One-step preparation of novel conjugated porous polymer with tubular structure

Article abstract of DOI:10.1007/s11426-013-4879-8

A shape-persistent dendritic molecule, tris(4-(2,7-dibromo-9-phenyl-9- fluoren-9-yl)phenyl)amine (TF-6Br), has been readily synthesized in high yield through a concise Friedel-Crafts reaction from triphenylamine and 2,7-dibromo(9-phenyl-fluoren-9-ol). It

Full text of DOI:10.1007/s11426-013-4879-8

SCIENCE CHINA
Chemistry
•
ARTICLES •
doi: 10.1007/s11426-013-4879-8
doi: 10.1007/s11426-013-4879-8
One-step preparation of novel conjugated porous polymer with
†
tubular structure
1
1
1
1*
1
ZHUANG XiaoDong , ZHANG Yi , CAO ChengAn , ZHANG Fan , WU DongQing ,
1
, 2*
FENG XinLiang
1
Institute of Advanced Organic Materials, School of Chemical and Chemical Engineering, Shanghai Jiao Tong University,
Shanghai 200240, China;
2
Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz, Germany
Received February 21, 2013; accepted March 22, 2013
A shape-persistent dendritic molecule, tris(4-(2,7-dibromo-9-phenyl-9-fluoren-9-yl)phenyl)amine (TF-6Br), has been readily
synthesized in high yield through a concise Friedel-Crafts reaction from triphenylamine and 2,7-dibromo(9-phenyl-fluoren-9-ol).
It was further employed as the key building block to achieve the synthesis of conjugated porous polymer via Sonogashira cou-
pling with 1,4-diethynylbenzene. Under experimental reaction conditions, the resulting porous polymer shows exceptionally
nanotubular morphology, which further allows for a template-free synthesis of porous carbon nanotubes via thermal treatment
at high temperature. The obtained nitrogen-doped carbon nanotubes feature with an improved porosity and high surface area.
fluorene, Friedel-Crafts reaction, porous polymer, carbon nanotube
1
Introduction
dant groups have been prepared [6]. Nevertheless, it has
been less explored regarding the synthesis of nonlinear
polymeric systems based on the building blocks of F-2Br
possessing multiple functional units via traditional synthetic
methods.
Fluorene based polymers have been extensively studied
owing to their unique optical and electrical properties across
a broad range of fundamental and technological potential
over the last few decades. Particularly, the incorporation of
functional monomers into polymer chains has resulted in
materials with some unusual and attractive characteristics
including chemical sensing, electroluminescent property,
resistive memory, and gas storage [1]. With respect to other
monomers containing benzene, carbazole and thiophene
unit, C-9 position of fluorene offers a great opportunity for
anchoring functional moieties, such as triphenylamine [2],
thiophene [3], pyrene [4] and carbazole [5] etc. By far, a
numerous of linear conjugated polymers based on
2
,7-dibromofluorene (F-2Br) derivatives with various pen-
*
†
Corresponding authors (email: fan-zhang@sjtu.edu.cn; feng@mpip-mainz.mpg.de)
Recommended by Prof. YAN Deyue (Shanghai Jiao Tong University)
Scheme 1 The structures of F-2Br, SF-4Br and TF-6Br.
©
Science China Press and Springer-Verlag Berlin Heidelberg 2013
chem.scichina.com www.springerlink.com

2
Zhuang XD, et al. Sci China Chem January (2013) Vol.56 No.1
F-2Br(2,7-dibromofluorene) [7] and SF-4Br(2,2′,7,7′-
were carried out on a AXIS Ultra DLD system from Kratos
with Al Kα radiation as X-ray source for radiation. Trans-
mission electron microscopy (TEM) characterizations were
conducted using a JEM-2100 (JEOL Ltd., Japan) with an
accelerating voltage of 200 kV. Raman spectra were ob-
tained using a SEN TERRA spectrometer (Bruker) employ-
ing a semiconductor laser (λ = 532 nm). The Brunauer-
Emment-Teller (BET) specific area was measured on ASAP
2010 M/C surface area and porosimetry analyzer (Mi-
tetrabromo-9,9′-spirobifluorene) [8] (Scheme 1 ) were first
reported in 1957 and 1990, respectively, and up to now,
have been widely employed to synthesize conjugated oli-
gomers and polymers given that the aromatic halides can
efficiently undergo typical transition metal-catalyzed cross
couplings. Additionally, the presence of side chains at C-9
position of fluorene moiety, perpendicular to the plane of
F-2Br, sterically repulses the close packing of the aromatic
moieties, and thus impedes aggregation tendency [9]. The
cromeritics Instrument Corporation, USA) based on N
sorption.
