclusion of guest molecules into such nanospaces
nano-layered
46ꢀ47
48
uid crystals
and thermotropic liquid crystals, is
1
1–14
15ꢀ16
structures,
Selective
an effective method for fabrication of size-controlled
nanoporous polymers, and the resulting nanoporous
polymer in which the pore wall is modified with
concentrated functional groups are potentially nanoma-
1
7ꢀ18
and
regulation of the properties of trapped molecules under
dynamic stimuli1
9–24
often results in innovative functions
including advanced sensing,2
5–27
materials sequestration,
28
4
9
terials for use as molecular sieves, in anisotropic
and controlled materials release especially of therapeu-
5
0–52
53
transportation,
enantioselection, or heterogeneous
tic substances.2
9–31
In particular, design and synthesis of
5
4
catalytic applications.
nanoporous materials of specific dimensions and surface
modification has been a subject of considerable research
interest over the past two decades, and various synthetic
Surface modification of nanoporous materials is a crit-
ical issue in the optimization of the affinity of the pore
toward guest molecules. In particular the pyridyl group,
as a typical ligand, is a valuable functional group for
the modification of pore walls due to its coordinative
∗
Authors to whom correspondence should be addressed.
J. Nanosci. Nanotechnol. 2012, Vol. 12, No. 10
1533-4880/2012/12/7885/011
doi:10.1166/jnn.2012.6600
7885

Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals
Ishihara et al.
properties towards metal ions or organometallics. Guest
molecules introduced into a nanopore are sterically and
electronically coupled to each other and are expected
to present cooperative catalytic or electromagnetic func-
tions, which are not present in the isolated unconstrained
hexafluorophosphate (Tokyo Chemical Industry Co., Ltd),
anhydrous potassium carbonate (Kanto Chemical Co.,
Inc), potassium hydrate (Kanto Chemical Co., Inc), anhy-
drous iron(III) chloride (Kanto Chemical Co., Inc), sodium
borohydride (Kanto Chemical Co., Inc), and thionyl chlo-
ride (Kanto Chemical Co., Inc) were used as received.
CHCl was distilled over P O , and all other solvents were
5
5–58
molecules.
In this paper, we report the template polymerization of
a hydrogen-bonded columnar liquid crystalline precursor
for construction of a nanoporous polymer in which the
pore wall is modified with pyridyl groups (Fig. 1). Subse-
quently, the coordinative ability of the nanoporous polymer
due to the pyridyl groups in the pore was confirmed in an
absorption experiment using zinc porphyrin.
3
2
5
used without purification. 21H, 23H-porphine P2H and
21H, 23H-porphine zinc(II) PZn were prepared according
5
9
to Neya’s method.
2.2. General Methods
1H-NMR spectra were recorded from solutions of analytes
2
. EXPERIMENTAL SECTION
dissolved in a deuterated solvent such as CDCl using a
3
JEOL JNM-LA 500 (500 MH ꢁ NMR spectrometer. Elec-
Z
2
.1. Materials
trospray ionization mass spectra (ESI-MS) were recorded
on a Thermo Quest FINNIGAN LCQ DECA mass spec-
trometer. Differential scanning calorimetry (DSC) was
measured on a Rigaku Thermo plus DSC 8230 with a heat-
2
-Methoxyphenol (Kanto Chemical Co., Inc), 1-
bromopentane (Kanto Chemical Co., Inc), trimethylsi-
lyl iodide (Tokyo Chemical Industry Co., Ltd), bro-
moacetic acid ethyl ester (Tokyo Chemical Indus-
try Co., Ltd), methanesulfonic acid (Kanto Chemical
Co., Inc), 3,4-dihydroxybenzaldehyde (Tokyo Chemi-
cal Industry Co., Ltd), 12-bromo-1-dodecanol (Tokyo
Chemical Industry Co., Ltd), benzoyl chloride (Kanto
Chemical Co., Inc), triethylamine (Kanto Chemical
ꢀ
−1
ꢀ
ꢀ
ing and cooling rate of 5 C min from −40 C to 60 C.
X-ray diffraction (XRD) patterns were recorded using a
RIGAKU R-AXIS RAPID-R with Cu Kꢂ radiation at
room temperature. An infrared (IR) spectrum was recorded
at room temperature with a JASCO FI/IR-410 Fourier
transform infrared spectrometer. Temperature dependence
of polarized optical microscopy textures was observed
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Co., Inc), 3,5-dihydroxybenzoic acid methyl ester
IP: 193.0.129.51 On: Thu, 26 May 2016 02:08:47
(
Tokyo Chemical Industry Co., Ltd), methacryloyl
using an OLYMPUS BX51 microscope equipped with a
cross-polarizing filter, an OLYMPUS CCD CS230B color
camera, and a KITAZATO MP-200 DMSH micro-heat
plate. UV-Vis spectra were recorded at room temperature
with a JASCO V-660 spectrophotometer.
Copyright: American Scientific Publishers
chloride (Tokyo Chemical Industry Co., Ltd), 2,6-
di-tert-butyl-p-cresol (Tokyo Chemical Industry Co.,
Ltd), 4-aminopyridine (Kanto Chemical Co., Inc), 1H-
benzotriazole-1-yloxytris(dimethylamino) phosphonium
Fig. 1. Template polymerization of the hydrogen-bonded columnar liquid crystalline precursor TP-DN for construction of the nanoporous polymer
Poly-DN.
