Conjugated microporous polymers consisting of tetrasubstituted [2.2]Paracyclophane junctions

Article abstract of DOI:10.1002/pola.26600

Conjugated microporous polymers (CMPs) were synthesized from the tetrasubstituted [2.2]paracyclophane skeleton as a tetra-functional building block using Hay coupling, Sonogashira-Hagihara cross-coupling, and Yamamoto coupling. The CMPs exhibited microporosity (less than 2 nm) and large surface areas (up to approximately 1000 m² g^-1). The CMPs consisted of relatively uniform particles and dispersed in organic solvents. Copyright

Full text of DOI:10.1002/pola.26600

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Conjugated Microporous Polymers Consisting of Tetrasubstituted
[2.2]Paracyclophane Junctions
Yasuhiro Morisaki, Masayuki Gon, Yoshiki Chujo
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku,
Kyoto 615-8510, Japan
Correspondence to: Y. Morisaki (E-mail: ymo@chujo.synchem.kyoto-u.ac.jp) or Y. Chujo (E-mail: chujo@chujo.synchem.kyoto-u.ac.jp)
Received 18 December 2012; accepted 24 January 2013; published online
DOI: 10.1002/pola.26600
KEYWORDS: conjugated polymers; micropore; networks; [2.2]paracyclophane; polycondensation
INTRODUCTION [2.2]Paracyclophane, which contains two
benzene rings,1 has attracted considerable attention with
regard to its structure, reactivity, and physical properties. A
number of [2.2]paracyclophane derivatives have been pre-
pared so far, and their unique properties derived from the
characteristic interactions between the stacked p-electron
systems have been investigated in detail.1–3 Recently, we
focused on [2.2]paracyclophane and synthesized through-
space conjugated oligomers and polymers by incorporating
[2.2]paracyclophane into the conjugated polymer back-
bone.4–7 These polymers exhibited an extension of p-conju-
gation length via the through-space interaction.8 In addition,
end-capping of the through-space conjugated polymers
allowed for fluorescence resonance energy transfer from the
stacked p-electron systems to the end-capped p-electron
systems.8,9
In this study, we focused on the structure of [2.2]paracyclo-
phane to construct a network for a CMP. In particular, we
selected
a 4,7,12,15-tetrasubstituted [2.2]paracyclophane
skeleton with a crisscross structure as the junction of the
CMP. Three types of CMPs consisting of tetrasubstituted
[2.2]paracyclophane junctions were synthesized from
[2.2]paracyclophane monomers with different sizes by Hay
coupling,50 Sonogashira–Hagihara cross-coupling,51,52 and
Yamamoto coupling.53 All CMPs were found to be micropo-
rous with large surface areas on the basis of nitrogen gas
sorption studies. Further characterization of the obtained
CMPs by cross-polarization magic angle spinning (CP/MAS)
13C NMR, FTIR, X-ray diffraction (XRD), and scanning elec-
tron microscopy (SEM) were also performed.
EXPERIMENTAL
General
Microporous polymers such as metal organic frameworks,10–20
porous coordination polymers,10–20 and microporous organic
polymers21–33 have been extensively investigated. Because
these polymers possess micropores and large surface areas, it
is expected that they can be applied as catalysts,34–38 gas stor-
age materials,26,31,33,39–43 and gas separation materials.34,44,45
Generally, they are composed of organic compounds whose
functional groups can be readily designed; thus, the sizes and
shapes of the micropores can be controlled at the molecular
level. Recently, p-conjugated frameworks have been used for
network polymers. This new class of microporous network
polymers is called conjugated microporous polymers
(CMPs),46,47 and they consist of only rigid p-conjugated skele-
tons and of micropores that can be readily fabricated. CMPs
have received considerable attention owing to their potential
application in the field of optoelectronics48,49 because of the
presence of delocalized p-electrons throughout their frame-
works as well as their rigid micropores.
1H and 13C NMR spectra were recorded on a JEOL JNM-
EX400 instrument at 400 and 100 MHz, respectively. Sam-
ples were analyzed in CDCl3, and the chemical shift values
were expressed relative to Me4Si as an internal standard.