2
ad-
o
monomer SF-4Br possessing a spiro structure with a 90
kink [1d, 10], is accessible for the formation of free volume
among polymeric chains, and thus has been utilized to con-
struct microporous polymers with high surface area, such as
poly(phenyleneethynylene) [11] and poly(9,9′-spirobifluo-
rene) [10]. Hyperbranched or star-shaped polymers through
coupling F-2Br with truxene [12], triphenylamine [13],
porphyrin [14], pyrene [4], tetraarylmethane and silane [15]
etc, have also been reported. Moreover, some unique den-
dritic architectures consisting of eight-arm polyhedral oli-
gomeric silsesquioxanes (POSS) [16] have also been
demonstrated as inorganic-organic hybrid networks.
2
9
.1 Preparation of 2,7-dibromo-(9-phenyl-9H-fluoren-
-ol) (2)
Bromobenzene (2.15 mL, 20.6 mmol) was added dropwise
over a few minutes to a stirred mixture of magnesium (0.67
g, 27.5 mmol) and anhydrous THF (50 mL) at room tem-
perature under nitrogen. The resulting mixture was heated at
50 °C for 3 h and then 2,7-dibromo-9H-fluoren-9-one (4.62
g, 13.7 mmol) in dry THF (20 mL) was added dropwise
over 10 min. The solution was then heated under reflux
In our attempt to synthesize novel porous polymers by
integrating the known building blocks of triphenylamine
and fluorene, we present herein the synthesis of dendritic
tris(4-(2,7-dibromo-9-phenyl-9-fluoren-9-yl) phenyl)amine
overnight. After cooling, aqueous NH
4
Cl solution was add-
ed and the mixture was extracted with EtOAc. The organic
extracts were washed with water and brine and then dried
over Na
pressure and the crude product was purified through column
chromatography (SiO , petroleum ether/acetic ether) to ob-
tain light yellow powder 2 (4.55 g, 80%).
2 4
SO . The solvent was removed under reduced
(
TF-6Br) containing six aromatic halides as coupling sites.
Boron trifluoride-diethyl etherate promoted Friedel-Crafts
reaction of triphenylamine and 2,7-dibromo(9-phenyl-
fluoren-9-ol) provides TF-6Br in high yield. This building
block was further subjected to the Sonogashira coupling
reaction with 1,4-diethynylbenzene, resulting into a conju-
gated porous polymer which shows remarkably tubular
morphology and high thermal stability. Therefore, nitrogen-
enriched porous carbon nanotubes were constructed in a
template-free manner via pyrolysis of the porous polymer.
The obtained nitrogen-enriched carbon nanotubes exhibit
highly porous features.
2
1
3
H NMR (400 MHz, CDCl , ppm): 7.51 (s, 2H), 7.50 (d,
J = 0.43 Hz, 2H), 7.43 (t, J = 1.23 Hz, 2H), 7.327.29 (m,
5H), 2.53 (s, 6H).
13
C NMR (100 MHz, CDCl , ppm): 152.3, 147.4, 138.1,
3
137.7, 132.6, 128.7, 128.5, 128.0, 122.7, 121.0, 74.5
2
.2 Preparation of tris(4-(2,7-dibromo-9-phenyl-9H-
fluoren-9-yl)phenyl)amine (TF-6Br)
A solution of boron trifluoride-diethyl ether complex (0.2
mL, 1.57 mmol) in appropriate dichloromethane (20
mL) was added dropwise to a mixture of 2,7-dibromo (9-
phenyl-fluoren-9-ol) (621 mg, 1.5 mmol) and triphenyl-
amine (122 mg, 0.5 mmol) in dry dichloromethane (100 mL)
under nitrogen atmosphere at room temperature. The re-
sultant mixture was stirred for 2 h at room temperature, and
then the reaction was quenched with ethanol (20 mL) and
water (100 mL) solution. The aqueous phase was extracted
three times with dichloromethane. The combined dichloro-
2
Experimental
All reactions were carried out under nitrogen atmosphere by
standard Schlenk techniques. All chemicals were purchased
from Aladdin Reagent Inc. and used as received, unless
otherwise noted. All organic solvents were purified and
dried under standard procedures.
