Synthetic Metals, 24 (1988) 329 - 341 329

RAMAN SPECTRA OF P O L Y P Y R R O L E AND ITS

2,5-13C-SUBSTITUTED AND C-DEUTERATED A N A L O G U E S IN DOPED
AND UNDOPED STATES

Y. FURUKAWA, S. TAZAWA, Y. FUJII* and I. HARADA**

Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980 (Japan)
(Received November 30, 1987; accepted December 15, 1987)

Abstract

Raman and optical absorption spectra were studied on electrochem-

ically polymerized polypyrrole in as-polymerized doped (highly conduc-
tive), partially undoped and substantially undoped 'neutral' (insulating)
states. Vibrational assignments were made on the basis of the data of 2,5-
13C-substituted and C-deuterated derivatives. The Raman result of the
neutral polymer is consistent with the ~,~'-linked all-s-trans coplanar and
conjugated structure. In the as-polymerized polymer there exist both
radical cation and dication in which the bond orders of C3C4 and inter-
ring CC are increased as compared to those in the neutral polymer. The
structural distortion in the dication is greater than that in the radical cation.
Changes in optical absorption and Raman spectra during reduction (undop-
ing) were explained by the conversions of the dication to the radical cation
and the radical cation to the neutral species.

Introduction

Doped polypyrrole obtained by electrochemical oxidative polymeriza-

tion of pyrrole exhibits high electrical conductivity at room temperature
[1 - 19]. It becomes insulating upon electrochemical reduction [6, 20].
According to '3C n.m.r, studies, the polymerization proceeds predo-
minantly through ~,~' coupling [6, 21]. An infrared study on undoped
(neutral) polypyrrole and oligomers (2,2'-bipyrrole and 2,2': 5',2"-terpyrrole)
has suggested that neutral polypyrrole has a planar all-s-trans structure
[22, 23]. E.s.r. and optical absorption observations on doped polypyrrole
have indicated the formation of radical cation (polaron) and dication
(bipolaron) [24 - 32]. However, the assignments of the optical spectra are

*Present address: Japan Control System, Inc., 3-35-8, Jingumae, Shibuya-ku, Tokyo
150, Japan.
**Author to whom correspondence should be addressed.

0379-6779/88/$3.50 © Elsevier Sequoia/Printed in The Netherlands

330

still controversial [24, 26, 27, 30]. A quantum chemical calculation on

pyrrole tetramer has predicted that heavy doping yields a bipolaron and
that all the bond lengths among the C and N atoms in it are significantly dif-
ferent from those in the neutral tetramer [33, 34]. The structure of the
radical cation, as well, is expected to be different from those of the dication
and neutral species.
Molecular vibrations are sensitive to the structure and such drastic
changes in bond nature as mentioned above must be reflected in the vibra-
tional spectra. In particular, the excitation-wavelength dependence of the
band intensities in the resonance Raman spectra is useful both in assigning
the broad and possibly overlapped optical absorptions to individual species
and in discriminating the Raman bands of one species from those of another.
In order to obtain detailed structural information from the vibrational
spectra [4, 6, 13, 22, 23, 35 - 40], it is necessary to know the vibrational
modes of doping-sensitive bands. We studied the Raman spectra of poly-
pyrrole and its 2,5-13C-substituted and C-deuterated analogues at neutral and
as-polymerized states and made the vibrational mode assignments on the
basis of the isotopic shifts of the peak wavenumbers. The spectra of neutral
polymers are reasonably understood as those of the a,a'-linked all-s-trans
coplanar and conjugated structures. Raman spectra of as-polymerized
polymers were complicated and drastically different from those of neutral
polymers. However, by studying the optical absorption and resonance
Raman spectra at various stages of reduction (various undoping levels), it
was possible to discriminate some of the Raman bands due to the dication
from those due to the radical cation, and to assign the optical absorption
bands to individual species. The drastic difference of the spectra between
neutral and doped polymers is explained by the difference in structure:
increased bond orders of C3 C4 and inter-ring CC and a possibly decreased
bond order of C2C 3 (CsC4) in the dication and radical cation as compared
with those in neutral segments.

Experimental
Electrochemical synthesis of doped polypyrrole (DPP) was performed
in an airtight cell containing a deoxygenated acetonitrile solution of pyrrole
(0.06 M, M = m o l / d m 3) and 0.1 M electrolyte (LiC104, LiBF4 or Et4NBF4).
Films were grown on the surface of a Pt or an In-Sn oxide (ITO) conducting
glass electrode. A Pt plate was used as the counter electrode. The films were
synthesized with either a constant current of 1 m A / c m 2 or a voltage of 3.5
V between the electrodes. No reference electrode was used to avoid
contamination.
The films of C-deuterated polypyrrole (DPPD) were prepared galvano-
statically from pyrrole-2,3,4,5-d 4. The m o n o m e r can be obtained by H/D
exchange reaction of pyrrole [41]. Acetonitrile and Et4NBF4 were used
as the polymerization solvent and electrolyte, respectively.
 331

