Synthesis of polyaniline with low polydispersity by using a supramolecular ionic assembly as the reaction medium

Article abstract of DOI:10.1002/chem.201204134

A supramolecular ionic assembly comprised of an anionic oligo(phenylene ethynylene) and anilinium cations provides a unique reaction medium in which anilinum cations are concentrated and aligned. The oxidative polymerization (see figure) of aniline using the supramolecular ionic assembly (gray) yielded polyaniline (green/blue) with a number-average molar mass of 20 500 and polydispersity of 1.3. Copyright

Full text of DOI:10.1002/chem.201204134

DOI: 10.1002/chem.201204134
Synthesis of Polyaniline with Low Polydispersity by Using a Supramolecular
Ionic Assembly as the Reaction Medium
Shaoan Xu,[a, b] Sanjib Das,[a, f] Soichiro Ogi,[a] Kazunori Sugiyasu,[a] Hiroyuki Okazaki,[c]
Yoshihiko Takano,[c] Takeshi Yasuda,[d] Kenzo Deguchi,[e] Shinobu Ohki,[e]
Tadashi Shimizu,[e] and Masayuki Takeuchi*[a, b]
Conducting polymers (CPs) are an important class of op-
toelectronic materials that have a number of advantages as
organic substances; namely, they are designable, flexible,
processible, and lightweight. These attractive features have
enabled the fabrication of new organic electronic devices,
such as light-emitting diodes, photovoltaics, transistors, and
actuators.[1] Polythiophenes (PTs), polyfluorenes (PFs), poly-
In 2004, the groups led by Yokozawa[3] and McCullough[4]
reported independently that a nickel-catalyzed coupling re-
action of 3-alkylthiophene-based monomers proceeded in
chain-growth manner, giving regioregular poly(3-alkyl thio-
phene)s with a PDI of close to unity. Recent development
of this method has further enabled the controlled polymeri-
zation of other CPs, such as polyphenylenes (PPs)[5] and
PFs.[6] Furthermore, Yu and Turner[7] have succeeded in
ring-opening metathesis polymerization (ROMP) of
[2.2]paracyclophanedienes, which afforded soluble PPVs
with a PDI of 1.2. Accordingly, the chain-growth polymeri-
zation of CPs has opened new doors in synthetic polymer
chemistry and organic electronics.[8] However, in principle,
the concept cannot be applied to the polymerization of ani-
line[9] because it proceeds through the oxidative coupling of
anilinium salts.
ACHTUNGTRENNUNG(phenACHTUNGTRENNUNGylene vinylene)s (PPVs), and polyanilines (PANIs) are
all representative CPs, and some are currently at a practical
application stage. To design and synthesize CPs with desired
functions, factors related to not only the electronic proper-
ties of the p-conjugated systems but also the structural char-
acteristics, such as the regioregularity and polydispersity, are
important because these structural qualities determine the
aggregation morphology and thus affect the bulk proper-
ties.[2] However, such controlled polymerization has not
been regarded as feasible because CPs are typically synthe-
sized through step-growth mechanisms. The polydispersity
index (PDI) of step-growth polymerization is predicted to
be 2.0 when the monomer conversion is 100%.
Recently, Lo and Sleiman[10] reported nucleobase-templat-
ed synthesis of poly(phenylene ethynylene)s (PPEs). Impor-
tantly, the PDI values of the daughter polymer (that is,
PPE) were close to unity, copying that of the template poly-
mer despite the step-growth nature of Sonogashira coupling
polymerization. Furthermore, other templating approaches
using porous coordination polymers (PCPs)[11] and block co-
polymer micelles[12] were found to be effective. In such
unique reaction media, the propagation reaction occurred
preferentially against other side reactions and achieved a
low PDI value. However, examples of conjugated polymer
synthesis are still limited.
