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Formation of 2,3-diaminophenazines and their

self-assembly into nanobelts in aqueous
medium

Article in European Polymer Journal September 2007

DOI: 10.1016/j.eurpolymj.2007.06.038

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 EUROPEAN
POLYMER
European Polymer Journal 43 (2007) 37033709
JOURNAL
www.elsevier.com/locate/europolj

Macromolecular Nanotechnology

Formation of 2,3-diaminophenazines and their

self-assembly into nanobelts in aqueous medium
Daiping He, Yu Wu, Bo-Qing Xu *

Innovative Catalysis Program, Key Lab of Organic Optoelectronics and Molecular Engineering,
Department of Chemistry, Tsinghua University, Beijing 100084, China

MACROMOLECULAR NANOTECHNOLOGY
Received 29 March 2007; received in revised form 16 June 2007; accepted 21 June 2007
Available online 7 July 2007

Abstract

One-dimensional (1D) nanobelts of several hundred micrometers in length, several hundred nanometers in width and
several hundred nanometers in height are obtained by direct mixing of ortho-phenylenediamine (oPD) and FeCl3 aqueous
solution at room temperature. The nanobelts were characterized by elemental analysis, liquid chromatography/mass spec-
trometry (LC/MS), NMR (1H and 13C), FT-IR, UVvis, thermogravimetric (TG) and conductivity measurement. The
nanobelts are identied as 2,3-diaminophenazine assemblies. The formation of the nanobelts involves two stages: (1) oxi-
dation of oPD by FeCl3, yielding individual 2,3-diaminophenazine molecules; and (2) self-assembly of the 2,3-diamino-
phenazine, forming the 1D nanobelts. The nanobelts exhibit fairly high thermal stability and show conductivity at the
level of semiconductors.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Ortho-phenylenediamine; Ferric chloride; 2,3-Diaminophenazine; Nanobelt

1. Introduction containing 2,3-diaminophenazine or quinoxaline

Conducting polymers (CPs) have attracted much
interest in recent years due to their high perfor-
mance in electrical, electronic, thermal and optical
application elds [1]. Polyaniline (PANI) is one of
the most studied CPs due to its chemical stability
and relatively high conductivity [2]. The success of
PANI has stimulated many studies in the chemis-
try and electrochemistry of PANI derivatives
[36]. Among them, poly(ortho-phenylenediamine)
(PoPD) is reported to be a highly aromatic polymer
*
Corresponding author. Tel./fax: +86 10 62792122.
E-mail address: bqxu@mail.tsinghua.edu.cn (B.-Q. Xu).
repeating unit and exhibiting high thermostability
[4], and has been used as an electrochemical reduc-
tion catalyst for dioxygen [5] and as a sensor for
some chemical species [6]. PoPD is usually prepared
by electrochemical polymerization of ortho-phenyl-
enediamine (oPD) [7]. Except direct formation of
lms of various CPs in electrochemical polymeriza-
tion, chemical oxidative polymerization has recently
been considered as a more feasible route for the pro-
duction of polymers on a large scale [8,9].
Researches into molecular wire have developed
largely since the discovery of carbon nanotubes
[10]. CPs also hold promise as advanced materials
in this area due to their long conjugated length and