The films of '2,5-13C-substituted polypyrrole' (DPPC) were prepared

galvanostatically in benzonitrile solution containing LiBF4 and a mixture of
pyrrole-2,5-13C 2 (83.7%), pyrrole-2-13C (15.5%) and pyrrole {0.8%). The
proportions of the three isotopomers were calculated from the purity of the
starting material, Na13CN {Merck Frosst Canada Inc., 91.5 atom% 13C).
Succinonitrile was prepared by the reaction of 1,2-dibromoethane and
Na13CN and reduced to succindialdehyde by diisobutylaluminum hydride.
Pyrrole was synthesized by the reaction of succindialdehyde and ammonium
carbonate.
Substantially undoped films were prepared by electrochemical
reduction: as-polymerized doped films were reduced in acetonitrile or benzo-
nitrile containing 0.1 M Et4NBF 4 until the colour of the films became
greenish yellow. These are termed 'neutral' polypyrrole (NPP) films in this
work. Films used for studying absorption and Raman spectra at partially
undoped states were prepared by electrochemical reduction in a different
way: an as-polymerized film was held at a potential (2.8 - 1.6 V) in the
polymerization cell until the reducing current fell to zero.
2,2'-Bipyrrole was synthesized according to the previous m e t h o d
[42].
Raman spectra of the films adhered to the surface of Pt plates were
recorded on a JEOL 400D spectrophotometer equipped with a photon-
counting device. An NEC GLG 3300 Ar ion laser {457.9, 488.0 and 514.5
nm) or a JEOL He-Ne laser {632.8 nm) was used as the light source. Visible
absorption spectra were measured in situ using a polymerization cell with an
ITO window on one side of the cell and a glass window on the other. A
film was prepared on the inner surface of the ITO window and the spectra
of the film at various stages of reduction were recorded.

Results and Discussion

Optical absorption spectra

Figure 1 shows absorption spectra of a CIO4--doped film on an ITO
electrode in the as-polymerized state [DPP(C104-)] (Fig. l(a)) [3, 6, 24
28] and at different stages of electrochemical reduction (Figs. l(b)-(f)).
The doping level decreases in alphabetical order in the Figure and Fig. l ( f )
is the spectrum of almost completely reduced NPP. As reduction proceeds,
the peak of the visible band (to be termed the B band) shifts from 462 nm to
longer wavelengths. The intensity first increases a little and then decreases
substantially. The intensity of the near-infrared band {C band) decreases
monotonically. A band is observed around 350 nm (A band) in Fig. 1(c) and
it exhibits bathochromic shifts toward 412 nm on further reduction, with
concomitant increases in intensity [24, 28].
The peak wavelength, 412 nm, of NPP is nearly equal to that in ref. 43
(410 nm), but is different from that in refs. 6 and 24 (3.2 eV (387 nm)).
These bands have been assigned to the ~-lr* transitions in the neutral parts
332

~1j2
, .... <,51

y, ~; s2o a
= 1.ok'"-",. ~, I 5,4?

< ~69k,~ ~':'~'-" d

#
f
0.0 i , , i ,
400 500 600 700 800
WQvelengt h Inm
Fig. i. Dependence of the absorption spectrum of C104--doped polypyrrole [DPP-
(CIO4-)] on the reduction potential: (a) DPP(C104-) prepared at a voltage of 3.5 V v s .
the counter electrode; (b) the film with a lowered potential of 2.8 V; (c) 2.5 V; (d) 2.2 V;
(e) 2.0 V; (f) 1.6 V (neutral, NPP). The doping level decreases in alphabetical order.

of the polymer [24] since 2,2'-bipyrrole and 2,2':5',2"-terpyrrole give such

peaks at 285 and 345 nm, respectively [43]. The bathochromic shift
mentioned above is understood as a result of elongation of the successive
neutral parts in the polymer in the course of reduction [24]. The peak at a
longer wavelength (e.g., 412 nm) indicates that the neutral polymer consists
of longer conjugated segments.
The origins of the visible band and broad near-infrared band extending
to the infrared are of particular interest in relation to the structure of the
doped part. Yakushi e t al. [24] have assigned the visible band to a 7r-Tr*
transition of conjugated cationic segments and proposed two possible assign-
ments on the near-infrared band: (1) a charge-transfer transition between
the conjugated segments located either on the same polymer chain or on dif-
ferent polymer chains; and (2) an electronic transition within the conjugat-
ed segments (intra-segment transition). Scott et al. [26] and Br~das et al.
[27] have attributed both the bands to the dication (at high doping levels)
and the radical cation (at low doping levels). Geni~s et al. [30] have
observed two bands at 540 and 440 nm and assigned the former to the
radical cation and the latter to the radical cation and dication.
A simple-minded interpretation of the monotonic decrease of the C
band intensity upon reduction is that the band arises mostly from one
species whose content decreases monotonically. On the other hand, the
complex behaviour of the B band during the reduction strongly indicates
the presence of species other than that giving rise to the C band. Between
the two possible species, the dication and radical cation, reported to exist
in the d o p e d polymer [24 - 32], the content of dication would be relatively
high at high doping levels [26, 27]. If the C band is mainly contributed by
the dication and the B band is an overlap of the bands of radical cations plus
the short-wavelength c o n t o u r of the C band, the spectral behaviours men-
 333

