Development in synthesis and electrochemical properties of thienyl derivatives of carbazole

Article abstract of DOI:10.1016/j.tet.2005.09.142

A convenient and higher yielding synthetic route to N-alkyl-bis(thiophene)- and N-alkyl-bis(ethylenedioxythiophene) carbazole derivatives is reported and their aggregation, and electrochemical properties are characterized. The key step in the synthesis of this group of compounds has been the Stille-type coupling reaction between the N-alkyldibromocarbazole and tin derivatives of thiophene or ethylenedioxythiophene, as the best way for preparation of conjugated N-alkylcarbazole derivatives. For this group of compounds we also present an electrochemical polymerization effect.

Full text of DOI:10.1016/j.tet.2005.09.142

Tetrahedron 62 (2006) 758–764
Development in synthesis and electrochemical properties
of thienyl derivatives of carbazole
a
Joanna Cabaj, Krzysztof Idzik, Jadwiga Sołoducho
a
a,
b
*
and Antoni Chyla
a
Institute of Organic Chemistry, Biochemistry and Biotechnology, Wrocław, University of Technology,
0-370 Wrocław, Wybrze z˙ e Wyspia n´ skiego 27, Poland
5
b
Institute of Physical and Theoretical Chemistry, Wroclaw, University of Technology, 50-370 Wrocław, Wybrze z˙ e Wyspia n´ skiego 27, Poland
Received 10 March 2005; revised 12 September 2005; accepted 29 September 2005
Available online 4 November 2005
Abstract—A convenient and higher yielding synthetic route to N-alkyl-bis(thiophene)- and N-alkyl-bis(ethylenedioxythiophene) carbazole
derivatives is reported and their aggregation, and electrochemical properties are characterized. The key step in the synthesis of this group of
compounds has been the Stille-type coupling reaction between the N-alkyldibromocarbazole and tin derivatives of thiophene or
ethylenedioxythiophene, as the best way for preparation of conjugated N-alkylcarbazole derivatives. For this group of compounds we also
present an electrochemical polymerization effect.
q 2005 Elsevier Ltd. All rights reserved.
1
. Introduction
derivatives of 2-thiophene- and 2-(3,4-ethylenedioxythio-
phene)carbazole, and their aggregation properties in LB
1
0–12
Since their discovery, conjugated monomers and their
polymers attract continuing interest as a result of their
suitability in a broad range of applications, such as
batteries, electroluminescent devices, field-effect transis-
tors and photovoltaics.
films.
In many photonic applications like photon
1
3
funnels or energy transfer controllers the concentration
of chromophore is essential as well as the knowledge of the
LB film architecture. We undertook the study of formation
of single and two-component Langmuir and LB films of
synthesized alkylheteroaromatic molecules. Particular
attention has been paid to the films containing alkylhetero-
aromatic compounds mixed with polyoctadecylthiophene
1
The need for sensitive and highly specific chemical sensors
is of growing importance in both the monitoring and control
of human exposure to chemicals present in environment and
medical technology. As a result of this great hopes and
expectations are associated with sensors based on organic
materials. The manufacture of high quality ultrathin,
anisotropic organic films by means of the Langmuir–
Blodgett (LB) technique is finding important practical
application in many fields including sensorics, electrooptics
(
(
PODT), docosanoic acid (DA) and 22-tricosenoic acid
TA), which are low molecular mass amphiphilic molecules
facilitating the deposition (DFs—Deposition Facilitators).
PODT was prepared by the typical chemical oxidative
polymerisation with FeCl , DA and TA (Aldrich) were
3
carefully recrystallised from chloroform.
1
–7
and electronic devices as well as biomimetic systems.
Since the Langmuir–Blodgett technique allows the
controlled, layer-by-layer deposition of ordered molecular
films on solid substrates, the films constructed by means of
this method are expected to be components for potential
Carbazole is a well-known hole-transporting and electro-
luminescent unit. Polymers containing carbazole moieties
either in the main or side chains have attracted much
attention because of their unique properties, which allow for
various photonic applications (photoconductivity, electro-
14
applications in sensorics, photonics or photoelectronics.
