Fluorescent, water dispersible polyaniline and its

composites with carbon nanotubes

Pablo Jiménez*, Wolfgang K. Maser, M. Teresa Martinez, Ana M. Benito
Instituto de Carboquímica (CSIC), Dept. of Nanotechnology
Miguel Luesma Castán 4, E-50018 Zaragoza, Spain
*e-mail: pablojm@icb.csic.es
Introduction
Polyanilines (PANI) are a singular class of conducting polymer since they are susceptible of both acid and redox doping
reactions and they present an enviromentally stable conducting state (emeraldine salt)*. Nanostructured polyaniline recently
emerged as a new kind of material, that combines the benefits of nanomaterials with an easy and low-cost production.
Among them PANI nanofibers stand out becouse its simple, template-free synthesis, and its high water dispersability. In this
work we present some attempts to introduce fluorescence in PANI, via copolymerization with carbazole derived compounds

Water dispersable, PANI / MWNT 1 Jiménez, P.; Maser, W. K.;

Castell, P.; Martínez, M. T.;
nanostructured PANI (previous work) water dispersable Benito, A. M. Macromolecular
Rapid Communications 2009,

(nf-PANI) composites1 30 (6), 418-422

Introduction of carbazole moieties

H
H H N
N Zn, HCl N 1. Cu(NO3)2, Ac2O/AcOH Synthesis
MeOH 2. NaOH(aq)
H2N NH2 O O2N NO2 )2
O O 3

u(N H
N C c O N
Zn, HCl N /A
O
Ac 2
MeOH
Copolymerization H2N NH2

2
3)
O2N NO2

O
with aniline

(N

H
N N

cO
Cu
Zn, HCl

/A
2O
Ac
MeOH
(NH4)S2O8
H2N NH2 O2N NO2
NH2
N H H
N N

Oxidative (commercially available) ‘polaron’ form

N N n
H H

polymerization in *Polyaniline, in emeraldine salt state:

NH2
acidic media (HCl 1M) H
N
H
N
‘bipolaron’ form
N N n
H H

Mixtures of PANI and fluorescent molecules

Fluorescent PANI- PANI- PANI- PANI-
Thorough washing of materials with organic solvents
products DAC ADAC EDAC EAC leaves pure PANI-ES and removes all fluorescence

Why they do not copolymerize?

Fluorescent polymers (and MWNT composites) Oxidized aminocarbazoles: R
N N
- Stable & fluorescent water dispersions -
vs.
5x105 3x105

1.8
H2N NH H2 N NH
l em= 450 nm
4x105 2x10
5
Absorbance (arb. units)

lexc= 400 nm N
Intensity (arb. units)
Intensity (arb. units)

3x105 2x105 Hypothesis: in the oxidative

pH = 2

1.2

reaction media DAC is more prone

445 nm
2x105 1x105

0.6 1x105
to give oxidized products similar to N NH
5x104
the phenazine-like molecules that
are supposed be formed in the first
0 0
aniline:DAC ratio 300 400 500 600 700 800 900 260 280 300 320 340 360 380 400 420 440 440 460 480 500 520 540
200:1 Wavelength (nm) Wavelength (nm) Wavelength (nm)
100:1 stages of PANI formation. In fact,
66:1
3:1 UV-Vis Excitation spectra Emission spectra DAC reduces greatly the induction
6
1x10
1x106
period of polymerizations. phenazine-type oligomer
1.8 8x10
5
lem= 450 nm
pH = 5

8x105
Absorbance (arb. units)

Intensity (arb. units)

Intensity (arb. units)

lexc= 313 nm
6x105
6x105

Conclusions
1.2
4x105 5
4x10

5
2x10 2x105
0.6

0 0

In the same conditions that generate nanofibrillar PANI,

300 400 500 600 700 800 900 260 280 300 320 340 360 380 400 420 360 380 400 420 440 460 480 500 520 540
Wavelength (nm) Wavelength (nm) Wavelength (nm)

Fluorescence due to carbazole moiety inside PANI chain we performed oxidative polymerizations of aniline in
Fluorescence in copolymer aqueous presence of various carbazole derivatives. Only in the
dispersions increases with ‘carbazole’ PANI-DAC case of 3,6-diaminocarbazole a true copolymer (PANI-
content, and it depends strongly on the pH 1x105
DAC) was obtained. Copolymers at different ‘carbazole’
Intensity (arb. units)

MWNTs have a quenching proportions were synthesized, and they showed a blue
effect on fluorescence PANI-DAC/MWNTs
emission in fluorescence due to carbazole moieties.
Our synthetic conditions enabled us to prepare PANI-
Acknowledgements DAC and (PANI-DAC)/MWNT composites with a good
0
440 460 480 500 520
Wavelength (nm)

Spanish MICINN under projects MAT2006-13167-C02-02 and MAT2007-66927-C02-01).

water dispersability.
Aragon Consolidated Group Programme DGA-T66 CNN and Aragon Project DGA-PI086/08.
P. Jiménez acknowledges Fundación Ramón Areces for his PhD grant