Inspired by the development of these templating ap-
proaches, we decided to pursue the synthesis of PANI with a
low PDI value, because PANI is one of the remaining CPs
for which such a polymerization has not yet been establish-
ed. The template-assisted polymerization of aniline has been
widely examined;[13] however, previous research focused on
creating PANI nanostructures that replicated the template
structures, and a characterization of the PANI including
PDI values has not been performed in detail. Herein, we
present a supramolecular ionic assembly composed of an
anionic p-conjugated backbone and anilinium cations that
could provide a unique polymerization medium in which the
anilinium cations are concentrated and aligned. Remarkably,
the oxidative polymerization of aniline using the supramo-
lecular template yielded PANI with a PDI value as low as
1.3 (Mn =20500).
[a] S. Xu, Dr. S. Das, Dr. S. Ogi, Dr. K. Sugiyasu, Prof. Dr. M. Takeuchi
Organic Materials Group
National Institute for Materials Science (NIMS)
Sengen 1-2-1, Tsukuba 305-0047 (Japan)
Fax : (+81)29-859-2101
E-mail: TAKEUCHI.Masayuki@nims.go.jp
[b] S. Xu, Prof. Dr. M. Takeuchi
Department of Materials Science and Engineering
Graduate School of Pure and Applied Sciences
University of Tsukuba
Tennoudai 1-1-1, Tsukuba 305-8571ACTHNUTRGNE(UNG Japan)
[c] Dr. H. Okazaki, Prof. Dr. Y. Takano
Nano Frontier Materials Group, NIMS
Sengen 1-2-1, Tsukuba 305-0047
ACHTUNGTRNE(NUNG Japan)
[d] Dr. T. Yasuda
Organic Thin-Film Solar Cells Group, NIMS
Sengen 1-2-1, Tsukuba 305-0047(Japan)
AHCTUNGTRENNUNG
[e] Dr. K. Deguchi, Dr. S. Ohki, Dr. T. Shimizu
High Field NMR Group, NIMS
Sakura 3-13, Tsukuba 305-0003 (Japan)
[f] Dr. S. Das
Present Address: Department of Colloids & Materials Chemistry
Institute of Minerals & Materials Technology—CSIR
Orissa (India)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201204134.
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Figure 1. a) An SEM image of a freeze-dried sample of 1 prepared in
water: [1]=0.2 mm, pH 2.5. b) The dynamic light scattering profile of the
supramolecular assembly of 1 prepared in water: [1]=0.2 mm, pH 2.5.
Scheme 1. Structures of compounds 1, 2, and 3. Anilinium chloride was
used for comparison.
We designed and synthesized oligo(phenylene ethynylene)
(OPE)-based anionic molecules that have anilinium cations
not only as counterions but also as monomers (Scheme 1).
To tune the balance between the hydrophobicity and hydro-
philicity of the molecules, which is essential for self-assem-
bly in water,[14] we introduced triethylene glycol and dodecyl
chains in 1 and two dodecyl chains in 2. Compound 3 was
prepared for control experiments and is analogous to 1 and
2 but does not assemble in water owing to its compact struc-
ture. All the compounds are characterized using the usual
methods (see Supporting Information).
Figure 2. Changes to the UV absorption spectrum of the supramolecular
assembly of 1 in water as the assembly is cooled from 75 to 58C: [1]=
0.2 mm, pH 2.5, l=1 mm.
We prepared the supramolecular assembly by dissolving 1
in water under sonication and maintaining the solution at
58C. Figure 1a shows
a scanning electron microscope
(SEM) image of a freeze-dried sample of the supramolecu-
lar assembly of 1 ([1]=0.2 mm, pH 2.5). We observed rec-
tangular structures with a width of about 200–400 nm. X-ray
diffraction (XRD) measurements indicated that the assem-
bly had a crystalline nature, although a detailed characteri-
zation was difficult owing to the complicated XRD profile
(Supporting Information, Figure S1). The size of the supra-
molecular assembly in solution was also evaluated using dy-
namic light scattering (DLS; Figure 1b). The average size
was about 300–500 nm, which is consistent with that ob-
served in the SEM images. Compound 2 ([2]=0.2 mm) was
too hydrophobic and could not be dissolved in water. In
contrast, composite 3 ([3]=0.2 mm) was soluble but did not
form any supramolecular assembly.
along with a new shoulder band at 399 nm. This indicates
the formation of a supramolecular assembly of OPE chro-
mophores[15] at 58C.