8
,9
Advantages in the processability of chemically polymerized
soluble thiophene derivatives, have been recognized by a
number of researchers in this field. But chemical polymeri-
zation enables the deposition of films on substrates by a
variety of methods, for example the Langmuir–Blodgett
technique. In this case electrochemical deposition
of polymer on platinum or ITO plates were used.
The photophysical properties of the thin film of monomers
luminescence, and photorefraction).
In this paper, supplementing our previous publications, we
report on the synthesis of novel amphiphilic, monomeric
Keywords: Electrochemical properties; Thienyl derivative; Carbazole.
*
Corresponding author. Tel.: C48 71 320 24 27; fax: C48 71 328 40 64;
e-mail: jadwiga.soloducho@pwr.wroc.pl
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.09.142

J. Cabaj et al. / Tetrahedron 62 (2006) 758–764
759
and polymers and their electrochemical properties were
then investigated.
ethylenedioxythiophene) derivatives of N-alkylcarbazoles
(4). Compound 4 was achieved with a high yield (90%)
using this method.
2
. Results and discussion
The structures of the synthesized compounds were
confirmed by H and C NMR, and elemental analysis.
1
13
2.1. Synthesis of bis(2-thiophene)- and
bis(2-(3,4-ethylenedioxythiophene))carbazoles
2.2. Langmuir films
1
5
Based of our previous work, we found that the Stille
procedure is a convenient method for the preparation of
another group of carbazole derivatives with aggregation
properties. One of them, N-nonyl-3,6-bis(2-thiophene)car-
bazole (TPC, 3c) was patented because of its gave
The molecular structures of the components for the binary
systems of interest are shown in Figure 1.
To obtain Langmuir films, the synthesized compounds
(Scheme 1): N-butyl-3,6-bis(2-thiophene)carbazole (3a),
N-butyl-3,6-bis(2-(3,4-ethylenedioxythiophene)carbazole
1
6
aggregation and electrochemical properties.
(
4a), N-amyl-3,6-bis(2-thiophene)carbazole (3b), N-amyl-
Scheme 1 illustrates the synthetic routes for the novel
N-alkyl-3,6-bis(2-thiophene)- or -(2-(3,4-ethylenedioxy-
thiophene))carbazoles. These compounds were synthesized
by a two-step procedure. N-alkylcarbazole (1) was
successfully brominated using N-bromosuccinimide
3,6-bis(2-(3,4-ethylenedioxythiophene)carbazole (4b),
N-nonyl-3,6-bis(2-thiophene)carbazole (3c), N-decyl-3,6-
bis(2-thiophene)carbazole (3d), N-decyl-3,6-bis(2-(3,4-
ethylenedioxythiophene)carbazole (4d), were dissolved in
chloroform (Aldrich, HPLC grade). Concentrations of
solutions were maintained at ca. 1 mg/ml.
1
7
(
NBS), to give the dibromo compound 2. A Stille-type
coupling reaction was employed to obtain 3,6-bis
2-thiophene)-N-alkylcarbazole (3) from 2-trimethyltinthio-
(
The films of desired composition were formed by dropwise
spreading of N-alkylcarbazole derivatives solutions, with or
without DFs (docosanoic acid, tricosenoic acid and
phene (Scheme 1) and 3,6-dibromo-N-alkyl-carbazole (2).
A similar procedure was used to synthesize the 2-(3,4-
S
Sn(CH3)3
S
S
o
3
DMF, 100 C
Pd(PPh ) /N
N
3
4
2
R
Br
Br
NBS
1
CHCl3
N
R
N
2
R
o
DMF, 100 C
Pd(PPh ) /N
2
R = a/C H ; b/C H ; c/C H19; d/C10H
O
4
9
5
11
9
21
O
S
3
4
O
O
Y; 2a = 80%, 2b = 78%, 2c = 83%, 2d = 81%
Y; 3a = 78%, 3b = 75%, 3c = 80%, 3d = 76%
Y; 4a = 90%, 4b = 88%, 4c = 91%, 4d = 89%
O
O
S
4
S
Sn(CH3)3
N
R
Scheme 1.