7886
J. Nanosci. Nanotechnol. 12, 7885–7895, 2012

Ishihara et al.
Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals
2
2
2
.3. Synthesis of TP
2.3.4. 2,6,10-Tris(ethoxycarbonylmethoxy)-3,7,11-
Tripentyloxytriphenylene
.3.1. 1-Methoxy-2-Pentyloxybenzene
2,6,10-Trihydroxy-3,7,11-tripentyloxytriphenylene
-Methoxyphenol (12.4 g, 0.100 mol), 1-bromopentane
(200 mg, 0.374 mmol), ethyl bromoacetate (200 mg,
(18.1 g, 0.121 mol), and anhydrous K CO (16.6 g,
2 3
1
.20 mmol), and anhydrous K CO (500 mg, 3.62 mmol)
2
3
ꢀ
0
.120 mol) were stirred in refluxing CH CN (150 ml)
3
were stirred in DMF (10 ml) at 65 C for 12 h. The result-
ing light yellow suspension was poured into 10% aqueous
for 12 h then the solvent was evaporated under reduced
pressure. The crude residue was dissolved in chloroform,
washed with 10% aqueous HCl, and dried over Na SO .
The light yellow solution was concentrated under reduced
pressure followed by purification by column chromatogra-
phy on silica gel (CHCl /hexane: 1/1) which afforded 1-
methoxy-2-pentyloxybenzene as a colorless liquid (23.1 g,
7
HCl and extracted twice with CHCl . The solution was
3
2
4
concentrated under reduced pressure and purified by col-
umn chromatography on silica gel (ethyl acetate/hexane:
1/3) to obtain 2,6,10-tris(ethoxycarbonylmethoxy)- 3,7,11-
3
tripentyloxytriphenylene as a white solid (199 mg, 67.1%).
1
H-NMR (500 MHz, CDCl ): ꢃ 7.95, 7.80 (2s, 6H, ArH),
3
1
9.0%). H-NMR (500 MHz, CDCl ): ꢃ 6.89 (m, 4H,
3
4
4
1
.86 (s, 6H, OCH COO), 4.30(q, 6H, COOCH CH ),
2
2
3
ArH), 3.85 (s, 3H, OCH ), 3.36 (t, 2H, OCH ), 1.98 (m,
3
2
.26(t, 6H, OCH ), 1.99(m, 6H, CH ) 1.57(m, 6H, CH ),
2
2
2
2
H, CH ), 1.58 (m, 2H, CH ), 1.47 (m, 2H, CH ), 0.99
2 2 2
.48(m, 6H, CH ), 1.32(t, 9H, COOCH CH ), 0.99(t, 9H,
2
2
3
+
(
t, 3H, CH ). ESI-MS: m/z = 293ꢄ6 [M+H] .
+
3
CH ). ESI-MS: m/z = 794ꢄ1 [M+H] .
3
2
.3.2. 2,6,10-Trimethoxy-3,7,11-
Tripentyloxytriphenylene
2
.3.5. 2,6,10-Tris(carboxymethoxy)-3,7,11-
Tris(pentyloxy)Triphenylene (TP)
Anhydrous FeCl3 (16.7 g, 0.103 mol) was added
to a stirred solution of 1-methoxy-2-pentyloxybenzene
2
,6,10-Tris(ethoxycarbonylmethoxy)-3,7,11-tris(pentyl
oxy)triphenylene (100 mg, 0.0252 mmol) and methane
sulfonic acid (1 drop) were dissolved in formic acid
(
10.0 g, 0.342 mmol) and H SO4 (1 drop) in CH Cl
2 2 2
(
24 ml). After 45 min, the reaction was quenched
(10 ml). The solution was refluxed for 24 h then cooled
ꢀ
with CH OH and left at 0 C for 1 h. The resulting
precipitate was filtered, and the residue was purified
by flash column chromatography on silica gel (chlo-
roform/hexane: 4/1) to obtain 2,6,10-trimethoxy-3,7,11-
tripentyloxytriphenylene (600 mg, 9.1%) as a light brown
solid. The structural isomer (2,6,11-trimethoxy-3,7,10-
3
to room temperature. Distilled water was then poured
into the solution, and the resulting white precipitate was
collected using a sintered glass filter, and washed with
distilled water three times. The white solid was dried
in vacuo. to obtain 2,6,10-tris(carboxymethoxy)-3,7,11-
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1
tris(pentyloxy)triphenylene TP (80.0 mg, 89.6%). H-
NMR (500 MHz, CDCl /CD OD: 4/1): ꢃ 7.91, 7.75
tripentyloxytriphenylene) was removed during this step.