Thermogravimetric analysis (TGA) of the samples was
measured using a Perkin-Elmer Pyris 1 thermo gravimetric
analyzer in flowing (100 mL/min) nitrogen atmosphere.
FT-IR spectra were recorded using Spectrum 100 (Perkin
Elmer, Inc., USA) spectrometer. X-ray diffraction (XRD)
measurements were carried out on a D/max-2200/PC
methane layers were washed, then dried with Na
last concentrated by rotary evaporation. The crude product
was purified by column chromatography (SiO , petroleum
ether/acetic ether) to yield crystal products (681 mg, Yield:
2 4
SO and at
2
9
5%).
1
(
Rigaku Corporation, Japan) using Cu (40kV, 30mA) radia-
H NMR (400MHz, DMSO-d
6
, ppm): 7.90–7.88 (d, J =
tion. X-ray photoelectron spectroscopy (XPS) experiments
8
.1 Hz, 6H), 7.56–7.53 (dd, J = 8.1; 1.6 Hz, 6H), 7.50 (d, J

Zhuang XD, et al. Sci China Chem January (2013) Vol.56 No.1
3
=
7
=
1.5 Hz, 6H), 7.22 (t, J = 7.1 Hz, 12H), 7.027.04 (dd, J =
.9; 1.7, 6H), 6.96–6.94 (d, J = 8.6 Hz, 6H), 6.84–6.81 (d, J
8.6 Hz, 6H).
2.4 Thermal pyrolysis of P1
00 mg P1 was placed in a quartz boat and heated to 800 °C
with a heating rate of 2 °C/min under an argon flow. The
sample was held at this temperature for 2 h. After cooling to
room temperature, the black powder was obtained, and
named as PyP1 in this work.
2
2.3 Preparation of porous polymer P1
A flame-dried Schlenk flask was charged with TF-Br (0.43
g, 0.3 mmol), 1,4-diethynylbenzene (151 mg, 1.2 mmol),
tetrakis(triphenylphosphine) palladium(0) (22 mg, 0.0196
mmol), tri-tert-butyl phosphonium tetrafluoroborate (26 mg,
3 Results and discussion
0
.93 mmol), and copper(I) iodide (7.2 mg, 0.038 mmol).
The synthesis of porous polymer P1 is illustrated in Scheme
The flask was equipped with a condenser and a magnetic
stirring bar, evacuated and re-filled with nitrogen at least for
three cycles. THF (40 mL) and triethylamine (10 mL) were
injected by syringe into the flask under nitrogen. The re-
sulting solution was vigorously stirred at room temperature
for 1 h to ensure in situ generation of phosphine; then the
temperature was raised to 70 °C. After stirring at this tem-
perature for 72 h, the mixture was cooled to room tempera-
ture. The porous polymer was isolated by filtration and
washed with THF, methanol and dichloromethane to re-
move any amine salts and catalyst residues. Further purifi-
cation of the sample was carried out by Soxhlet extraction
with THF. The product was recovered and dried under re-
duced pressure at 60 °C overnight.
2
. First, 2,7-dibromo(9-phenyl-fluoren-9-ol) 2 was produced
via an addition reaction of the Grignard reagent, phenyl-
magnesium bromide, with 2,7-dibromofluorenone (Scheme
2
). Afterwards, using a modified previous procedure [3],
TF-6Br was synthesized in high yield via BF ·OEt
promoted Friedel-Crafts reaction of triphenylamine and 2.