t i o n e d a b o v e are e x p l a i n e d as a result o f d i c a t i o n - > radical c a t i o n and

radical c a t i o n -+ n e u t r a l f o r m processes. T h e changes in p e a k w a v e l e n g t h and
i n t e n s i t y in t h e B a n d A b a n d regions are d u e t o t h e changes in c o m p o s i t i o n s
of various radical c a t i o n s a n d n e u t r a l species w h o s e a b s o r p t i o n w a v e l e n g t h s
are d e p e n d e n t o n t h e c o n j u g a t i o n lengths [ 2 4 ] . It is i n t e r e s t i n g to n o t e t h a t
a f t e r t h e d i c a t i o n is p r a c t i c a l l y d i m i n i s h e d , a nearly isosbestic p o i n t is
o b s e r v e d at 4 6 9 n m . As will be d e s c r i b e d later, t h e R a m a n o b s e r v a t i o n s are
c o n s i s t e n t w i t h this i n t e r p r e t a t i o n .

Raman spectra of neutral polypyrrole and the assignments

Figure 2 s h o w s r e s o n a n c e R a m a n s p e c t r a ( 4 5 7 . 9 n m e x c i t a t i o n ) o f NPP,
NPPC a n d N P P D , a n d t h e R a m a n s p e c t r u m o f 2 , 2 ' - b i p y r r o l e . T h e b r o a d
f e a t u r e s o f t h e 1 5 2 8 a n d 1 3 0 3 c m -1 b a n d s in Fig. 2(b) are c o n s i d e r e d to
arise f r o m t h e i s o t o p i c i n h o m o g e n e i t y o f t h e p a r e n t m o n o m e r . It is n o t t h e
p u r p o s e o f t h e p r e s e n t p a p e r to i n t e r p r e t the b a n d b r o a d e n i n g s , h o w e v e r ,

¢'4 ¢O

I ~ \ ~ /~A ~ a0
I"- co ~ , "."----....~ T
~ ~ I I
i,.o"1
b o
f \~ o o

t"

"" O

I1 , q I / ,JL-A-___N II I ~" hi h'l ~ I r "~ I , T

' 'ls'o'o ' ' '1"oo'o ' ' ' soo' ' '
Wavenumberlcm -1
Fig. 2. Raman spectra (457.9 nm excitation, 80 K) of neutral polypyrroles and 2,2'-
bipyrrole: (a) neutral polypyrrole (NPP) prepared by undoping of DPP(BF4-), which was
polymerized in CH3CN; (b) 2,5- 1;3 C-substituted
•
t
analogue (NPPC); (e) C-deuterated ana-
. .

logue (NPPD); (d) 2,2 -blpyrrole (sohd). The bands marked with a cross are emission lines
of an Ar ion laser.
334