3
3
1
H-NMR (500 MHz, CDCl ): ꢃ 7.85, 7.82 (2S, 6H, ArH),
3
(2s, 6H, ArH), 4.86 (s, 6H, OCH COO), 4.26 (t, 6H,
2
4
.26 (t, 6H, OCH ), 4.10 (s, 9H, OCH ), 1.97 (m, 6H,
2
3
OCH ) 1.98 (m, 6H, CH ),1.57 (m, 6H, CH ), 1.48
2
2
2
CH ), 1.58 (m, 6H, CH ), 1.51 (m, 6H, CH ), 0.87 (t, 9H,
13
2
2
2
(m, 6H, CH ), 0.99 (t, 9H, CH ). C-NMR (500 MHz,
2
3
+
CH ). ESI-MS: m/z = 599ꢄ8 [M+Na] .
3
CDCl /CD OD): ꢃ 171.8, 149.7, 147.5, 125.6, 123.2,
3
3
110.8, 100.9, 69.5, 68.0, 29.2, 28.5, 22.7, 14.1. ESI-MS:
−
2
.3.3. 2,6,10-Trihydroxy-3,7,11-
Tripentyloxytriphenylene
m/z = 707ꢄ6 [M−H] . Anal. calcd. for C H O : C,
3
9
48 12
66.09; H, 6.83; O, 27.09. Found: C, 67.2; H, 6.93.
Trimethylsilyl iodide (1.04 g, 5.20 mmol) was added
to stirred solution of 2,6,10-trimethoxy-3,7,11-
2.4. Synthesis of DN
a
tripentyloxytriphenylene (600 mg, 1.04 mmol) in chlo-
roform (10 ml) at room temperature, and the solution
was stirred at 45 C for 2 h. Then, the solution was
2
.4.1. 3,4-Bis(12-Hydroxydodecyloxy)Benzaldehyde
ꢀ
3,4-Dihydroxybenzaldehyde (3.45 g, 0.0250 mol), 12-
bromo-1-dodecanol (13.3 g, 0.0500 mol), and anhydrous
K CO (13.9 g, 0.100 mol) were stirred in DMF (150 ml)
at 70 C for 4 h, and then H O was added to the solution.
The precipitation was collected on a sintered glass filter,
poured into 10% aqueous HCl, and extracted with CHCl3
three times. The solution was dried with MgSO , and
4
2
3
ꢀ
concentrated under reduced pressure. The purification of
the brown solid by column chromatography on silica gel
2
(ethyl acetate/hexane: 1/5) afforded 2,6,10-trihydroxy-
and washed with H O twice. The crude product was dis-
2
3
3
6
,7,11-tripentyloxytriphenylene as a white solid (200 mg,
solved in CHCl , and then recrystalized from CH OH to
3
3
1
6.0%). H-NMR (500 MHz, CDCl ꢁ: ꢃ 7.85, 7.77 (2S,
afford 3,4-bis(12-hydroxydodecyloxy)-benzaldehyde as a
3
1
H, ArH), 5.93 (s, 3H, OH), 4.17 (t, 6H, OCH ), 1.92
white solid (11.2 g, 88.5%). H-NMR (500 MHz, CDCl ):
2
3
(
m, 6H, CH ), 1.48 (m, 12H, CH ), 0.99 (t, 9H, CH ).
ꢃ 9.82 (s, 1H, CHO), 7.41 (dd, 1H, ArH), 7.39 (d, 1H,
2
2
3
+
ESI-MS: m/z = 535ꢄ8 [M+H] .
ArH), 6.95 (d, 1H, ArH), 4.07 (t, 2H, ArOCH ), 4.05
2
J. Nanosci. Nanotechnol. 12, 7885–7895, 2012
7887

Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals
Ishihara et al.
(
t, 2H, ArOCH ), 3.63 (t, 4H, CH OH), 1.84 (m, 4H, 2.4.5. 3,5-Bis-[3,4-bis-(12-Benzoyloxydodecyloxy)
2
2
CH ), 1.56 (m, 4H, CH ), 1.47 (m, 4H, CH ), 1.35–1.28
Benzyloxy]Benzoic Acid Methyl Ester
2
2
2
+
(
br, 28H, CH ). ESI-MS: m/z = 507ꢄ9 [M+H] .
2
3
,4-Bis(12-benzoyloxydodecyloxy)benzyl chloride was
added to a suspension of 3,5-dihydroxybenzoic acid
methyl ester (1.17 g, 0.00696 mol) and K CO (2.00 g,
2
.4.2. 3,4-Bis(12-Benzoyloxydodecyloxy)-Benzaldehyde
2
3
Benzoyl chloride (6.70 g, 0.0477 mol) was added
to a stirred solution of 3,4-bis(12-hydroxydodecyloxyl)-
0.0144 mol) in DMF (100 ml). The solution was stirred
ꢀ
for 24 h at 75 C. H O was added to the solution and
2
benzaldehyde (11.0 g, 0.0217 mol) and triethylamine
the precipitate was collected on a glass filter, and washed
ꢀ
(
5.10 g, 0.0504 mol) in CH Cl2 (100 ml) at 0 C.