3
2
-
Single crystal of TF-6Br was obtained by slowly diffus-
ing hexane into its chloroform solution [18]. The crystal
structure is shown in Figure 1. The fluorene plane is almost
perpendicular to the mean plane of triphenylamine moiety,
and C–Br bonds at the C-2 and C-7 positions [3, 4] of the
three fluorene units are stretched out of the molecular center
in a parallel fashion (Figure 1a, b). The bond lengths and
angles are in the typical range of previously reported similar
molecules [19]. Based on the packing diagram, two fluorene
units of the neighboring molecules are stacked in a face-to-
face arrangement with a distance of 3.053 Å, providing a
1
FT-IR (KBr, cm ): 3444, 3058, 3030, 2921, 2855, 1600,
504, 1455, 1402, 1385, 1319, 1263, 1185, 1115, 1064,
017, 874, 819, 755, 727, 701, 643, 539.
1
1
Scheme 2 Synthesis of TF-6Br and P1.

4
Zhuang XD, et al. Sci China Chem January (2013) Vol.56 No.1
Figure 2 TGA of P1 under nitrogen flow at a heating rate of 10 °C/min.
Figure 1 Single crystal structure (a: top view; b: side view) and molecu-
lar packing diagram (c, d) of TF-6Br (atom color code in a, b and c: brown,
gray, white and pink refer to bromine, carbon, hydrogen and nitrogen,
respectively; blue and green refer to TF-6Br and hexane solvent molecules,
respectively, in the packing view for (d).
strong intermolecular interaction. Very interestingly, the
packing mode creates free channels filled with hexane mol-
ecules. Therefore, it can be concluded that TF-6Br with
shape-persistent dendritic structure is suitable for con-
structing 3D porous materials [20].
In view of good solubility and high reactivity with aro-
matic halides, the rigid monomer 1,4-diethynylbenzene was
employed to couple with TF-6Br for achieving three-
dimensional extended conjugated structure via the So-
nogashira reaction [17] . After one-day reaction, the result-
ing product P1 (Scheme 2) was precipitated directly from
the reaction system as yellowish solid. Then, the solid was
grinded to fine powder and purified by Soxhlet extraction
for 3 days using THF to remove small oligomers and cata-
lytic residues. Thermogravimetric analysis (TGA) reveals
that P1 loses merely 10% of its weight at 450 °C, and about
2
0% after the temperature rises up to 800 °C (Figure 2).
This result strongly suggests that P1 has a high thermal sta-
bility, and can be feasibly transformed into carbon materials.
Considering that the original polymer P1 possesses nitrogen
moieties, it renders the fabrication of nitrogen-doped porous
carbon materials. With this in mind, the porous polymer P1
was subjected to thermal treatment at 800 °C for two hours
under nitrogen atmosphere, resulting into black powder
PyP1. The elementary analyses of P1 and PyP1 are sum-
marized in Table 1. The relative content of carbon changed
very little, while the nitrogen ratio reduced from 0.75 to
Figure 3 (a) SEM image of P1; (b), (c) TEM images of P1; (d), (e) TEM
images of PyP1 (the yellow arrows mark the enlarging effect of the corre-
sponding parts in the yellow square frames).
0.40 % after thermal treatment.
The morphology and microstructure of P1 were exam-
Table 1 Elementary analysis of carbon and nitrogen in P1 and PyP1
ined by means of scanning electron microscopy (SEM) and
transmission electron microscopy (TEM). SEM image
shows the nanowire structure with a length of up to 20 mi-
crons (Figure 3(a)). TEM images (Figure 3(b, c)) of P1 fur-
ther manifest the exceptionally hollow tubular structure.
C
N
Run
At (%)/Mass (%)
At (%)/Mass (%)
P1
94.60/93.05
94.58/92.96
0.75/0.86
0.40/0.44
PyP1

Zhuang XD, et al. Sci China Chem January (2013) Vol.56 No.1
5
Compared with P1, there is no obvious change of the nano-
tube morphology for PyP1 as shown in Figure 3(d), sug-
gesting that the morphology of P1 can be well preserved
during the thermal treatment. It is worth noting that the
nanotubes of PyP1 have diameters of 50–200 nm, inner
channels of 10–40 nm and the longest length of approxi-
mately 10 microns, all of which are slightly decreased in
comparison to those of P1. High magnification TEM of
PyP1 (see Figure 3(e)) further manifests the alternating
light and dark contrast on the walls of the nanotubes, which
is characteristic of porous materials. The outer and inner
diameters in a relatively broad range for both P1 and PyP1
is presumably associated with the poorly controlled
polymerization degree of P1 owing to the quick precipita-
tion of the product from solution, and a thermal dynamic
process during polymerization.