O
O
O
O
S
S
S
S
3c
N
4a
N
5
6
7
S
n
HOOC
HOOC
Figure 1. The binary system components: 3c, N-nonyl-3,6-bis(2-thiophene)carbazole (TPC); 4a, N-butyl-3,6-bis(2 (3,4-ethylenedioxythiophene) carbazole
DTPC); 5, PODT; 6, TA; 7, DA.
(

760
J. Cabaj et al. / Tetrahedron 62 (2006) 758–764
polyoctadecylthiophene) on high purity water at 295 K. The
binary systems were mixed to obtain resulting molar
compositions of the deposition mixture of 2:1, 1:1 and
1
:2. The electrical conductivity of this quartz double
K5
distilled, deionized water was lower than 10 S/m. The
p–A isotherms were measured by means of a commercial
LB trough (KSV, System 5000), using a Pt hydrophilic
Wilhelmy plate. The compression rates used in our
experiments ranged between 5 and 100 mm/min, depending
on the rigidity of the films. From the measured p–A
isotherms of all synthesized derivatives of N-alkylcarbazole
it was clear that the derivatives with an even number of C
1
8
atoms in alkyl chains do not form stable Langmuir films.
Therefore N-nonyl-3,6-bis(2-thiophene)carbazole (TPC)—
the derivative with odd number of C atoms in the alkyl
chains was chosen for further experiments. Properties of the
other derivatives are still under investigation. Figure 3
shows the p–A isotherms of the investigated binary systems
of TPC. For comparison the p–A isotherm of pure TPC is
shown in Figure 2. Although pure TPC forms good
Langmuir films their LB films are not very stable because
the transfer occurs under a relatively low surface pressure.
The surface pressure p is generally considered to be equal
to the reduction of the pure liquid surface tension by the
film, i.e. pZs Ks, where s is the surface tension of the
Figure 4. The computer-generated models of TPC.
In Figure 4 a computer-generated (optimization structure-
AM1, Gaussian03, Molekel) model of the TPC molecule is
presented. If the average plane of all aromatic rings
(hydrophilic part of molecule) was laid flat on the water,
the aliphatic chain would be elevated by 358. In such an
arrangement calculated area per molecule equals ca.
1
2
.1 nm , which is also confirmed by p–A isotherm.
During compression, molecules can slip each under the
other forming a ‘spoon like’ stacking and in close packed
phase (liquid condensed) both calculated and measured,
0
0
pure liquid and s is the tension of the film covered surface.
from p–A isotherm, the area per molecule amounts to ca.
0
binary systems of interest. Tricosenoic and docosanoic
acids, the model amphiphiles can also be effectively used
for creation of binary systems of interest.
9
8
7
6
5
2
.4 nm . In Figure 5 we propose LB film structures for the
4
3
2
1
0
1
TPC
–
0
0.2 0.4 0.6 0.8
A [nm2]
1
1.2
Figure 2. p–A Isotherm of TPC.
TPC – PODT
TPC – TA
TPC - DA
Comparison of p–A isotherms of Figure 3 shows that when
using binary films, one can obtain much higher surface
pressures and therefore closer packing, and PODT
facilitates this process the most effectively. This is caused
by synergy between the structures of TPC and PODT.
Figure 5. LB films structures of measured binary systems.
In our case the deposited LB films are complete and of high
quality, as confirmed by additivity of UV–vis spectra
(
Fig. 6).
6
5
4
3
2
1
0
0
0
0
0
0
Contrary to TPC, DTPC does not form any stable Langmuir
films, neither alone nor in binary systems. In solution it
forms dimers, as confirmed by 2D photoluminescence
spectra. The 2D photoluminescence spectrum together with
excitation and emission spectra are shown in Figure 7.
TPC - DA 1:1
TPC - PODT 1:1
TPC - TA 1:1
In the excitation spectrum of DTPC (Fig. 7) one can observe
two strong, specific regions, a monomer region (ca. 330 nm),
and one corresponding to the dimer (ca. 400 nm). In the
emission spectrum, the monomer region is at a characteristic
wavelength at ca. 380 nm whereas the second region
(470 nm) is covered by the absorbance of the dimer.