twice with H O. The crude product was purified by col-
2
2
The solution was allowed to warm to room tempera-
ture, and then stirred for an additional 3 h. Then the
solution was washed with 10% aqueous HCl, dried with
Na SO , and the solvent was evaporated under reduced
umn chromatography on silica gel (ethylacetate/hexane:
1/2) affording 3,5-bis[3,4-bis(12-benzoyloxydodecyloxy)
benzyloxy]benzoic acid methyl ester as pale yellow wax
1
2
4
(6.12 g, 56.1%). H-NMR (500 MHz, CDCl ): ꢃ 8.03 (d,
3
pressure. The crude residue was purified by column chro-
matography on silica gel (ethylacetate/hexane: 1/5) to
afford 3,4-bis(12-benzoyloxydodecyloxy)benzaldehyde as
8H, BzH), 7.54 (t, 4H, BzH), 7.43 (t, 8H, BzH), 7.28 (d,
2H, ArH), 6.95-6.86 (m, 6H, ArH), 6.79 (t, 1H, ArH),
4.96 (s, 4H, Bzl-H), 4.30 (2t, 8H, ArOCH ), 3.99 (m, 8H,
2
1
a white solid (13.1 g, 84.4%). H-NMR (500 MHz,
ArOCH ), 3.90 (s, 3H, COOCH ), 1.81 (m, 8H, CH ),
2
3
2
CDCl ): ꢃ 9.83 (s, 1H, CHO), 8.03 (d, 4H, BzH), 7.54
3
1.76 (m, 8H, CH ), 1.44 (m, 16H, CH ), 1.34–1.29 (br,
2
2
(
6
t, 2H, BzH), 7.43 (t, 4H, BzH), 7.41-7.26 (m, 2H, ArH),
.94 (d, 1H, ArH), 4.31 (t, 4H, CH OBz), 4.07 (t, 2H,
+
4
8H, CH ). ESI-MS: m/z = 1566ꢄ9 [M+H] .
2
2
ArOCH ), 4.04 (t, 2H, ArOCH ), 1.84 (m, 4H, CH ), 1.76
2
2
2
2
.4.6. 3,5-Bis[3,4-bis(12-Hydroxydodecyloxy)
(
m, 4H, CH ), 1.44 (m, 8H, CH ), 1.35–1.29 (br, 24H,
2
2
Benzyloxy]Benzoic Acid
+
CH ). ESI-MS: m/z = 715ꢄ8 [M+H] .
2
KOH (3.0
was added to
benzoyloxydodecyloxy)benzyloxy]benzoic acid methyl
g
0.0535 mol) in H O (15 ml)
2
2
.4.3. 3,4-Bis(12-Benzoyloxydodecyloxy)Benzyl Alcohol
a
solution of 3,5-bis[3,4-bis(12-
Sodium borohydride (3.00De gl i ,v e r0e. 0d 7 b9 3y In mg oe ln) ta wt oa :s Purdue University Libraries
ester (5.00 g, 0.00319 mol) in THF/CH OH (100 ml/
3
slowly added to
benzoyloxydodecyloxy)benzaldehyd Ce o( 1p3 y. 0r i gg ,h 0t :. 0 A1 8m 2e mr i oc la) n Scientific Publishers
in THF/ ethanol (200 ml/ 40 ml) at 0 C, and the solution
a
s oI Pl u:ti 1o 9n 3.0 o. 1f 29 .35 , 41 - bOi sn( 1: 2T -hu, 26 May 2016 02:08:47
30 ml) and the solution was refluxed for 12 h. The organic
solvent was evaporated under reduced pressure and the
ꢀ
solid was washed with 3% NaOH aq. on a sintered glass
filter. The solid was dissolved in CHCl3 and washed
with 10% HCl. The solution was dried with Na SO ,
and concentrated under reduced pressure. The white
solid was dried in vacuo to afford 3,5-bis[3,4-bis(12-
hydroxydodecyloxy)benzyloxy]benzoic acid as a white
solid (3.35 g, 92.4%). H-NMR (500 MHz, CD OD):
ꢃ 7.29 (d, 2H, ArH), 6.98-6.87 (m, 6H, ArH), 6.78 (t,
was stirred for 2 h at room temperature. Then the solution
ꢀ
was cooled to 0 C, and 10% HCl aq. was slowly added.
2
4
After the generation of H2 gas had ceased the organic
solvent was removed under reduced pressure. The result-
ing precipitate was collected on a glass filter, and washed
twice with water. The product was dried in vacuo to
1
3
afford 3,4-bis(12-benzoyloxydodecyloxy)benzyl alcohol
as a white solid (12.8 g, 98.1%). 1H-NMR (500 MHz,
1H, ArH), 4.96 (s, 4H, Bzl-H), 3.99 (m, 8H, ArOCH ),
2
CDCl ): ꢃ 8.04 (d, 4H, BzH), 7.54 (t, 2H, BzH), 7.43 (t,
3
3.56 (t, 8H, CH OH), 1.80 (m, 8H, CH ), 1.54 (m, 8H,
2
2
4
2
H, BzH), 6.92 (s, 1H, ArH), 6.85 (s, 2H, ArH), 4.60 (d,
H, CH OH), 4.31 (t, 4H, CH OBz), 3.99, 3.98 (2t, 4H,
CH ), 1.47 (m, 8H, CH ), 1.29 (br, 56H, CH ). ESI-MS:
m/z = 1134ꢄ5 [M−H] .