We also conducted variable-temperature (VT) 1H NMR
measurements of the supramolecular assembly of 1. Fig-
ure 3a shows partial 1H NMR spectra of 1, for which the
proton signals of the OPE backbone became broad for tem-
peratures below 458C, indicating the formation of the supra-
molecular assembly. Importantly, a shift in the proton signals
of the anilinium cation in 1 was scarcely observed during
this process, while the chemical shifts of those in anilinium
chloride and compound 3 moved to higher frequencies (a
lower magnetic field) upon cooling (Figure 3b; Supporting
Information, Figure S2). The change in the chemical shifts
with temperature is rationalized by the hydration-induced
shift of the free anilinium cations. These results in turn sug-
gest that within the anionic supramolecular assembly of 1,
anilinium monomers would form contact ion pairs with the
Figure 2 shows the variable-temperature (VT) ultraviolet
(UV) absorption spectra of the supramolecular assembly of
1. By lowering the temperature of the solution of 1 from
75 to 58C, a red-shift in the p–p* transition of OPE in 1
from 363 to 368 nm with isosbestic points was observed
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M. Takeuchi et al.
Figure 4. a) Absorption spectra of 1 (black line), PANI-ES (green line),
and PANI-EB (blue line) obtained through the templating approach.
PANI-ES and PANI-EB were diluted from 1 mL to 4 mL by addition of
H2O (3 mL); l=1 cm. (b) GPC profiles of the PANI-EB obtained
through the templating approach (c) and commercially available
PANI-EB (a, PDI (Mw) >1.8 (20000)).
at a peak wavelength (lmax) of 777 nm (1.6 eV), which is at-
tributable to the emeraldine salt form of PANI (namely,
PANI-ES; Figure 4a). Importantly, neither anilinium chlo-
AHCTUNGTREGrNNUN ide nor compound 3 could be polymerized under the same
conditions, which is probably due to the low monomer con-
centration and temperature ([anilinium cation]=0.4 mm, 0–
58C, pH 2.5). We infer from this that the supramolecular
template can locally concentrate the monomers and facili-
tate the polymerization. The addition of potassium hydrox-
ide solution rendered the resultant solution basic and de-
doped the PANI-ES, transforming it into the emeraldine
base form [(PANI-EB), lmax =563 nm (2.2 eV)] without any
precipitation. The PANI-EB was then precipitated out by
adding dimethylformamide (DMF) to the PANI-EB solu-
tion, filtered, and washed with methanol and water, and
freeze-dried (yield 85%). The anionic template was readily
isolated from the filtrate by evaporating solvents, and it can
be re-used for further synthesis of polyaniline after complex-
ation with anilinium cations.[16]
Figure 3. a) Changes to the 1H NMR spectrum of the supramolecular as-
sembly of 1 in water with temperature: Sodium [2,2,3,3-D4]-3-3-(trimeth-
ylsilyl) propanoate was used as an internal standard; [1]=0.2 mm, pD=
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
2.5. b) Plots of the chemical shifts of p-H in anilinium salts against tem-
~
perature: anilinium chloride ( [anilinium chloride]=0.4 mm, pD=2.5),
&
*
compound 3 ( [3]=0.2 mm, pD=2.5), and compound 1 ( ).
anionic OPE backbone. Therefore, the supramolecular as-
sembly of 1 provides the anilinium monomers with different
surroundings from those in the bulk solution. We expect
that oxidative polymerization of aniline in such a unique re-
action medium can afford PANI in a controlled manner.