0
0
0.5
A [nm2]
1
1.5
Figure 3. p–A Isotherms of TPC–DA, TPC–PODT, TPC–TA complexes.

J. Cabaj et al. / Tetrahedron 62 (2006) 758–764
761
0.6
0.5
0.4
0.3
0.2
0.1
0
TPC - PODT, 7LB
TPC - PODT, 5LB
TPC - PODT, 3LB
200
400
600
800
Wavelength (nm)
Figure 6. UV–vis spectra of binary complex’s (TPC–PODT) LB films.
Figure 8. Repeating potential scanning polymerization of 0.01 mol TPC in
0.1 M tetrabutylammonium perchlorate/acetonitrile (TBAP/CH
scan rate of 100 mV/s.
3
CN) at a
The preferred method of polymer synthesis for optimum
film formation was the application of potential near 1.4 V in
an electrolyte solution of (Bu) N(BF ) 0.2 M/acetonitrile.
4
4
The deposition of PTPC was found to proceed rapidly and
the synthesis of thick PTPC films was not complicated and
we were able to obtain homogenous and stable electro-
K8
conductive polymer (sZ6.25!10 S/cm).
Figure 9 shows the conductivity dependence as a current–
voltage plot, which is linear over the range of film thickness.
1
2
0
8
6
4
2
0
1
0
1
2
3
4
5
6
7
Voltage [V]
Figure 9. Current–voltage characteristic of electropolymer PTPC.
Figure 7. 2D Photoluminescence spectrum of DTPC.
In our case we were only able to measure the spectro-
electrochemistry of an electrochemically prepared film of
PTPC (Fig. 10). The absorption spectra of solutions of
PTPC were not obtained, due to the insoluble nature of the
polymer.
2
.3. Electrochemical characterization of PTPC
To enable a comparison of the conductivity of LB films in
different binary systems, electrochemically deposited
poly(N-nonyl-3,6-bis(thiophene)carbazole) (PTPC) films
were generated. The electrochemical synthesis of PTPC
was carried out by the galvanostatic method on both
platinum and ITO-coated glass substrates.
The absorbance spectrum of the thin PTPC layer suggests a
ground state electronic structure with minimal interchain
1
9
aggregation in the condensed state.
At Figure 8 is shown the repeated potential scan
polymerization for TPC in 0.1 M tetrabuthylammonium
perchlorate/acetonitrile. The polymerization begins at an
Eonset,m of 0.09 V with an Ep,m at 0.15 V. Carbazoles
electropolymerize at much lower potential and relative
rapidly compared to the single-ring monomers such as
pyrrole, or EDOT.
The dark PTPC polymer is illustrated by the photograph in
Figure 11.
2
0
From our previous experience and theoretical calculations
we can say that the structure of TPC should be almost
planar, whereas the dihedral angle between the central ring
(carbazole) and lateral one (thiophene) is 27.58 (Fig. 12).

762
J. Cabaj et al. / Tetrahedron 62 (2006) 758–764
2.7
in CDCl3 using TMS as internal standard. Column
chromatography was carried out on Merck Kiesel silica
gel 60. Dry DMF was used immediately after distilling from
a solution containing benzophenone-sodium. Other starting
materials, reagents and solvents were used as received from
suppliers.
1.94
The purity of the products was checked by thin layer
chromatography, and their molecular structures were
1
13
confirmed by H NMR and C NMR spectroscopy as
well as by elemental analysis and UV–vis spectroscopy.
1
.18
2
00
430
660
Wavelength (nm)
4
4
.2. Synthesis
Figure 10. The UV–vis spectrum of electropolymer PTPC film.
.2.1. Compound a. The procedure for preparation of
N-alkylcarbazoles (1a–1d). N-Alkylation of aromatic
compounds involving nitrogen heterocycles such as carba-
zole with alkyl halide in presence of based solution and
benzyl triethyl ammonium chloride (BTEAC) as phase-
transfer catalyst readily proceeded under mild conditions,
1
7
starting from 1 g of carbazole.