0014-3057/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2007.06.038
 3704 D. He et al. / European Polymer Journal 43 (2007) 37033709
metallic conductive property [11]. Zhang et al. fabri-
cated conducting polymer nanowires (278 nm in
length) with soft lithography [12]. Polypyrrole nano-
tubes with ca. 95 nm in diameter and more than 5 lm
in length have been fabricated by reverse microemul-
sion polymerization in an apolar solvent [13]. With
the use of b-naphthalene sulfonic acid to serve as a
dopant and surfactant, Wan and co-workers synthe-
sized PANI microtubes (76650 nm in diameter) [14].
Carswell et al. reported that PANI nanowires with
sub-100-nm features could be formed on at surface
with the help of controlled adsorption of surfactants
[15]. Tubes, bers, or laments of polypyrrole,
poly(3-methylthiophene), polyacetylene, and PANI
have been successfully prepared with a template-
MACROMOLECULAR NANOTECHNOLOGY
based method [16]. However, a rather tedious post-
treatment was often required to remove the template
used. Also, the nanotubes or nanobers preformed
may be destroyed or form undesirable aggregates
when released from the template. Therefore,
although chemical synthesis of conducting polymers
with 1D structure is a very interesting project, seek-
ing a simple and eective synthetic approach is still
a main challenge for materials chemists.
Sun et al. recently developed a simple method for
the production of PoPD nanobelts by directly mixing
HAuCl4 and oPD aqueous solutions at room temper-
ature without the introduction of any surfactants or
templates and speculated that the formation of PoPD
nanobelts was attributed to a gold-catalyzed oriented
growth of PoPD polymers [17]. The authors pro-
posed that Au nanoparticles were produced together
with the formation of oPD oligomers at the early
stage of the oxidative polymerization of oPD. The
as-formed Au particles then served as active catalysts
for the oriented oxidative polymerization of the
remaining oPD monomers along the oligomers pro-
duced, resulting in the formation of PoPD nanobelts.
Here, we report that the PoPD nanobelts can be
obtained by directly mixing of FeCl3 and oPD aque-
ous solutions at room temperature. The formation of
the 1D nanobelts involves two stages: (1) oxidation
of oPD by FeCl3, yielding individual 2,3-diamino-
phenazine; and (2) self-assembly of the 2,3-diamino-
phenazine, forming the 1D nanobelts.
2. Experimental
2.1. Materials and preparation of samples
oPD and FeCl3 were purchased from Beijing
Chem. Co. All reagents were used as received with-
out further purication. In a typical experiment,
6 ml of 0.08 M FeCl3 aqueous solution was rapidly
added into 30 ml of 0.02 M oPD aqueous solution
under vigorous stir. A quick color change from pur-
ple black to reddish brown was observed upon the
addition of FeCl3. The solution mixture was seen
to generate a large quantity of solid precipitate after
standing for 5 h under ambient conditions. The pre-
cipitate was washed three times with deionic water
and then separated by centrifugation and used for
further characterization.
2.2. Characterization of samples
For characterization by scanning electron micros-
copy (SEM) and atomic force microscopy (AFM)
the precipitate was resuspended in deionic water by
shaking, and a drop of this suspension was placed
on a single crystalline silicon slide and air-dried at
room temperature. SEM observation was made on
a JSM-7401F at an accelerating voltage of 20 kV.
AFM image was taken with a commercial instru-
ment, Nanoscope IV. 1H and 13C NMR spectra were
recorded on a JEOL ECA600 NMR spectrometer in
deuterated dimethylsulfoxide (DMSO-d6). Elemen-
tal analysis was performed by using an EAI CE-
440 Elemental Analyzer. Molecular weight was
determined on a Thermo Electron Finnigan LTQ
instrument. FT-IR spectra were recorded on a Per-
kin Elmer GX FT-IR system using KBr pellets in a
range of 4004000 cm1 with 4 cm1 resolution.
UVvis spectra of dilute solutions of the precipitate
in DMSO were collected by using a UV-2102 PC
spectrophotometer over the wavelength range of
200800 nm. Thermogravimetric (TG) analysis of
the precipitate was carried out on a Mettler Toledo
DTA/SDTA851 instrument with a heating rate of
10 C min1 in static air. The direct current conduc-
tivity of the precipitate was measured at room tem-
perature using standard four-probe method.
3. Results and discussion
3.1. Characterization of the precipitate
The morphology of the precipitates isolated from
the reaction of the oPD with FeCl3 was characterized
by SEM and AFM. It can be seen from Fig. 1a that
the precipitate from the reaction between 30 ml of
0.02 M oPD and 6 ml of 0.08 M FeCl3 aqueous
solutions consists of a large quantity of 1D structure.
Higher magnication SEM (Fig. 1b) and AFM
 D. He et al. / European Polymer Journal 43 (2007) 37033709 3705

MACROMOLECULAR NANOTECHNOLOGY
Fig. 1. SEM images of the precipitates prepared from two mixtures of aqueous oPD and FeCl3: (a) 30 ml of 0.02 M oPD aqueous solution
mixed with 6 ml of 0.08 M FeCl3 aqueous solution; (c) 30 ml of 0.02 M oPD aqueous solution mixed with 2 ml of 0.08 M FeCl3 aqueous
solution. (b) SEM image of sample (a) obtained at a higher resolution.