and only some comments are made here. Since the parent m o n o m e r of
NPPC is a mixture of pyrrole-2,5-13C2 (83.7%t, pyrrole-2-13C (15.5%t and
pyrrole (0.8%), the inter-ring CC bonds (C'C') in the polymer can be either
of d o m i n a n t 13C13C, minor 13C12C or minimal 12C12C. Interruption of con-
secutive 13C13C sequences by the 13C12C and 12C12C bonds yields various
short homogeneous segments. Vibrational bands in isotopic copolymers
exhibit one-mode behaviour or two-mode behaviour depending on the
vibrational couplings and dispersions [44]. Knowledge of the force field
and data on various copolymers are needed to interpret the observed be-
haviours ( 45 ].
Most of the bands of polymers are straightforwardly assigned on the
basis of the isotopic shifts in observed wavenumbers. All the ag modes
expected in the region for the idealized infinite all-s-trans (D2h) planar
structure are observed: namely, bands at 1562 (to be termed v3), 1526
(v4), 1319 (Vs), 1044 (v6), 998 (vT) and 385 (Vs) c m - k The weak band at
634 cm -1 is assigned to the ring deformation in big species.
Now we examine the vibrational modes in ag species in some detail.
The v3 band shifts down by 34 and 3 cm -1 on 13C-substitution and
C-deuteration, respectively. The 13C-shift is greater than that expected for
a pure 13 C12 C stretching vibration. The largest 13C-shift, the small D-shift
and the high wavenumber indicate t h a t the band arises from a mixed mode
of the C2=C3 (Cs---C4) stretching (termed Vcc') and inter-ring CC stretching
(Vc'c') vibrations. The corresponding band in 2,2'-bipyrrole is observed at
1618 cm -1 (Fig. 2(d)), implying that the wavenumber of this vibration
becomes high as the conjugation length shortens. In support of this inter-
pretation, it is interesting to note t h a t the peak wavenumber is shifted up by
11 cm -1 with 632.8 nm excitation. This is because at this off-resonance
condition (see Fig. l(f)) the bandshape reflects the distribution of the
existing conjugated segments and the peak wavenumber lies at that of the
major c o m p o n e n t absorbing at 412 nm, whose conjugation length is shorter
than t h a t giving rise to the resonantly enhanced peak in Fig. 2(a).
The weak band at 1526 cm -1 shifts down to 1490 cm -1 on C-deutera-
tion. The 13C-shift is obscure because of the overlap by the broad v3 band.
We tentatively assign this band (v4) to a mixed mode of the NC' stretch
(VNc') and the C3C 4 stretch (Vcc). The corresponding band in 2,2'-bipyrrole
appears at 1479 cm -1, indicating t h a t the wavenumber of this band becomes
low as the conjugation length shortens.
The 13C- and CD-shifts of v s at 1319 cm -1 are --16 and --42 cm -1,
respectively. This band is reasonably assigned to a hybrid mode of Vc, c,
and Vcc. The band shifts down to 1312 cm -1 with 632.8 nm excitation,
indicating that the wavenumber becomes low as the conjugation length
shortens. The corresponding band in NPPD (1277 cm -1) is shifted up by 13
cm -1 with 632.8 nm excitation, implying a change in the vibrational mode
upon deuteration.
The 1044 cm -1 band (v6) is due to the CH in-plane bending (6cn)
vibration because it shifts down to 768 cm -1 on C-deuteration.
 335

The band at 998 cm -1 (vT) with the 13C- and CD-shifts of --8 and --7
cm -1, respectively, is assigned to the ring deformation (Srm~).
A very weak band at 385 cm -1 (Ps) is assigned to the skeletal deforma-
tion (SNC'C').

Raman spectra of as-polymerized doped and partially undoped polypyrrole

In Figs. 3 - 5 are shown the resonance Raman spectra of polypyrrole
in as-polymerized and electrochemically reduced states excited at 632.8,
514.5 and 457.9 nm, respectively. Figures 3(a), 4(a) and 5(a) are the spectra
of as-polymerized C104--doped sample [DPP(C104-)]. Each reduction state
((b) to (f)) in the Figures corresponds approximately to that in Fig. 1.
Notable spectral changes from Fig. 3(a) to (c) are related to the signifi-
cant decrease in absorbance of the C band during the initial stages of reduc-
tion and the concomitant change in the B band (Figs. l(a)-(c)), because the
excitation wavelength, 632.8 nm, lies at the short-wavelength side of the C
band and the long-wavelength side of the B band, and the intensities of the
Raman bands related to the C band are expected to decrease and those re-
lated to the B band to change. Hence, the bands at 1369, 1229, 1082 and 931
cm -1 in Fig. 3(a) are assigned to the species that gives rise to the C band,
presumably the dication. The 1580 cm -1 band is assigned to an overlap of

¢-
(D
E

1600 1400 1200 1000 800

Wavenumber / crn -1
Fig. 3. Raman spectra (632.8 nm excitation, 80 K) of as-polymerized C104--doped poly-
pyrrole [DPP(CIO4-)] and films at various stages of electrochemical reduction: (a)
DPP(CIO4-); (b) 2.8 V; (c) 2.5 V; (d) 2.2 V; (e)2.0 V (see the caption of Fig. 1). Each
spectrum was measured for a different film.
336

r~
tt~ o~

IZ) ~ 0") 0 I

I I I

I "T'r .T ~- T

~ ~¢~ 0 I I O~

~ 0
f Ao
LO
~
(~
~
M"
~= QO M"
I I ~- I 03

i i i i i i i
1600' 1400' 1200' ' 10100' 800
W Q v e n u m b e r / c m -1
Fig. 4. Raman spectra (514.5 nm excitation, 80 K) of as-po]ymerized C]O4--doped
polypyrrole [DPP(C104-)] and films at various stages of electrochemical reduction: (a) -
(e) the same films as those in Fig. 3; (f) 1.6 V.

bands arising f r o m the radical c a t i o n and d i c a t i o n (vide infra). Figures