Figure 11. PTPC polymer films electrochemical deposited on ITO glass
after electrical measurements.
1
Selected data for 1c. YZ81% (1.41 g), mp 23–24 8C, H
NMR (CDCl ) d 8.10 (d, JZ7.8 Hz, 2H, arom. H), 7.49–
3
7
.37 (m, 4H, arom. H), 7.25–7.19 (m, 2H, arom. H), 4.27 (t,
JZ7.2 Hz, 2H, CH ), 1.84 (q, JZ7.2 Hz, 2H, CH ), 1.46–
2
2
1
3
1
.24 (m, 12H, CH ), 0.87 (t, JZ7.2 Hz, 3H, CH ). C NMR
2 3
(
CDCl ) d 140.4, 140.0, 125.7, 123.0, 120.5, 118.8, 108.8,
3
43.1, 32.0, 29.6, 29.6, 29.4, 29.3, 29.1, 27.4, 22.8, 14.4. For
C H N calcd C, 85.95; H, 9.27; N, 4.77, found; C, 85.70,
H, 9.05, N, 4.67.
2
1 27
4
.2.2. Compound b. The procedure for preparation of
N-alkyl-3,6-dibromocarbazole (2a–2d). N-Alkylcarbazoles
were converted to dibromocarbazole derivatives in presence
of NBS in anhydrous chloroform, starting from 1 g of 1a–
1
7
1
1
d. Selected data for 2b. YZ78% (1.30 g), mp 72 8C, H
NMR (CDCl ) d 8.04 (s, 2H, arom. H), 7.47 (d, JZ9.1 Hz,
3
2
H, arom. H), 7.16 (d, JZ10.1 Hz, 2H, arom. H), 4.15 (t,
Figure 12. Fully optimized geometries (AM1 level of theory) of N-nonyl-
3,6-bis(2-thiophene)carbazole, TPC.
JZ7.2 Hz, 2H, CH ), 1.75 (q, JZ7.2 Hz, 2H, CH ), 1.30–
2
2
3
1
1
.20 (m, 4H, CH ), 0.79 (t, JZ6.8 Hz, 3H, CH ). C NMR
2 3
(
CDCl ) d 139.3, 129.0, 123.4, 123.3, 111.9, 110.4, 43.3,
3
29.3, 28.6, 22.5, 13.9. For C H N calcd C, 86.02; H, 6.80;
17 19
N, 5.90, found; C, 85.9; H, 6.75; N, 5.79.
3. Conclusions
A series of N-alkylcarbazole derivatives have been syn-
thesized using the Stille condensation reaction. This
methodology provides a convenient route to obtain the title
compounds, which could find applications for example in
sensoric and active materials. Carbazole derivatives mixed
with substances facilitating film building gave stable and
good quality Langmuir and Langmuir–Blodgett films of
desired composition. We examined the electroconductivity
of LB films built with TPC monomer in a binary system. The
electrical properties of a thin polymer film of PTPC, obtained
by electrochemical polymerization, were determined.
1
Compound 2c. YZ83% (1.28 g), mp 46–47 8C, H NMR
CDCl ) d 8.06 (s, 2H, arom. H), 7.48 (d, JZ6.7 Hz,
(
3
2
7
H,arom. H) 7.19 (d, JZ8.6 Hz, 2H, arom. H), 4.15 (t, JZ
.2 Hz, 2H, CH ), 1.76 (q JZ7.1 Hz, 2H, CH ), 1.25–1.17
2
1
2
2
1
3
(
m, 12H, arom. H), 0.82 (t, JZ6.5 Hz, 3H, CH3). C NMR
CDCl ) d 139.3, 129.0, 123.4, 123.2, 111.9, 110,4, 43.3,
(
3
3
1.8, 29.4, 29.3, 29.2, 28.7, 27.2, 22.6, 14.1. For
C H NBr calcd C, 55.89; H, 5.58; N, 3.10, found; C,
21 25
2
5
5.76; H, 5.48; N, 3.00.