(Fig. 2) images reveal that these 1D nanobelts are of
several hundred micrometers in length, several hun-
dred nanometers in width, and several hundred
nanometers in height. The amount of oPD and FeCl3
has considerable inuence on the morphology of the
precipitate thus formed. When the amount of aque-
ous FeCl3 solution was reduced to 2 ml, we obtain
bunchy aggregates of 1D structures (Fig. 1c).
The chemical composition of the as-prepared
nanobelts was determined using an elemental
analyzer. C, H and N elements are detected in the
nanobelts, and the experimental C/H/N ratio of
the nanobelts based on elemental analysis data is
3/2.5/1. We further determine the molecular weight
of the nanobelts by LC/MS. The obtained spectrum
shows an intense quasi-molecular ion peak (M+H)+
centered at 211, suggesting that the molecular for-
mula for the as-prepared nanobelts is C12H10N4.
The 13C NMR spectrum of the nanobelts in
DMSO-d6 (Fig. 3) shows six peaks, three being
low intensity and situated at lower magnetic elds
in comparison with the other three peaks with
higher intensity. It is possible, by an inspection of
the 13C NMR spectrum, to recognize the presence
of any carbon atom with no carbon-hydrogen
(CH) bond because of its low intensity. The pres-
ence of equivalent carbon atoms in a molecule
results in a discrepancy between the number of car-
bon NMR peaks and the number of carbon atoms
in the molecule. A carbon atom having a chemical
bond with a hetero-atom would show a NMR signal
at lower eld, whereas a carbon atom having a CH
bond would show a NMR signal at higher eld. The
13
C NMR spectrum of pyrazine [18] shows only one
resonance of low intensity at 145.6 ppm which is
comparable to the resonances of carbon c and d in
the product of this present study at 146.8 and
140.0 ppm, respectively. Thus the other chemical
shifts of 135.4, 127.7, 124.8 and 98.8 ppm could be
assigned to the carbon atoms at the positions of a,
 3706 D. He et al. / European Polymer Journal 43 (2007) 37033709
MACROMOLECULAR NANOTECHNOLOGY

Fig. 4. 600 MHz 1H NMR spectra of the nanobelts dissolved in

DMSO-d6.

nanobelts as shown in Fig. 4. The spectrum is char-

acterized by four peaks with the following chemical
shifts: d = 7.99 (m, 2H, Hf), d = 7.67 (m, 2H, He),
d = 7.00 (s, 2H, Hb) and d = 7.38 (s, 4H, NH2).
Thus, our data of elemental analysis, LC/MS 13C
NMR and 1H NMR measurements are consistent
in showing that the as-prepared nanobelts consist
of 2,3-diaminophenazine units.
Further evidences that are in support of the 2,3-
Fig. 2. AFM measurements of the precipitate obtained with 6 ml diaminophenazine units in the nanobelts can be
of 0.08 M FeCl3 aqueous solution and 30 ml of 0.02 M oPD
deduced from the IR and UVvis spectra of the
aqueous solution.
as-prepared nanobelts. The infrared spectra
(Fig. 5) of the samples prepared using dierent
127.708