2
2
2
2
2
−
ArOCH ), 1.83–1,73 (m, 8H, CH ), 1.49–1.42 (m, 8H,
2
2
CH ), 1.38–1.28 (br, 24H, CH ). ESI-MS: m/z = 718ꢄ2
2
2
+
[
M+H] .
2.4.7. 3,5-Bis[3,4-bis(12-Methacryloxydodecyloxy)
Benzyloxy]Benzoic Acid
2
.4.4. 3,4-Bis(12-Benzoyloxydodecyloxy)Benzyl Chloride
Methacryloyl chloride (220 mg, 2.10 mmol) was added
Thionyl chloride (10.0 g, 0.0840 mol) was slowly added
to a solution of 3,4-bis(12-benzoyloxydodecyloxy)benzyl
alcohol (10.0 g, 0.0139 mol) and one drop of DMF in
to a stirred CH Cl solution (50 ml) of 3,5-bis[3,4-bis
2 2
(12-hydroxydodecyloxy) benzyloxy]benzoic acid (400 mg,
0.352 mmol), triethylamine (214 mg, 2.10 mmol), and
ꢀ
CHCl (100 ml), and the solution was refluxed for 3 h.
2,6-di-tert-butyl-p-cresol (10 mg, 0.0454 mmol) at 0 C,
3
Then the solution including the excess thionyl chloride was
and then the solution was stirred at room temperature
for 8 hr. The solution was washed with 10% HCl aq.,
and dried over Na SO . Solvents were evaporated under
removed under a dried N stream. Quantitative conversion
2
to the benzyl chloride derivative was confirmed by thin
layer chromatography, and all of the pale yellow residue
was used in the next synthesis without further purification.
2
4
reduced pressure, and the residue dissolved in pyridine
(30 ml). To the stirred pyridine solution, 3 ml of H O
2
7888
J. Nanosci. Nanotechnol. 12, 7885–7895, 2012

Ishihara et al.
Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals
and 2,6-di-tert-butyl-p-cresol (10 mg, 0.0454 mmol) were
added, and the mixture was refluxed for 10 min. The solu-
tion was extracted with CHCl /10%HCl aq., and the crude
3
product was purified by column chromatography on silica
gel (CHCl /CH OH: 20/1), and the product freeze dried
3
3
from benzene to afford 3,5-bis[3,4-bis(12-methacryloxy
dodecyloxy)benzyloxy]benzoic acid as a white powder
(
0
280 mg, 56.5%). The product was stored with care at
ꢀ
1
C in the dark. H-NMR (500 MHz, CD Cl ꢁ: ꢃ 7.35
2 2
(
d, 2H, Ar-H), 6.98-6.86 (m, 6H, Ar-H), 6.83 (t, 1H,
Ar-H), 6.09 (s, 4H, OCO(CH3ꢁ CH ), 5.53 (m, 4H,
2
OCO(CH3ꢁ CH ), 4.97 (s, 4H, Bzl-H), 4.13 (2t, 8H,
2
ArOCH CH ), 4.00, 3.98 (2t, 8H, CH OCO(CH ) CH ),
2
2
2
3
2
1
.93 (s, 12H, OCO(CH3) CH ), 1.67 (m, 8H, CH ), 1.63
2
2
(
m, 8H, CH ), 1.36–1.25 (br, 56H, CH ꢁ.
2
2
Fig. 2. IR spectra of the 1:3 (red line), 1:1 (green line), and 2:1 (blue
line) molar complex of TP and DN.
2
.4.8. 3,5-Bis-[3,4-bis-(12-Methacryloxydodecyloxy)-
Benzyloxy]-N-pyridin-4-yl-Benzamide (DN)
2
1
5
1
1
6
.01 (s, 12H, OCO(CH3) CH ), 1.88 (m, 8H, CH ),
3
,5-Bis[3,4-bis(12-methacryloxydodecyloxy)benzyloxy]
2
2
.75 (m, 8H, CH ), 1.56 (m, 8H, CH ), 1.47–1.39 (br,
benzoic acid (250 mg, 0.178 mmol), 1H-benzotriazole-
-yloxytris(dimethylamino)phosphonium hexafluorophos-
phate (102 mg, 0.231 mmol), and triethylamine (23.4 mg,
.231 mmol) in CH Cl2 (10 ml) and DMF (5 ml)
2
2
1
3
6H, CH ). C-NMR (500MHz, CD Cl ): ꢃ 167.7, 166.1,
1
2
2
2
60.7, 151.0, 149.71, 149.68, 145.59, 137.2, 136.7, 129.3,
25.0, 121.0, 114.15, 114.10, 114.01, 106.7, 106.0, 70.9,
0
2
9.7, 69.6, 65.1, 30.00, 29.97, 29.92, 29.79, 29.76, 29.74,
were stirred for 10 min at room temperature. Then 4-
aminopyridine (165 mg, 1.75 mmol) was added, and the
mixture was stirred for 12 h at room temperature. The light
yellow suspension was poured into distilled water, and the
precipitate was washed with distilled water an a sintered
+
29.65, 18.4. ESI-MS: m/z = 1485ꢄ5 [M+H] . Anal. calcd.
for C90
H N O15: C, 72.84; H, 9.10; N, 1.89; O, 16.17.