3(c) - (e) are m o s t l y c o n t r i b u t e d b y the radical c a t i o n species absorbing at
t h e long-wavelength side o f t h e B band. It should be p o i n t e d o u t t h a t t h e
band a r o u n d 9 3 4 - 9 3 0 cm -1 in Figs. 3 ( c ) - ( e ) is d u e n o t to the dication
b u t t o the radical cation, because t h e 1082 cm - ] band o f t h e dication is n o t
observed in t h e Figures.
T h e spectral changes f r o m Fig. 5(c) to (f) are related to a decrease
o f the c o n t r i b u t i o n f r o m the B band and an increase o f the c o n t r i b u t i o n
f r o m the A b a n d to t h e a b s o r b a n c e at 4 5 7 . 9 n m during the final stages o f
r e d u c t i o n . T h e b r o a d b a n d c e n t r e d at 1581 cm -1 with a s h o u l d e r at 1 5 6 2
cm -1 in Fig. 5(c) is shifted to a band c e n t r e d at 1 6 5 6 cm -1 in Fig. 5(d) and
the b a n d c o n t i n u e s t o n a r r o w in Figs. 5(e) and (f), the latter being m o s t l y
due to the n e u t r a l species. On t h e o t h e r hand, Figs. 5(a) and (b) are domi-
n a t e d b y t h e bands o f the radical c a t i o n species absorbing at the short-
wavelength side o f t h e B band.
T h e e x c i t a t i o n wavelength, 514.5 nm, lies in the range o f the B band.
The spectral p a t t e r n s o f Figs. 4(a) - (e) are similar to o n e a n o t h e r apart f r o m
some changes in p e a k w a v e n u m b e r s , w h i c h are related to the c o m p l e x
b e h a v i o u r o f t h e B b a n d during the r e d u c t i o n . Hence, t h e spectra are assign-
ed t o radical cations e x c e p t t h e bands a r o u n d 1563 - 1566 cm -1 (in Figs.
 337

T
C
~D
¢-

1600 1400 1200 1000 800

WQvenumber/cm -1
Fig. 5. Raman spectra (457.9 nm excitation, 80 K) of as-polymerized CIO4--doped poly-
pyrrole [DPP(ClO4-)] and films at various stages of electrochemical reduction. All the
films are the same as those in Fig. 4.

4(c) - (e)), which are considered to arise f r om the neutral species. Some of
the intensities around 1044 cm -1 may also be due to the neutral species. Con-
sistent with the view m e n t i o n e d in the section on optical absorption, the
Raman results indicate that the structure of radical cations in the p o l y m e r
films is n o t unique but that there exist radical cations with different struc-
tures and excited electronic states. For example, Figs. 3(c), 4(c) and 5(c)
are similar to one a not he r in the spectral patterns but some peak wave-
numbers are significantly different, indicating the coexistence of radical
cations with different structures at this reduction state. Such electronic
and structural natures of radical cations are responsible for the spectral dif-
ferences in Figs. 3(c) - (e), 4(a) - (e) and 5(a) - (c), all of which are consid-
ered to arise p r e d o m i n a n t l y from the radical cation parts in the p o l y m e r
film. Tracing back the spectral pattern from Fig. 4(f) to Fig. 4(a), it is
possible to assign the radical cation bands corresponding to v3 to v 7 in
NPP, although the vibrational modes may not necessarily be similar: 1581
(v3), 1443 (v4), 1335 (Vs), 1057 (v6) and 979 cm i (vv) in Fig. 4(b) in Fig.
4(a) some co n tr ibut i on from the dication is noticed around 1080 c m - l ) .
Concerning the origin of the remaining bands in Fig. 4(b), it might be con-
ceived that the centre of inversion s y m m e t r y present in the neutral species
was lost in the radical cation and the modes corresponding to the ungerade
338

ones in neutral species were observed as the Raman bands. However,

mutual exclusion between the Raman and infrared [13] activities generally
holds well for doped polypyrrole. A possible origin is that the electronic
excited states in the radical cation are drastically changed from those in the
neutral species and the Raman bands belonging to the in-plane big species
become enhanced through vibronic interactions between the electronic
excited states.
To summarize this section, Raman spectra of as-polymerized doped
and partially u n d o p e d polypyrrole can be explained by the coexistence, with
different proportions, of dication, radical cation and neutral species. Upon
electrochemical reduction, the dication is converted to the radical cation and
the radical cation to the neutral form.

Vibrational modes and structures o f the dication and radical cation

In Figs. 6 and 7 are shown the spectra of DPP(BF4-), DPPC(BF4-)
and DPPD(BF4-) with 632.8 and 514.5 nm excitation, respectively. The
intensities and peak wavenumbers of some of the bands in Figs. 6(a) and
7(a) are different from those in Figs. 3(a) and 4(a), correspondingly, reflect-
ing the difference in compositions of the dication and radical cations, which
depend on the synthetic conditions. Judging from the intensity of the 933
cm -1 peak in Fig. 6(a) as compared with that of the 931 cm -1 peak in Fig.
3(a), the content of dication in the BF~--doped film is much higher than

a a. r-~
~ ~"" ¢~1 ~1.~ ~... I ~. 0

~ ( ~ O~
, ~,~,
r~D N

1
Le) I P--I ~ i 1
i P o+3

•~ r~ ~
E

E O"J O 0 ~ OD

C ~ ~ I
C ~ m oe4

~-- ~:) ( ~ t"~

I I I CO

,'
1500 1000 500 1500 1000 500
W a v e n u m b e r / cm -~ W o v e n u m b e r / c m -1