e d b
ppm

f N c a NH2 amount of oPD and FeCl3 solutions appear similar

f a NH2
e d N c
b
b
Transmittance
124.778

98.792
146.806

139.954
135.445

a
896
1692 839
1636 1151
1242 752
3310 1375
3192 1525

150.0 140.0 130.0 120.0 110.0 100.0 90.0 4000 3000 2000 1000
Chemical shift, (ppm) Wavenumber /cm-1
Fig. 3. 600 MHz 13C NMR spectra of the nanobelts dissolved in Fig. 5. FT-IR absorption spectra of the samples prepared from
DMSO-d6. The inset shows the molecular structure of the sample. two mixtures of aqueous of oPD and FeCl3: (a) 6 ml of 0.08 M
FeCl3 aqueous solution and 30 ml of 0.02 M oPD aqueous
b, e and f, respectively. We also collected the 1H solution; (b) 2 ml of 0.08 M FeCl3 aqueous solution and 30 ml of
NMR spectrum (in DMSO-d6) of the dissolved 0.02 M oPD aqueous solution.
 D. He et al. / European Polymer Journal 43 (2007) 37033709 3707

5
451 0.01

Deriv. Weight /mg/C

485 4 TG DTG
Absorbance

0.00

Weight /mg
3
-0.01
b
2
-0.02
a 1
-0.03
0
300 400 500 600 700 800 -0.04
Wavelength /nm 0 200 400 600 800
Temperature /C
Fig. 6. UVvis absorption spectra of the samples prepared from
two mixtures of aqueous of oPD and FeCl3: (a) 6 ml of 0.08 M Fig. 7. Thermogravimetric curve of the nanobelts precipitate.
FeCl3 aqueous solution and 30 ml of 0.02 M oPD aqueous

solution; (b) 2 ml of 0.08 M FeCl3 aqueous solution and 30 ml of
0.02 M oPD aqueous solution.
to each other. The major absorption peaks are
observed at 752, 839, 896, 1151, 1242, 1375, 1525,
1636, 1692, 3192 and 3310 cm1. The two peaks
between 3450 and 3150 cm1 are due to NH
stretching vibrations of amino groups, which are
indicative of NH2 groups in the structural units
of the nanobelts. The bands at 839 and 896 cm1
are assigned to the out-of-plane bending vibrations
of the CH bonds in the 1,2,4,5-tetrasubstituted
benzene ring of the phenazine unit. This suggests
that the nanobelt units have the phenazine skeleton.
The absorptions at 752 cm1 due to the out-of-plane
bending vibration of the CH bonds in the 1,2-
disubstituted benzene ring, at 1525 cm1 due to
the stretching vibration of C@C bonds on the aro-
matic ring, at 1636 cm1 due to C@N bonds, and
at 1242 cm1 due to the stretching vibration of
CN bonds in the benzenoid structure are also
clearly observed [19]. Fig. 6 exhibits the UVvis
spectra of the samples prepared using dierent
amount of aqueous oPD and FeCl3. It can be seen
that the UVvis spectra of the samples are also sim-
ilar. The strong absorption band at 451 nm and its
shoulder at 485 nm are assigned to pp* transitions
associated with the phenazine ring conjugated to the
two lone pairs of electrons on the nitrogen atoms in
the NH2 groups.
MACROMOLECULAR NANOTECHNOLOGY
loss features on the TG curve, which are clearly
shown by the two negative DTG peaks at 260
and 520 C. The weight loss at lower temperatures
is associated with the DTG peak at 260 C, which
is 15% of the initial sample weight, could arisen
from a loss of the NH2 groups in the phenazine
skeleton of the nanobelts. The weight loss at higher
temperatures is associated with the DTG peak at
520 C may be due to an occurrence of oxidative
decomposition of the nanobelts in air. Indeed, it
was seen that the nanobelt 1D structure was
destroyed after a calcination in air of the precipitate
sample at 280 C (Fig. 8). It can be seen from the
TG and DTG curves that the nanobelts are ther-
mally stable upto 210 C.
The direct current conductivity of the nanobelts,
measured at room temperature using standard four-
probe method, is 1.38 106 S cm1, indicating that
the conductivity of the nanobelts is at the level of
semiconductors.