1
Compound 2d. YZ81% (1.23 g), mp 54–56 8C, H NMR
CDCl ) d 8.14 (s, 2H, arom. H), 7.56 (d, JZ6.7 Hz, 2H,
(
3
4. Experimental
arom. H), 7.27 (d, JZ8.7 Hz, arom. H), 4.45 (t, JZ7.0 Hz,
H, CH ), 1.81 (q, JZ7.1 Hz, 2H, CH ), 1.35–1.19 (m, 14H,
CH ), 0.91 (t, JZ6.8 Hz, 3H, CH ). C NMR d 140.5,
2
2
2
1
3
4
.1. General
2
3
125.6, 122.9, 120.4, 118.8, 108.7, 43.1, 31.9, 29.6, 29.6,
29.4, 29.0, 27.4, 22.8, 14.3. For C H NBr calcd C, 56.78;
H, 5.85; N, 3.015, found; C, 56.70; H, 5.75; N, 2.95.
Melting points are uncorrected. All NMR spectra were
acquired a Brucker VXR-300 at 300 ( H) and 75 ( C) MHz
2
2
27
2
1
13

J. Cabaj et al. / Tetrahedron 62 (2006) 758–764
763
4.2.3. Compound c. The procedure for preparation of
N-alkyl-3,6-(2-thiophene)carbazoles (3a–3d). Monomers
were synthesized according to our previous method by a
coupling reaction of N-alkyl-2,7-dibromocarbazoles (2a–
arom. H), 7.15 (d, JZ8.7 Hz, 2H, arom. H), 6.3 (s, 2H,
arom. H), 4.13 (m, 10H, CH ), 1.73 (q, JZ7.2 Hz, 2H,
2
15
CH ), 1.28–1.21 (m, 4H, CH ), 0.81 (t, JZ6.8 Hz, 3H,
2
2
1
CH3). C NMR (CDCl ) d 141.8, 139.3, 129.0, 123.4,
3
3
2
2
d) with 2-trimethyltin-thiophene, starting from 1 g of 2a–
d. Selected data for 3a. YZ78% (0.79 g), mp 110 8C, H
123.2, 111.9, 110.4, 99.7, 64.7, 43.3, 29.4, 28.6, 22.5, 13.9.
For C H NS O calcd C, 67.23; H, 5.26; N, 2.71 found C,
66.89; H, 4.66; N, 2.67.
1
2
9
27
2 4
NMR (CDCl ) d 8.35 (d, JZ7.1 Hz, 2H, arom. H), 7.75 (d,
3
JZ10.3 Hz, 2H, thioph. H), 7.41–7.37 (m, 4H, arom, H),
1
7
.27 (d, JZ7.2 Hz, 2H, thioph. H), 7.13 (d, JZ6.4 Hz, 2H,
Compound 4c. YZ91% (1.16 g), oil, H NMR (CDCl ) d
3
thioph. H), 4.30 (t, JZ7.2 Hz, 2H, CH ), 1.90–1.66 (m, 2H,
8.04 (s, 2H, arom, H), 7.46 (d, JZ6.8 Hz, 2H, arom. H),
7.16 (d, JZ8.7 Hz, 2H, arom. H), 6.25 (s, 2H, arom. H),
4.12 (t, JZ7.2 Hz, 10H, CH ), 1.73 (t, JZ7.0 Hz, 2H, CH ),
2
CH ), 1.64–1.32 (m, 4H, CH ), 0.95 (t, JZ7.3 Hz, 3H,
2
2
1
CH3). C NMR (CDCl ) d 140.4, 125.5, 122.8, 120.3,
3
3
2
2
3
1
1
7
18.6, 108.6, 42.7, 31.1. 20.5, 13.8. For C H NS calcd C,
2
4.38; H, 5.46; N, 3.61; found C, 74.60; H, 5.68; N, 3.20.