Solid state cross-polarization/magic-angle-sample-spinning
(CP/MAS) 13C NMR spectra were obtained on a Bruker
Avance III spectrometer operated at 100 MHz, and CP/MAS
1
spectra were recorded at the MAS rate of 7 kHz with the H
decoupling field amplitude of 57 kHz. The contact time and
the repetition time were fixed as 2 ms and 5 s, respectively.
Analytical thin layer chromatography was performed with
silica gel 60 Merck F254 plates. Column chromatography
was performed with Wakogel C-300 SiO2. High-resolution
mass spectra (HRMS) were obtained on a Thermo Scientific
MALDI LTQ Orbitrap XL hybrid mass spectrometer. The
adsorption isotherms of nitrogen at 77 K were measured
with a BELSORP-18PLUS instrument, and N2 gas of high pu-
rity (99.9999%) was used. Prior to the adsorption
Additional Supporting Information may be found in the online version of this article.
C
V
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SCHEME 1 Synthesis of monomer 3.
measurements, the sample was treated under reduced pres-
sure (<10–2 Pa) at 423 K for 5 h. SEM measurement was
carried out on a JEOL JSM-5600B system. Samples were put
on a conducting carbon tape attached by a SEM grid, and
then coated with platinum. XRD data were obtained on a
Rigaku MiniFlex diffractometer using CuKa radiation in a
range of 3ꢀꢁ2yꢁ60ꢀ at intervals of 0.01ꢀ at a scanning rate
of 0.25ꢀ min–1. Elemental analyses were performed at the
Microanalytical Center of Kyoto University.
SCHEME 3 Synthesis of CMP
2 by Sonogashira–Hagihara
cross-coupling.
mercially, and used after purification by distillation.
4,7,12,15-Tetraethynyl[2.2]paracyclophane (1)55 was pre-
pared from the corresponding tetrabromo[2.2]paracyclo-
phane56 as described in the literature.
Monomer Synthesis
Compound 3
Materials
The mixture of 1 (0.363 g, 1.19 mmol), 2 (1.486 g, 5.25
mmol), Pd2(dba)3 (109 mg, 0.12 mmol), PPh3 (125 mg, 0.45
mmol), and CuI (46 mg, 0.24 mmol) were placed in a 50 mL
Pyrex flask equipped with a magnetic stirrer bar. The equip-
ment was purged with Ar, followed by adding THF (40 mL)
and NEt3 (10 mL) at 0 ꢀC. The reaction was carried out at
room temperature for 3 h. The reaction mixture was concen-
trated in vacuo to afford the crude product, which was puri-
fied by SiO2 column chromatography (hexane/CHCl3, v/v ¼
8/1 as an eluent) and recrystallization from CHCl3 and
MeOH to afford 3 as a pale yellow solid (476 mg, 0.52
mmol, 43%). Rf ¼ 0.24 (hexane/CHCl3, v/v ¼ 8/1).
THF and Et3N were purchased and purified by passage
through purification column under Ar pressure.54 Dehy-
drated CH2Cl2 and DMF were obtained commercially, and
used after degassing. Pd2(dba)3, Pd(PPh3)4, Ni(cod)2, PPh3,
CuI, N,N,N0,N0-tetramethylethylenediamine (TMEDA), 2,20-
bipyridine, 1-bromo-4-iodobenzene (2), and 1,4-diiodoben-
zene (4) were obtained commercially, and used without fur-
ther purification. Cyclooctadiene (COD) was obtained com-
1H NMR (CDCl3, 400 MHz): d 3.07 (t, J ¼ 8.0 Hz, 4H), 3.54
(t, J ¼ 8.0 Hz, 4H), 7.10 (s, 4H), 7.41 (d, J ¼ 8.0 Hz, 8H),
7.53 (d, J ¼ 8.0 Hz, 8H); 13C NMR (CDCl3, 100 MHz): d 32.7,
90.3, 93.6, 122.3, 122.7, 125.0, 131.7, 132.8, 134.6, 141.8.