Fig. 6. R a m a n spectra (632.8 n m excitation, 80 K) of (a) as-polymerized B F 4 - - d o p e d

p o l y p y r r o l e [ D P P ( B F 4 - ) ] , (b) its 2 , 5 : 3 C - s u b s t i t u t e d analogue [DPPC(BF4-)] and (c)
C-deuterated analogue [ D P P D ( B F 4 - ) ].
Fig. 7. R a m a n spectra (514.5 nm excitation, 80 K) of (a) DPP(BF4-), (b) DPPC(BF4-)
and (c) DPPD(BF4-).
 339

t h a t in t h e C 1 0 4 - - d o p e d film. In Fig. 6 ( b ) t h e b a n d s a r o u n d 1 0 5 5 a n d 967

c m -1 o f radical c a t i o n c o r r e s p o n d i n g to t h o s e in Fig. 6(a) are absent. In Fig.
7(b) t h e d i c a t i o n b a n d at 1 0 8 0 c m -1 is s t r o n g e r t h a n the 1051 c m - l radical
c a t i o n b a n d a n d t h e i n t e n s i t y o f t h e 931 c m -1 b a n d relative to t h a t o f t h e
973 c m -1 o n e d u e to t h e radical c a t i o n is g r e a t e r t h a n t h a t in Fig. 7(a).
T h e s e o b s e r v a t i o n s indicate t h a t t h e c o n t e n t o f d i c a t i o n in the DPPC film
is even higher t h a n t h a t in t h e DPP film. T h e e n h a n c e m e n t o f the d i c a t i o n
b a n d s w i t h 5 1 4 . 5 n m e x c i t a t i o n m a y indicate t h e p r e s e n c e o f d i c a t i o n
a b s o r p t i o n in t h e r e l e v a n t region o v e r l a p p e d b y t h e a b s o r p t i o n o f radical
cation.
N o w , we e x a m i n e t h e v i b r a t i o n a l m o d e s o f t h e ag b a n d s o f t h e radical
c a t i o n in Fig. 7. T h e b a n d at 1 5 8 7 c m -1 shifts d o w n b y 20 c m -1 on 13C-
s u b s t i t u t i o n {taking t h e w a v e n u m b e r o f t h e c e n t r e o f t h e b r o a d b a n d in Fig.
7(b)). T h e shift is t h e s e c o n d largest a m o n g t h e o b s e r v e d bands, a l t h o u g h
m u c h smaller t h a n t h a t o f u3 in NPP, a n d indicates a relatively large contri-
b u t i o n o f t h e C' m o t i o n . A 9 c m -1 d o w n s h i f t o n C - d e u t e r a t i o n , on t h e
o t h e r h a n d , is m u c h larger t h a n t h e c o r r e s p o n d i n g shift of 3 c m -1 in NPP.
This o b s e r v a t i o n implies t h a t Vcc also c o n t r i b u t e s to t h e m o d e . Since the
p e a k w a v e n u m b e r is 25 c m -1 higher t h a n t h a t o f v3 o f NPP, t h e b o n d orders
o f CC m u s t be increased in t h e radical c a t i o n , p o s s i b l y at the e x p e n s e o f a
small decrease in t h e CC' b o n d order, as c o m p a r e d w i t h t h o s e in NPP. T h e
1 4 6 4 c m -~ b a n d shifts d o w n b y 13 c m -~ on C - d e u t e r a t i o n . If this corres-
p o n d s to t h e 1 5 2 6 c m -1 b a n d (Pa) in NPP, t h e p e a k w a v e n u m b e r is signifi-
c a n t l y d o w n s h i f t e d o n doping. This m a y be an i n d i c a t i o n o f a decrease in
b o n d o r d e r o f NC'.
T h e 1 3 4 6 c m ~ b a n d shifts d o w n b y 39 c m -1 o n 13C-substitution and
by 34 c m -~ o n C - d e u t e r a t i o n , w h i c h indicates m u c h m o r e c o n t r i b u t i o n f r o m
Uc'c' to this b a n d c o m p a r e d to us o f NPP at 1 3 1 9 c m -~. T h e u p s h i f t o n dop-
ing b y 27 c m -1 indicates an increase in t h e C'C' b o n d order. T h e 13C-shift
( - - 1 2 c m -1) a n d D-shift ( - - 2 8 7 c m - 1 ) o f t h e 1063 c m 1 b a n d are similar to
t h o s e o f P6 (SCH) o f NPP. T h e 973 c m -1 b a n d , w h i c h d o e s n o t shift on
13C-substitution a n d d o w n s h i f t s b y 3 c m -1 o n C - d e u t e r a t i o n , is assigned to
t h e ring d e f o r m a t i o n in w h i c h t h e ~3C m o t i o n s d o n o t p a r t i c i p a t e . T h e
a p p a r e n t d o w n s h i f t ( - - 2 5 c m -1) o f this b a n d f r o m v7 o f NPP indicates t h a t
the ring is m o r e flexible in t h e d i r e c t i o n o f this n o r m a l m o d e t h a n t h a t in t h e
n e u t r a l species.
In Fig. 3(a) t h e 1 5 8 0 c m -1 b a n d has b e e n assigned to an overlap o f t h e
b a n d s o f t h e d i c a t i o n and radical cation. In Fig. 6(b), o n t h e o t h e r h a n d , t h e
strong 1 5 6 8 c m -~ b a n d is assigned to t h e d i c a t i o n because t h e s p e c t r u m
is d o m i n a t e d b y t h e d i c a t i o n bands. A c c o r d i n g l y , it is certain t h a t the 1593
c m -1 b a n d in Fig. 6(a) is also significantly c o n t r i b u t e d b y t h e d i c a t i o n b a n d .
T h e D-shift o f - - 1 8 c m -1 a n d t h e 13C-shift o f - - 2 5 c m -~ are b o t h larger t h a n
t h o s e in t h e radical c a t i o n , indicating a larger c o n t r i b u t i o n f r o m Vcc a n d
p o s s i b l y f r o m Uc, c, to this vibration. T h e u p s h i f t u p o n d o p i n g 6 c m
g r e a t e r t h a n t h a t in t h e radical c a t i o n is c o n s i s t e n t w i t h m o r e change o f struc-
t u r e in t h e d i c a t i o n . T h e 1 3 2 7 c m - l b a n d shows t h e largest d o w n s h i f t (36
340