134 2
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Found: C, 74.1; H, 9.31.
IP: 193.0.129.51 On: Thu, 26 May 2016 02:08:47
Copyright: American Scientific Publishers
glass filter three times. The solid was dissolved in CHCl3
and dried over MgSO . The concentrated residue was puri-
2.5. Preparation of TP-DN
4
fied by flash column chromatography on silica gel (chloro-
form/methanol: 15/1), and then freeze dried from benzene
to afford 3,5-bis[3,4-bis(12-methacryloxydodecyloxy)
benzyloxy]-N-pyridin-4-yl-benzamide (160 mg, 60.6%) as
Just before mixing, DN was purified by column chro-
matography on silica gel (CHCl /CH OH: 20/1) to
3
3
remove the stabilizer, 2,6-di-tert-butyl-p-cresol, and then
DN was freeze dried from benzene in vacuum. Pow-
dered TP (7.1 mg, 0.01 mmol) and DN (44.6 mg,
0.03 mmol) were mixed in a 1:3 molar ratio, and dis-
ꢀ
a white powder. The product was stored with care at 0 C
1
in the dark. H-NMR (500 MHz, CD Cl ): ꢃ 8.60 (d, 2H,
2
2
Pyridine-H), 8.20 (s, 1H, CONH), 7.69 (d, 2H, Pyridine-
H), 7.17 (d, 2H, Ar-H), 7.06-6.97 (m, 6H, Ar-H), 6.89
solved in benzene/CH OH. The organic solvents were
3
ꢀ
evaporated at 30 C in dark. The residue was again
(
t, 1H, Ar-H), 6.15 (s, 4H, OCO(CH3) CH ), 5.63 (m,
2
4
H, OCO(CH3) CH ), 5.01 (s, 4H, Bzl-H), 4.19 (m,
2
8
H, ArOCH CH ), 4.07 (t, 8H, CH OCO(CH ) CH ),
2
2
2
3
2
Table I. Phase transition and lattice parameters of TP-DN, Poly-TP-
DN, and Poly-DN estimated by DSC and XRD experiments.
Phase
Lattice
Diffraction
Compound
transition
constant (Å) obsd (Å) Miller index
TP-DN
G-12 (-8.7) →
43.6
37.8
(100)
(100)
Col 39
hd
(-0.4) →Iso
Poly-TP-DN
Poly-DN
—
—
42.5
41.4
36.8
35.9, 20.7, (100), (110)
3.9 (210)
1
ꢀ
(
a) Transition temperatures ( C) and enthalpies in parentheses (cal/g) were mea-
ꢀ
sured by DSC (second heating scan at 5 C/min). The designation G, Col , and Iso
represent glassy, hexagonal disordered columnar, and isotropic phases, respectively.
ꢀ
Fig. 3. DSC trace of TP-DN at a scan rate of 5 C/min.
J. Nanosci. Nanotechnol. 12, 7885–7895, 2012
7889

Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals
Ishihara et al.
Fig. 4. Thermal phase transition behaviors of TP-DN observed by variable temperature polarized optical microscopy.
dissolved in benzene, and freeze dried in vacuum. The
viscous solid TP-DN was stored at –20 C in the dark.
work by taking a cooperative hydrogen-bonding system
ꢀ
60ꢀ61
and molecular symmetry into account.
The estimated
diameter of the pore prepared by the cross-linking pho-
topolymerization followed by the removal of the template
TP is approximately 1.5 nm. Based on the size of the
template TP, the resulting nanopore should be large
enough to accept heterogeneous guest molecules such as
zinc porphyrin PZn.
2
.6. Photo-Polymerization of TP-DN
TP-DN was sandwiched between two glass slides and
heated at 50 C. The hot melt sample was cooled to room
ꢀ
ꢀ
temperature, and then cooled to −20 C for 24 hr in the
dark. Then the sample was allowed to warm up at room
temperature. The sample was irradiated using an ultravi-
The liquid crystalline properties of TP-DN were charac-
terized by infrared spectroscopy (IR), differential scanning
calorimetry (DSC), polarized optical microscopy (POM),
and X-ray diffractometry (XRD). The phase transition
behavior and lattice parameter of TP-DN are summarized
ꢀ
olet light at 0 C (365 nm, 5 W) for 180 min. The two
adhered glass slides were mechanically separated, and the
glass slide attached with the polymeric film was soaked
in methanol. The free-standing film Poly-TP-DN with a
thickness of c.a. 15 ꢅm was obtained. The time course IR
spectra of TP-DN during UV irradiation were measured to
investigate the progress of photopolymerization. The liq-
uid crystalline thin film of TP-DN was cast on a NaCl
crystal and IR spectra were recorded over time.
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in Table I. An IR study on TP-DN (Fig. 2) proved the
IP: 193.0.129.51 On: Thu, 26 May 2016 02:08:47
Copyright: American Scientific Publishers
formation of complementary hydrogen bonding between
the carboxylic acid of TP and the pyridyl group of DN.