With the above information in mind, we conducted oxida-
tive polymerization of aniline. We added ammonium persul-
fate (APS, 0.4 mm, 1.0 equiv/aniline) to a solution of the su-
pramolecular assembly of 1 (0.2 mm, pH 2.5, 0–58C). The
mixture was stirred for 24 h at 0–58C, yielding a green-col-
ored solution without any precipitation. An absorption spec-
trum of the resultant solution showed maximum absorption
Solid-state 15N NMR spectrum of the resultant PANI-EB
with anionic OPE showed a single peak at 70.75 ppm, which
is most likely due to rapid imine–amine interconversion at
room temperature, and peaks assignable to the branched
structures were not detected (Supporting Information, Fig-
ure S3).[17] A gel permeation chromatography (GPC) profile
of the obtained PANI-EB is shown in Figure 4b. Remark-
AHCTUNGTRENNUNG
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Polyaniline with Low Polydispersity
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standards). This value is significantly smaller than that of
commercially available PANI-EB (PDI (Mw)=1.8 (20000)).
Among several syntheses of PANI-EB under identical con-
ditions of [1]=0.2 mm at 0–58C, variations of Æ6% in the
obtained Mn value were observed (Supporting Information,
Table S1). It should be mentioned that the length of the
PANI calculated from the Mn value is not consistent with
the size of the supramolecular assembly of 1 (Figures 1a,b).
A similar inconsistency between the Mn value and template
size has also been observed in other systems.[18] Therefore,
we expect that the supramolecular assembly plays an impor-
tant role in influencing the polymerization kinetics rather
than defining the length of the PANI by copying its size.
The time evolution of the polymerization, starting with
the addition of one equivalent of APS toward aniline, was
therefore monitored using absorption spectroscopy
(Figure 5). After an induction period of 4 h, features related
form in the redox equilibrium because PANI-ES can be
easily oxidized into PANI-PN (step 3). During polymeriza-
tion, the oxidation of the monomer is mediated by the
redox couple of PANI-PN and PANI-ES (step 4), which ac-
celerates the polymerization. Polymerization ends when all
the APS is consumed; consequently, only the PANI-ES re-
mains in the solution, upon which the absorption maximum
shifts from 740 nm (PANI-PN) to 777 nm (PANI-ES). The
PANI-ES can be dedoped and transformed into PANI-EB,
accompanied by a color change from green to blue, by treat-
ment with potassium hydroxide solution (step 5). Interest-
ingly, the polymerization took place even with the addition
of only 0.2 equiv of APS (Supporting Information, Fig-
ure S4). Moreover, the addition of another 0.2 equiv of APS
restarted the polymerization. If the APS oxidizes the anilini-
um monomers randomly and sparsely in the supramolecular
assembly of 1, polymerization should not take place with a
deficiency of APS. Therefore, it should be reasonable to
conclude from these results that the polymerization pro-
ceeds at the surface of the supramolecular assembly of 1.
We deduce that the PANI-ES, polymerized at the surface,
would dissociate from the supramolecular assembly along
with anionic PPEs as solubilizing agent, which then exposes
a fresh surface of anilinium monomers for subsequent poly-
merization. Accordingly, a plausible mechanism for the con-
trolled polymerization using the supramolecular reaction
medium is depicted in Scheme 2b. As discussed, the anilini-
um monomer is oxidized by the PANI-PN. Because the dif-
fusion of anilinium monomer would be suppressed in the su-
pramolecular assembly, the propagation reaction should
occur at the chain end of PANI (Step 4 in Scheme 2b). Such
a kinetically controlled process is likely to give rise to the
narrow polydispersity of the resultant PANI. Given this
plausible mechanism, the temperature and concentration
should influence the quality of the resultant PANI, as these
factors will affect not only the formation of supramolecular
assembly (Supporting Information, Table S1 and Figure S5)
but also the polymerization kinetics. In fact, as the polymeri-
zation temperature or concentration of 1 was increased, Mn
and the PDI also increased. Under such conditions, even
anilinium chloride could be polymerized in some degree,
and such bulk polymerization would deteriorate the struc-
tural quality of PANI. The relationships between the con-
centration of 1, Mn, and PDI are shown in Figure 6. The
PDI value can be as low as 1.3 provided that the concentra-
tion of 1 is kept below 1 mm.