cm -1) on 13C-substitution, indicating the largest contribution from Vc'c'

to this mode. The D-shift is not clear due to the unresolved nature of the
band in the 1500 - 1000 cm -~ region, v6 and v7 are at 1086 and 933 cm -1
in DPP and at 1083 and 933 cm -~ in DPPC, respectively. These two modes
in DPPD couple with each other due to the downshift of v6 to the v7 region
and give two peaks at 947 and 881 cm -1. Anyway, the shifts of the two
modes upon doping are greater than those in the radical cation.

Conclusion

Raman bands of neutral polypyrrole have been assigned to the ag and

big modes of ~,~'-linked all-s-trans structure (D2h symmetry) on the basis of
the wavenumber shifts upon 2,5-13C-substitution and C-deuteration. Optical
absorption and Raman spectra of as-polymerized doped and partially
u n d o p e d states indicate that dicationic and radical cationic species coexist
in as-polymerized films and, as the reduction proceeds, dications are convert-
ed to radical cations and radical cations to neutral species. The ag vibrations
in the radical cation and dication are also assigned on the basis of the
isotopic shifts. The changes in structure on going from neutral species to
radical cation and dication are increases in bond orders of the inter-ring CC
and C3C4 and decreases in those of CN and C2Ca. Structural deformation is
larger in the dication than in the radical cation.

Acknowledgement

This work was supported in part by a Grant-in-Aid for Special Project

Research on Properties of Molecular Assemblies (No. 59212001) from the
Ministry of Education, Science and Culture.

References

1 A. F. Diaz, K. K. Kanazawa and G. P. Gardini, J. Chem. Soc. Chem. Commun.,

(1979) 635.
2 K. K. Kanazawa, A. F. Diaz, R. H. Geiss, W. D. Gill, J. F. Kwak, J. A. Logan, J. F.
Rabolt and G. B. Street, J. Chem. Soc. Chem. Commun., (1979) 854.
3 K. K. Kanazawa, A. F. Diaz, W. D. Gill, P. M. Grant, G. B. Street, G. P. Gardini and
J. F. Kwak, Synth. Met., 1 (1979/1980) 329.
4 A. Watanabe, M. Tanaka and J. Tanaka, Bull. Chem. Soc. Jpn., 54 (1981) 2278.
5 G. Tourillon and F. Garnier, J. Electroanal. Chem., 135 (1982) 173.
6 G. B. Street, T. C. Clarke, M. Krounbi, K. K. Kanazawa, V. Lee, P. Pfluger, J. C.
Scott and G. Weiser, Mol. Cryst. Liq. Cryst., 83 (1982) 1285.
7 M. Salmon, A. F. Diaz, A. J. Logan, M. Krounbi and J. Bargon, Mol. Cryst. Liq.
Cryst., 83 (1982) 1297.
8 K. Kaneto, K. Yoshino and Y. Inuishi, Jpn. J. Appl. Phys., 21 (1982) L567.
9 F. Devreux, F. Genoud, M, Nechtsehein, J. P. Travers and G. Bidan, J. Phys. (Paris)
Colloq., 44 (1983) C3-621.
 341