Figure 5 XPS survey spectra of P1 and PyP1.
binding configurations of P1 and PyP1. Elemental analyses
(via XPS survey scan quantification) reveal that the nitrogen
contents of P1 and PyP1 are 0.75% and 0.39% (atomic)
respectively. These values are coincided with the elemen-
tary analytical results (Table 1). In addition, the N1s photo-
electron envelopes of PyP1 demonstrates the presence of
pyridinic nitrogen (398.4 eV) and quaternary nitrogen
The adsorption/desorption isotherm of P1 is featured
with a slow rise under low pressure and an adsorp-
tion/desorption hysteresis at higher pressure (in Figure 4(a)),
typical for microporous materials [21]. The BET surface
2
area and pore volume of P1 are 289 m /g and 0.21 mL/g,
respectively. Differently, in the case of PyP1, the BET sur-
2
face area reaches 470 m /g, and the pore volume decreases
(401.0 eV) [22] with the ratio of 1/12.5 (shown as Figure
to 0.15 mL/g. This result can be ascribed to the removal of
some residual components (Figure 5) or further conversion
into porous carbon components during the pyrolysis pro-
cess.
3
4
(b)), suggesting an aromatic transformation of sp -type
nitrogen in the original polymer P1 under pyrolysis condi-
tions.
In order to gain further insight into the structural features
upon thermal treatment, XPS surface analysis was per-
formed to probe the elemental composition and nitrogen
4
Conclusions
In summary, we have successfully synthesized a shape-
persistent dendritic molecule, tris(4-(2,7-dibromo-9-phenyl-
9
-fluoren-9-yl) phenyl)amine as a key building block for the
construction of conjugated porous polymer. The resulting
porous polymer shows remarkable tubular morphology, and
enables a template-free synthesis of porous carbon nano-
tubes through thermal treatment. The generated nitrogen-
enriched carbon nanotubes exhibit highly porous features
which may hold the potential for different electrochemical
applications.
The research was financially supported by the China Postdoctoral Science
Foundation (2011M500767), Natural Science Foundation of China (NSFC,
2
1174083), Key Program of Science and Technology Commission Founda-
tion of Shanghai (11JC1405400) and Shanghai Jiao Tong University (211
Project).
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Zhuang XD, et al. Sci China Chem January (2013) Vol.56 No.1
7
ZHANG Fan (left), received his B.Eng. degree in electrochemistry from Shanghai Jiao Tong University in 1991, and his
PhD degree in organic chemistry from Jilin University in 2000. After more than eight years of research experience in Ger-
many and the United States, he was promoted to a Research Professor in School of Chemistry and Chemical Engineering of
Shanghai Jiao Tong University, China. His research interests span from organometallic catalysis, olefin polymerization to
organic -conjugated functional materials for energy conversion and storage.
FENG Xinliang (center), after obtaining his Master's degree in organic chemistry from Shanghai Jiao Tong University in
March 2004, joined the group of Prof. K. Müllen at the Max Planck Institute for Polymer Research (MPIP) and obtained his
PhD degree in April 2008. Since December 2007, he has been a group leader at MPIP. Since June 2010, he has been a pro-
fessor of Shanghai Jiao Tong University and was appointed as director for the Institute of Advanced Organic Materials. His
current scientific interests include graphene, two-dimensional nanomaterials, organic conjugated materials, carbon-rich mol-
ecules and materials for electronic and energy-related applications.
ZHUANG Xiaodong (right), received his PhD degree from East China University of Science and Technology in 2011 and
was supervised by Prof Yu Chen. He is currently a postdoctoral fellow in Shanghai Jiaotong University (co-supervisor: Prof
Xinliang Feng). He has published 20 articles in the international journals such as Adv. Mater., J. Am. Chem. Soc., Adv. Funct.
Mater., Chem. Mater. and others. His main research interest includes polymer synthesis, graphene chemistry, and porous
polymers/carbons for resistive memory, energy storage and electrochemical catalysis.