Figure 5. a) Changes to the absorption spectrum observed during poly-
*
merization. b) Plots of the absorbance at 800 nm ( ) and absorption
*
maximum against time ( : [1]=0.2 mm, [APS]=0.4 mm, pH 2.5 at 58C,
l=1 cm.
to the absorption of the pernigraniline form of PANI
(PANI-PN) appeared in the spectra and gradually increased
in strength. This process was accompanied by a small peak
shift from 700 nm to 740 nm, which is indicative of the for-
mation and elongation of p-conjugated systems. The in-
crease in the absorbance was eventually saturated and the
lmax shifted to 777 nm, at which point the polymerization fin-
ished (Figure 5b). The peak shift observed in the last stage
of the polymerization indicates the transformation of PANI-
PN to PANI-ES. This kinetic analysis of the PANI formation
is consistent with the reported mechanism[19] and is ex-
plained as follows (Scheme 2a). An induction period is ob-
served because the initiation step (that is, oxidation of the
anilinium monomer) is generally slow (step 1). Once poly-
merization has commenced (step 2), PANI-PN is the main
As Mn and the structural quality of CPs profoundly influ-
ence the electrical properties,[1g,20] we measured the conduc-
tivity of the PANI-ES obtained from the supramolecular
ionic assembly of 1. PANI-ES films were prepared from
PANI-EB (PDI=1.3, Mn =20500) by doping with camphor-
sulfonic acid (CAS) in meta-cresol; this sample was drop-
cast onto a silicon wafer (see the Supporting Information).
We measured the electrical conductivity of the PANI-ES
film to be 190 ScmÀ1 at 258C using a four-terminal tech-
AHCTUNGTRENNUNG
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M. Takeuchi et al.
Scheme 2. The oxidative polymerization process of aniline and a plausible mechanism in this system.
reaction medium, which afforded PANI-EB with Mn =20500
and a PDI of 1.3. We deduce that anilinium monomers form
contact ion pairs with the anionic OPE backbone and are lo-
cally concentrated along the ionic assembly of 1; such a sit-
uation eventually enables the facilitation of the polymeriza-
tion reaction and would suppress side reactions. The conduc-
tivity of the PANI-EB doped with CAS in meta-cresol was
estimated to be 190 ScmÀ1, which was higher than commer-
cially available PANI. At this stage, we have not succeeded
in controlling Mn significantly; however, the control of su-
pramolecular ionic assemblies would lead to the synthesis of
higher molecular weight PANI-ES with a low PDI, which
should exhibit better conductivity. Our approach basically
permits the utilization of this unique ionic assembly for the
synthesis of other conducting polymers. Such research is
now in progress.
~
&
Figure 6. Plots of Mn
concentration of 1.
( ) and the PDI ( ) of PANI as a function of the
the same procedure, was evaluated to be 28 ScmÀ1 (its GPC
is shown in Figure 4b). In the case for PANI, there is a rela-
tionship between the Mn and the electrical conductivity;[20a–d]
our system would contribute to reveal the correlation be-
tween the PDI of PANI and the electrical conductivity.
In conclusion, we have demonstrated oxidative polymeri-
zation of aniline using a supramolecular ionic assembly as a
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Polyaniline with Low Polydispersity
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Keywords: conducting polymers
assembly · supramolecular chemistry
·
polyaniline
·
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Received: November 19, 2012
Revised: February 22, 2013
Published online: March 20, 2013
Chem. Eur. J. 2013, 19, 5824 – 5829
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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