HRMS (MALDI) calcd for
C48H28Br4, 919.8919; found
919.8878 [M]þ. Anal. calcd for C48H28Br4: C 62.37 H 3.05 Br
34.58, found: C 62.64 H 3.27 Br 34.48.
Polymer Synthesis
CMP 1
CuCl2 (99 mg, 1.00 mmol), TMEDA (116 mg, 1.00 mmol),
and CH2Cl2 (5.0 mL) were placed in a 50 mL Pyrex flask
equipped with a magnetic stirrer bar, and the mixture was
bubbled with O2 for 30 min. To this solution compound 1
(126 mg, 0.42 mmol) in CH2Cl2 (2.0 mL) was added. After
the reaction was carried out at room temperature for 72 h,
SCHEME 2 Synthesis of CMP 1 by Hay coupling.
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SCHEME 4 Synthesis of CMP 3 by Yamamoto coupling.
aqueous NH3 (28%) was added. The pale yellow solid was
collected by filtration and washed with THF, hexane, CHCl3,
H2O, and MeOH. Then, the solid was further washed with
CHCl3 for 24 h and MeOH for 24 h using a Soxhlet extractor.
ppm. FTIR (KBr): 833, 905, 1508, 1593, 2195, 2930, 3032,
and 3296 cm–1.
CMP 3
ꢀ
The solid was dried at 150 C in a vacuum oven for 24 h to
A mixture of Ni(cod)2 (309 mg, 1.12 mmol), and 2,20-bipyri-
dine (175.7 mg, 1.12 mmol) was placed in a round-bottom
flask equipped with a magnetic stirring bar and a reflux con-
denser. The equipment was purged with Ar, followed by add-
ing DMF (30 mL) and COD (0.14 mL, ꢀ1.12 mmol), and then,
the mixture was stirred for 1 h at 80 C. To the mixture was
added compound 3 (200 mg, 0.22 mmol). The reaction was
carried out at 80 ꢀC for 72 h. To the mixture, conc HCl aq
(6.0 mL) was added, and the mixture was stirred for 8 h at
room temperature. The pale yellow solid was collected by fil-
tration and washed with THF, hexane, CHCl3, H2O, and
MeOH. Then, the solid was further washed with CHCl3 for 24
h and MeOH for 24 h using a Soxhlet extractor. The solid
was dried at 150 ꢀC in a vacuum oven for 24 h to afford
CMP 3 (120 mg, 91%). Solid state CP/MAS 13C NMR: 31.6,
96.5, 126.1, 130.5, 140.1 ppm. FTIR (KBr): 822, 1497, 1601,
2181, 2930, 3028 cm–1.
afford CMP 1 (112 mg, 90%). Solid state CP/MAS 13C NMR:
31.7, 82.7, 125.2, and 141.1 ppm. FTIR (KBr): 903, 1470,
1573, 2158, 2929, and 3290 cm–1.
CMP 2
A mixture of 1 (72 mg, 0.24 mmol), 8 (157 mg, 0.48 mmol),
Pd(PPh3)4 (27.4 mg, 0.024 mmol), CuI (4.5 mg, 0.024 mmol),
Et3N (1.9 mL), and DMF (2.85 mL) was placed in a round-
bottom flask equipped with a magnetic stirring bar and a
reflux condenser. After degassing the reaction mixture sev-
eral times, the reaction was carried out at 80 ꢀC for 72 h
with stirring. The reaction mixture was cooled to room tem-
perature, and 1.0 N HCl (10 mL) was added to the mixture.
The pale yellow solid was collected by filtration and washed
with THF, hexane, CHCl3, H2O, and MeOH. Then, the solid
was further washed with CHCl3 for 24 h and MeOH for 24 h
using a Soxhlet extractor. The solid was dried at 150 C in a
1H and 13C NMR spectra of 3, and solid state CP/MAS 13C
NMR spectra and FTIR spectra of CMPs 1–3 are shown in
Supporting Information.
ꢀ
vacuum oven for 24 h to afford CMP 2 (124 mg, 116%).