3.2. Properties of the nanobelts

Thermogravimetric (TG) analysis was performed

upto 900 C to gain information on the stability of
the nanobelts. Fig. 7 shows the TG and DTG curves Fig. 8. SEM image of the precipitate after a calcination at
of the as-prepared nanobelts. There are two weight 280 C.
 3708 D. He et al. / European Polymer Journal 43 (2007) 37033709
3.3. Possible mechanism of formation of the nanobelts
According to the mechanism of formation of
polyaniline or substituted polyaniline compounds
by oxidative polymerization from their monomers
[4], the formation of the 2,3-diaminophenazine mol-
ecules may at least involve two steps (Scheme 1): (1)
oxidation of oPD molecules by ferric ions to form
radical cations or semiquinone radicals; and (2)
dimerization or coupling of the radical cations,
forming the 2,3-diaminophenazine. The 2,3-diami-
nophenazine thus formed is rich in p-bonding and
proton donor and acceptor sites. It may be expected
that these functional sites would induce self-assem-
bly of the 2,3-diaminophenazine molecules to form
MACROMOLECULAR NANOTECHNOLOGY
the nanobelt precipitate through intermolecular
pp interactions and hydrogen bonding. Very inter-
estingly, we have observed that decreasing the solu-
tion pH can result in a disassembly of the as-formed
nanobelts in aqueous medium. When pH decreases,
the concentration of H 3 O ions in solution increases,
which results in the protonation of the amine groups
in the 2,3-diaminophenazine units of the nanobelts.
Subsequently, the 2,3-diaminophenazine units
would, at suciently lower pHs, become highly pos-
itively charged and strongly repel each other. It is
therefore not surprising that the nanobelts break
apart when the intermolecular pp interactions can-
not counteract the intermolecular electrostatic repul-
sion interactions. When the solution pH was
increased again, precipitation to form nanobelts
appeared again, because the highly positively
charged 2,3-diaminophenazine units were deproto-
nated and the intermolecular repulsion interactions
were not strong enough to counteract the intermo-
lecular pp interactions. Therefore, the formation
of the nanobelt 1D structures from individual 2,3-
diaminophenazine molecules requires some bal-
NH2 Fe3+ NH2
NH2 - 2e- NH2
3+
Fe - 2e
e d b
f N c a NH2
2,3-diaminophenazine
f a NH2
e d N c b
self-assembly
one-dimensional nanobelts
Scheme 1.
anced cooperation between the pp interactions
and electrostatic repulsion interactions. In other
words, hydrogen bonding interactions between 2,3-
diaminophenazine molecules play also an important
role in the formation of the 1D nanostructures. As it
is illustrated in Scheme 1, the process leading to the
formation of the nanobelt 1D structures from oPD
involves two stages. In the rst stage, the oxidation
of oPD by FeCl3 results in the formation of 2,3-
diaminophenazine. In the second stage, the 2,3-dia-
minophenazine molecules undergo a self-assemble
chemistry to form 1D nanobelts via pp interactions
and hydrogen bonding interactions.
In a further set of experiments, we used Fe(NO3)3
and Fe2(SO4)3 as the alternative of FeCl3, respec-
tively, and obtained very similar 1D nanobelt prod-
uct. These results indicate that the Fe3+ ions play an
important role in the oPD oxidation to 2,3-
diaminophenazine.
4. Conclusions
One-dimensional nanobelts of several hundred
micrometers in length, several hundred nanometers
in width and several hundred nanometers in height
have been obtained by direct mixing of oPD and
FeCl3 aqueous solution at room temperature. The
nanobelt formation includes an oxidation of oPD
monomers by ferric ions to form 2,3-diaminophen-
azine, followed by self-assembly of the as-formed
2,3-diaminophenazine molecules. The nanobelts
exhibit fairly high thermal stability and show con-
ductivity at the level of semiconductors, showing a
good potential as molecular wire material because
of its 1D structure and conductivity.
Acknowledgements
This work was supported nancially by the
NH3 National Natural Science Foundation (NSF) (grant:
20573062), and the Ministry of Education (Grant:
NH3
SRFDP 20040003036) of China. We thank Mr. Sen-
-
lin Chen and Mr. Bo Song (Professor Xi Zhangs
group) for their kind assistance in acquiring the
AFM data. We also thank Prof. Guangtao Li for
helpful discussion.
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