−1
The IR absorption peak of TP at 1729 cm , assigned to
the free C O stretching, disappeared after being mixed
with more than three equivalents of DN. The IR absorp-
tion peak assigned to the hydrogen-bonded C O stretch-
ing should have shifted to a lower frequency compared to
that of the free C O stretching and, in this case, became
completely overlapped with the other strong IR absorption
peaks derived from ester and amide bonds. A DSC study
2
.7. Removal of TP from Poly-TP-DN
Poly-TP-DN was soaked in 4 ml CH Cl /CH OH (1:1
2
2
3
in volume), and TP was extracted to the solution. The
time course UV-vis spectra were measured to estimate
the percentage of TP extracted into solution. Thus, the
nanoporous polymer Poly-DN was obtained.
3. RESULTS AND DISCUSSION
3
.1. Synthesis and Assembly
Our synthetic strategy for constructing a nanoporous
polymer is summarized in Figure 1. The hydrogen-bonded
columnar liquid crystalline precursor TP-DN composed
of the proton donating triphenylene derivative TP [2,6,10-
tris(carboxymethoxy)-3,7,11-tris(pentyloxy)triphenylene]
and three equivalents of the proton accepting den-
dritic amphiphile bearing a pyridyl head group and
four polymerizable aliphatic chains DN [3,5-bis-[3,4-
bis-(12-methacryloxydodecyloxy)-benzyloxy]-N-pyridine-
4
-yl-benzamide] were designed based on our previous
Fig. 5. 2D-XRD pattern of TP-DN.
7890
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Ishihara et al.
Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals
ꢀ
measurements on a thin film of TP-DN at 20 C (Fig. 5)
are consistent with formation of a hexagonal disordered
columnar liquid crystal. The X-ray diffraction pattern of
TP-DN gave a sharp peak at 37.8 Å and a diffuse halo
peak around 4.4 Å. The sharp peak at 37.8 Å is assigned
to the diffraction from the d100 face of a hexagonal lattice.
The other diffraction peaks (e.g., d110) were too weak to be
detected in the low angle region due to a minimum in the
6
2
form factor. The diffuse halo was assigned to aliphatic
chain packing in a molten state, and the absence of sharp
diffraction peaks in the wide angle region indicates an
unequally-spaced intracolumnar packing.
Covalent fixation of the hydrogen-bonded columnar liq-
uid crystalline precursor TP-DN was accomplished by
photopolymerization. The liquid crystalline thin film TP-
DN prepared between two slide glasses was mechanically
sheared to clarify the birefringence, and the film was irra-
Fig. 6. The time course IR spectra of TP-DN during
photopolymerization.
ꢀ
diated using ultraviolet light (365 nm, 5 W) at 0 C for
1
80 min. The time course IR spectra (Fig. 6) of TP-DN
−1
on TP-DN (Fig. 3) demonstrated its thermotropic liquid
around the IR band at 937 cm (assigned to the C
C
ꢀ
ꢀ
crystalline properties between −12 C and 37 C on heat-
stretching vibration of the methacryloyl groups) revealed
that about 80% of the methacryloyl groups finally con-
tributed to the cross-linking photopolymerization. After the
two slide glasses were mechanically separated, the slide
glass holding the polymerized liquid crystalline film was
ing. A single phase transition from an isotropic state to a
ꢀ
crystalline state was observed at −17 C on cooling, prob-
ably because the methacryloyl group at the tail of alkyl
chains obstructs sterically the self-organization process.
POM observation of TP-DN (Fig. 4) also supports the
soaked in CH OH to peal off the polymerized film from
3
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DSC result since TP-DN exhibited birefringence up to
the glass slide. Thus, a free standing film of Poly-TP-DN
(ca. 15 ꢅm thick) was successfully obtained (Fig. 7(a)).
The resulting film was insoluble in most organic solvents
IP: 193.0.129.51 On: Thu, 26 May 2016 02:08:47
ꢀ
5 C on heating, and the polarized texture was isotropic
3
Copyright: American Scientific Publishers
ꢀ
at 0 C on cooling from a hot melt state. X-ray diffraction
Fig. 7. Images of (a) Poly-TP-DN, (b) Poly-DN, (c) Poly-DN after soaking in PZn solution, and (d) Poly-DN after soaking in P2H solution.
J. Nanosci. Nanotechnol. 12, 7885–7895, 2012
7891

Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals
Ishihara et al.
Fig. 8. (a) 2D-XRD pattern and (b) polarized optical microscopic observation both of Poly-TP-DN.
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Copyright: American Scientific Publishers
Fig. 9. (a) Time dependency of UV-Vis spectra and (b) percentage of extracted template TP from Poly-TP-DN into extractant solvent CH Cl /CH OH.
2
2
3
Fig. 10. (a) 2D-XRD pattern and (b) polarized optical microscopic observation of Poly-DN.
7892
J. Nanosci. Nanotechnol. 12, 7885–7895, 2012

Ishihara et al.
Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals
as usually are cross-linked polymers. The POM texture
and XRD pattern of Poly-TP-DN were almost identical
to those of TP-DN prior to photopolymerization (Fig. 8).