Solid state CP/MAS 13C NMR: 31.7, 94.6, 123.4, 130.1, 140.2
TABLE 1 Results of Polymerization and Surface Areas of CMPs
Elemental analysis
Reaction
Efficiencyb
H (%) Found,
Calcd
C (%) Found,
Calcd
Halogen (%)
Found, Calcd
CMP
Yielda (%)
SBET (m2 g–1
)
SLangmuir (m2 g–1
)
1
2
3
a
90
116
91
0.72
0.94
4.05, 4.03
4.72, 4.46
4.98, 4.67
90.55, 95.97
85.32, 95.54
87.93, 95.33
–
889
840
956
1,156
1,285
1,231
Iodine: 3.37, 0
Bromine: 0.24, 0
>0.99
Isolated yield calculated on the basis of weight.
from the FTIR absorption peak of the terminal alkyne CAH stretching
for CMP 1.
b
Calculated from the elemental analysis data for CMPs 2 and 3, and
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RESULTS AND DISCUSSION
[2.2]Paracyclophane-based monomer 1 was prepared from
4,7,12,15-tetrabromo[2.2]paracyclophane56 using the proce-
dure reported in the literature.55 The Sonogashira–Hagihara
cross-coupling51,52 of compound 1 with 1-bromo-4-iodoben-
zene (2) proceeded chemoselectively to give monomer 3 in
43% isolated yield, as shown in Scheme 1. Schemes 2–4 show
the syntheses of target CMPs 1–3. Hay coupling50 of 1
(Scheme 2), Sonogashira-Hagihara cross-coupling of 1 with 4
(Scheme 3), and Yamamoto coupling53 of 3 (Scheme 4)
afforded the corresponding CMPs 1–3, respectively. After the
coupling reaction, the crude products were washed with or-
ganic solvents and H2O using a Soxhlet extractor to yield the
CMPs as pale yellow powders. The polymerization results are
listed in Table 1. The reaction efficiencies of the CMPs were
calculated according to the FTIR absorption peak of the CAH
stretching vibration of the terminal alkyne (CMP 1) and the
elemental analysis data (CMPs 2 and 3). Generally, the isolated
yield of a CMP synthesized by palladium-catalyzed cross-cou-
pling is greater than 100% because of the presence of
unreacted halogens such as bromine and iodine. Thus, in our
case, CMP 2 possessed 3.37% iodine according to the result of
elemental analysis. On the other hand, Yamamoto coupling
proceeded smoothly to provide CMP 3 (Scheme 4) with high
reaction efficiency (>0.99), although this reaction required a
stoichiometric amount of the Ni complex. Almost all of the Br
FIGURE 2 Nitrogen adsorption–desorption isotherms of CMPs
1–3 at 77 K; a filled symbol and an open symbol indicate
adsorption and desorption isotherms, respectively.
species reacted, and the elemental analysis showed that only
0.24 wt % of Br remained in the sample. It is desirable to
remove residual halogens from the viewpoint of the possible
application of the CMPs to optical materials.
The structures of the obtained CMPs were confirmed by
solid-state CP/MAS 13C NMR and FTIR spectroscopies. As a
representative example, the solid-state CP/MAS 13C NMR
spectrum of CMP 2 is shown in Figure 1(A). The signal posi-
tions for various types of carbons were as follows. The rela-
tively sharp peak at 31.7 ppm was assigned to the bridge
methylene carbons of cyclophane units. The small signals of
the CAC triple bond carbons appeared at around 95 ppm.
Finally, the peaks at 120–145 ppm were assignable to the ar-
omatic carbons. The FTIR spectra were obtained using KBr
pellets of the CMPs. The spectrum of CMP 2 is shown in Fig-
ure 1(B), and the spectra of CMPs 1 and 3 are shown in
Supporting Information. For all samples, the peaks of the
stretching vibration of the CAC triple bond appeared around
2200 cmꢂ1 and that of the CAC double bonds of phenylenes
appeared around 1580 and 1480 cmꢂ1. The peaks attribut-
able to the stretching vibrations of the CAH bonds in the
cyclophane units were observed at 2850–2950 cmꢂ1. In the
FTIR spectra of CMPs 1 (Fig. S4 in Supporting Information)
and 2 [Fig. 1(B)], the CAH stretching vibration of unreacted
terminal alkynes appeared at around 3250 cm–1. Thus, the
reaction efficiencies of CMPs 1 and 2 could be calculated
from the absorbance of the terminal alkyne CAH stretching.