10 S. Hotta, T. Hosaka and W. Shimotsuma, Synth. Met., 6 (1983) 319.

11 W. Wernet, M. Monkenbusch and G. Wegner, Makromol. Chem., Rapid Commun.,
5 (1984) 157.
12 M. Ogasawara, K. Funahashi and K. Iwata, Mol. Cryst. Liq. Cryst., 118 (1985) 159.
13 K. Hyodo and A. G. MacDiarmid, Synth. Met., 11 (1985) 167.
14 X. Bi, Y. Yao, M. Wan, P. Wang, K. Xiao, Q. Yang and R. Qian, Makromol. Chem.,
186 (1985) 1101.
15 M. Satoh, K. Kaneto and K. Yoshino, Synth. Met., 14 (1986) 289.
16 M. Takakubo, Synth. Met., 18 (1987) 53.
17 Y. Shen, K. Carneiro, C. Jacobsen, R. Qian and J. Qiu, Synth. Met., 18 (1987) 77.
18 K. Bender, E. Gogu, I. Hennig, D. Schweitzer and H. Mtinstedt, Synth. Met., 18
(1987)85.
19 S. Kuwabata, K. Okamoto, O. Ikeda and H. Yoneyama, Synth. Met., 18 (1987) 101.
20 A. F. Diaz a n d J . I. Castillo, J. Chem. Soc. Chem. Commun., (1980)397.
21 F. Devreux, G. Bidan, A. A. Syed and C. Tsintavis, J. Phys. (Paris), 46 (1985) 1595.
22 G. B. Street, S. E. Lindsey, A. I. Nazzal and K. J. Wynne, Mol. Cryst. Liq. Cryst., 118
(1985) 137.
23 A. I. Nazzal, G. B. Street and K. J. Wynne, Mol. Cryst. Liq. Cryst., 125 (1985) 303.
24 K. Yakushi, L. J. Lauchlan, T. C. Clarke and G. B. Street, J. Chem. Phys., 79 (1983)
4774.
25 J. C. Scott, P. Pfluger, M. T. Krounbi and G. B. Street, Phys. Rev. B, 28 (1983)2140.
26 J. C. Scott, J. L. Br~das, K. Yakushi, P. Pfluger and G: B. Street, Synth. Met., 9
(1984) 165.
27 J. L. Br4das, J. C. Scott, K. Yakushi and G. B. Street, Phys. Rev. B, 30 (1984)
1023.
28 J. H. Kaufman, N. Colaneri, J. C. Scott and G. B. Street, Phys. Rev. Lett., 53 (1984)
1005.
29 F. Genoud, M. Guglielmi, M. Nechtschein, E. Geni~s and M. Salmon, Phys. Rev. Lett.,
55 (1985) 118.
30 E. M. Geni~s and J.-M. Pernaut, J. Electroanal. Chem., 191 (1985) 111.
31 M. Nechtschein, F. Devreux, F. Genoud, E. Vieil, J. M. Pernaut and E. Geni~s, Synth.
Met., 15 (1985) 59.
32 F. Devreux, F. Genoud, M. Nechtschein and B. Villeret, Synth. Met., 18 (1987) 89.
33 J. L. Br~das, B. Th4mans and J. M. Andre, Phys. Rev. B, 27 (1983)7827.
34 J. L. Br~das, B. Th~mans, J. G. Fripiat, J. M. Andr~ and R. R. Chance, Phys. Rev.
B, 29 (1984)6761.
35 K. K. Kanazawa, A. F. Diaz, M. T. Krounbi and G. B. Street, Synth. Met., 4 (1981)
119.
36 L. Oddi, R. Capelletti, R. Fieschi, M. P. Fontana, G. Ruani, V. Bocchi and G. P.
Gardini, Mol. Cryst. Liq. Cryst., 118 (1985) 179.
37 M. Ogasawara, K. Funahashi, T. Demura, T. Hagiwara and K. Iwata, Synth. Met., 14
(1986) 61.
38 S. J. Hahn, W. J. Gajda, P. O. Vogelhut and M. V. Zeller, Synth. Met., 14 (1986) 89.
39 T. Inoue, I. Hosoya and T. Yamase, Chem. Lett., (1987) 563.
40 K. M. Chenung, B. J. E. Smith, D. N. Batchelder and D. Bloor, Synth. Met., 21
(1987) 249.
41 F. A. Miller, J. Am. Chem. Soc., 64 (1942) 1543.
42 H. Rapoport, N. Castagnoli, Jr. and K. G. Holden, J. Org. Chem., 29 (1964) 883.
43 A. F. Diaz, J. Crowley, J. Bargon, G. P. Gardini and J. B. Torrance, J. Electroanal.
Chem., 121 (1981)355.
44 H, Takeuchi, Y. Furukawa, I. Harada and H. Shirakawa, J. Chem Phys., 80 (1984)
2925.
45 H. Takeuchi, Y. Furukawa, I. Harada and H. Shirakawa, J. Chem. Phys., 84 (1986)
2882.