Moreover, the invariable POM texture and XRD patterns
Poly-DN (0ꢄ91 ꢅmol based on pyridine units) was soaked
in a concentrated CH Cl solution of TP (3ꢄ7 ꢅmol),
2
2
Py (17ꢄ0 ꢅmol), and DN (28ꢄ1 ꢅmol), UV-vis measure-
ment revealed that TP was selectively adsorbed by Poly-
DN (Fig. 11(a)). Subsequent extraction of the contents
absorbed in the pores with CH OH/CH Cl and analysis
ꢀ
of Poly-TP-DN at 100 C, which is above the melting
point of TP-DN, proved the robust fixation of the colum-
nar structure by cross-linked photo-polymerization.
Subsequent removal of TP from Poly-TP-DN was con-
ducted by selective cleavage of hydrogen-bonding with
3
2
2
of the extract by using UV-Vis spectrometry (Fig. 11(b))
revealed that the extract was identical with simple TP, and
the binding affinity of TP to Poly-DN was at least ten
times higher than that of Py. In addition, Poly-DN quan-
titatively absorbed the original template TP. These results
indicate that Poly-DN memorizes the conformation of the
TP template molecule leading us to the assumption that
the diameter of the pores are approximately 1.5 nm and
that the pyridyl groups within the pore are arranged in a
quite symmetric manner reflecting the conformation of TP.
Finally, we investigated the coordinative ability of Poly-
DN to zinc porphyrin. The molecular diameter of the por-
phyrin ring is approximately 1 nm, and so it is small
enough to be accommodated in the nanoporous polymer
formed after the removal of the 1.5 nm template TP. Poly-
DN films were soaked in a 20 ꢅM solution of zinc por-
phyrin PZn or free-base porphyrin P2H for 3 hr, and the
color variations of the films derived from absorption of
the porphyrin were observed. Poly-DN film soaked in PZn
solution became deep purple whereas Poly-DN soaked in
a polar-protic solvent such as CH OH. The time course
3
plots (Fig. 9) of the percentage of TP extracted into
CH OH/CH Cl solution, which was measured by UV-Vis
3
2
2
titration at 277 nm and 303 nm, indicate that about 82%
of TP was finally removed from Poly-TP-DN. In addi-
tion, the colorless transparent appearance of the resulting
film Poly-DN compared with the light brown film Poly-
TP-DN also strongly suggest that most of the TP was
removed. (Fig. 7(b)). X-ray diffraction patterns of Poly-
DN (Fig. 10(a)) revealed three distinct peaks at 35.9 Å,
2
1
0.7 Å, and 13.9 Å, with the ratios of d-spacing values at
−1/2
−1/2
: 3
: 7 . Thus, the peaks could be assigned to the
d100, d110, and d210 faces of a hexagonal columnar lattice,
respectively. In addition, the column diameter of Poly-DN
is identical to that of Poly-TP-DN. Therefore, we can state
that the removal of the template TP was successful and
did not cause decomposition of the hexagonal structured
framework. Only minor changes were detected in POM
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P2H solution stained light pink, indicating that coordina-
IP: 193.0.129.51 On: Thu, 26 May 2016 02:08:47
tion of zinc with pyridine is a crucial factor for the strong
images (Fig. 10(b)).
Copyright: American Scientific Publishers
absorption of the porphyrin molecules (Figs. 7(c and d)).
The solid state UV-Vis spectra of PZn in Poly-DN con-
tained a Q-band at 537 nm and Soret band at 408 nm,
(Fig. 12(a)). The Q-band at 537 nm is identical with that
3
.2. Guest Binding
The construction of nanopores that reflect the confor-
mation of the template TP was confirmed by competi-
tive absorption experiments between the original template
TP and pyrene butyric acid Py. Py is an ideal com-
petitive guest molecule against TP since it possesses a
carboxylic acid moiety, is of smaller size than TP, and
has a characteristic UV-Vis spectrum. When a piece of
of PZn in pyridine/CH Cl (1:10), proving that all PZn
2 2
molecules absorbed in Poly-DN were coordinated by the
pyridyl groups. The Soret-band at 408 nm was still red-
shifted by 3 nm compared with that of PZn at 405 nm in
pyridine/CH Cl (1:10), suggesting that PZn in Poly-DN
2
2
Fig. 11. (a) Time dependency of UV-Vis spectra of a CH Cl solution containing TP (0ꢄ06 ꢅmol), Py (0ꢄ27 ꢅmol), and DN (0ꢄ45 ꢅmol) after the
2
2
addition of Poly-DN (0ꢄ7 ꢅmol based on pyridine unit); (b) UV-Vis spectra of the contents extracted from Poly-DN which was soaked in a concentrated
CH Cl solution of TP (3ꢄ7 ꢅmol), Py (17ꢄ0 ꢅmol), and DN (28.1 mmol) for 1 h (solid line). The dotted line is UV-Vis spectrum of a diluted portion
2
2
of the original immersion solution.
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Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals
Ishihara et al.
Fig. 12. (a) UV-Vis spectrum of PZn in Poly-DN (solid line) and PZn in CH Cl -pyridine (dashed line); (b) Estimated structure of PZn coordinated
2
2
in the nanoporous polymer Poly-DN. One PZn molecule in the pore occupies two stratum of column.
is arranged to form a J-aggregated superstructure accord-
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Received: 29 May 2012. Accepted: 19 June 2012.
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