The CMPs were analyzed by nitrogen gas sorption. The nitro-
gen adsorption/desorption isotherms of CMPs 1–3 obtained
at 77 K are shown in Figure 2. According to the IUPAC clas-
sification reported in 1985,57 all isotherms of CMPs 1–3
exhibited a type I nitrogen gas sorption profile. This result
clearly indicates that the obtained CMPs are microporous
FIGURE 1 (A) Solid state CP/MAS 13C NMR spectrum of CMP
2; CP/MAS 7 kHz, asterisk denotes spinning sidebands. (B) FTIR
spectrum of CMP 2 (KBr).
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ACKNOWLEDGMENTS
network polymers comprised only micropores with diame-
ters of less than 2 nm. The Brunauer–Emmett–Teller (BET)
Financial support ‘‘Grant-in-Aid for Young Scientists (A) (No.
21685012)’’ from the Ministry of Education, Culture, Sports,
Science and Technology, Japan is gratefully acknowledged. This
work was partially supported by The Asahi Glass Foundation
and ‘‘Grant-in-Aid for Young Scientists (A) (No. 24685018)’’
from the Ministry of Education, Culture, Sports, Science and
Technology, Japan. The authors are grateful to Professor Sus-
umu Kitagawa and Dr Munehiro Inukai (Department of Syn-
thetic Chemistry and Biological Chemistry, Kyoto University)
for solid state CP/MAS 13C NMR spectroscopy and valuable
discussions.
surface areas (SBET) and Langmuir surface areas (SLangmuir
)
of CMPs 1–3 were estimated, and the results are shown in
Table 1. All of the CMPs exhibited large BET surface areas
greater than 840 m2 g–1. CMP 3, which was obtained by
Yamamoto coupling, exhibited the highest SBET value of
approximately 1000 m2g–1. Pore size distribution curves of
CMPs 1–3 were obtained by the micropore method, and they
are shown in Figure S9 in Supporting Information. The pores
were mainly observed in the mesopores range from 0.5 to
1.1 nm. The pore diameters of the CMPs increased as the
distance between [2.2]paracyclophane junctions became lon-
ger. For example, the pore diameters of CMPs 2 and 3 were
estimated to be approximately 1.0 nm.
REFERENCES AND NOTES
The powder XRD patterns of CMPs 1–3 exhibited the hollow
peaks as shown in Figure S10 in Supporting Information,
indicating that they were completely amorphous. SEM
images of CMPs 1–3 providing morphological information
are shown in Supporting Information Figures S11(A–C),
respectively. The morphology of CMP 2 obtained by cross-
coupling polymerization suggested the presence of various
chunks consisting of small plates and blocks [Fig. S11(B)]. In
contrast, the SEM image of CMP 1 showed aggregates con-
sisting of small blocks [Fig. S11(A)], and that of CMP 3,
which was prepared by the Yamamoto coupling, showed rel-
atively uniform particles with approximately 0.2 lm in size
[Supporting Information Fig. S11(C)]. Thus, CMP 3 was read-
ily dispersed in common organic solvents such as CHCl3 and
CH2Cl2. In addition, there was little residual Br in CMP 3;
therefore, its optical properties were investigated. As shown
in Supporting Information Figure S12(A), CMP 3 dispersed
in CH2Cl2 exhibited a broad absorption band with a peak top
at around 420 nm. As shown in Supporting Information Fig-
ure S12(B), upon excitation at the absorption peak maxi-
mum, a broad and featureless emission spectrum was
observed with a peak top at around 530 nm (fluorescence
quantum yield of 2%) derived from the stacked and aggre-
gated structures of the p-conjugated frameworks. Encapsula-
tion of guest molecules into this class of CMPs and their
application as a light-harvesting antenna are the next target.
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