1.24–1.17 (m, 14H, CH ), 0.81 (t, JZ6.8 Hz, 3H, CH ). C
4
21
2
2
3
NMR (CDCl ) d 141.8, 139.3, 129.0, 123.5, 123.2, 111.9,
3
110.4, 99.7, 64.7, 43.4, 31.8, 29.4, 29.3, 29.2, 28.8, 27.2,
22.6, 14.1. For C H NS O calcd C, 69.08; H, 6.15; N,
2.44 found C, 68.70; H, 5.73; N, 2.04.
1
Compound 3b. YZ75% (0.76 g), mp 63 8C, H NMR
3
3
35
2 4
(CDCl ) d 8.05 (s, 2H, arom. H), 7.49 (d, JZ6.8 Hz, 2H,
arom. H), 7.31–7.29 (m, 2H, arom. H), 7.19–7.16 (m, 4H,
arom. H), 7.09–7.07 (m, 2H, arom.H), 4.13 (t, JZ7.2 Hz,
3
1
Compound 4d. YZ89% (1.12 g), mp 55 8C, H NMR
2
H, CH ), 1.75 (q, JZ7.4 Hz, 2H, CH ), 1.46–1.22 (m, 4H,
(CDCl ) d 8.05 (s, 2H, arom. H), 7.47 (d, JZ6.8 Hz, 2H,
arom. H), 7.18 (d, JZ8.7 Hz, 2H, arom. H), 6.26 (s, 2H,
2
2
3
1
3
CH ), 0.82 (t, JZ6.9 Hz, 3H, CH ). C NMR, (CDCl ) d
2
3
3
1
2
5
39.3, 129.0, 126.9, 125.2, 123.5, 123.3, 111.9, 110.4, 43.3,
9.4, 28.6, 22.5, 13.9. For C H NS calcd C, 74.80; H,
.77; N, 3.49; found C, 74.40; H, 5.20; N, 3.30.
arom. H), 4.13 (t, JZ7.2 Hz, 2H, CH ), 1.74 (q, JZ7.1 Hz,
2
2H, CH ), 1.24–1.16 (m, 14H, CH ), 0.81 (t, JZ6.8 Hz, 3H,
2
5
23
2
2
2
1
3
CH3). C NMR (CDCl ) d 141.8, 139.3, 129.0, 1253.5,
3
123.3, 111.9, 110.4, 99.7, 64.7, 43.4, 31.9, 29.5, 29.4, 29.3,
29.2, 28.8, 27.2, 26.7, 14.1. For C H NS O calcd C,
69.49; H, 6.35; N, 2.38; found, C, 69.30; H, 6.20; N, 2.27.
1
Compound 3c. YZ80% (0.81 g), mp 193–195 8C, H NMR
CDCl ) d 8.05 (s, 2H, arom. H), 7.47 (d, JZ6.8 Hz, 2H,
3
4
37
2 4
(
3
arom. H), 7.32–7.29 (m, 2H, arom. H), 7.17 (d, JZ8.7 Hz,
2
2
H, arom. H), 7.09–7.07 (m, 2H, arom. H), 4.13 (t, JZ7.2 Hz,
H, CH ), 1.75 (q JZ7.1 Hz, 2H, CH ), 1.25–1.19 (m, 12H,
4
.3. Oxidative polymerization
2
2
1
3
CH ), 0.81 (t, JZ6.8 Hz, 3H, CH ). C NMR (CDCl ) d
2
3
3
Monomer TPC was electrochemically polymerized using
repeated potential scan polymerization with a standard
three-electrode. Electropolymerization of TPC was carried
on in 0.1 M tetrabuthylammonium perchlorate/acetonitrile
at a scan rate of 100 mV/s.
1
2
7
39.3, 126.9, 125.1, 123.5, 123.3, 111.9, 110.4, 43.4, 31.9,
9.5, 29.3, 28.8, 27.2, 22.7, 14.1. For C H NS calcd C,
6.13; H, 6.83; N, 3.06; found C, 75.90; H, 6.50; N, 2.88.
2
9
31
2
1
Compound 3d. YZ76% (0.77 g), mp 189–191 8C, H NMR
(
CDCl ) d 8.05(s, 2H, arom. H), 7.48(d, JZ6.8 Hz, 2H, arom.
3
4
.4. Electrochemical polymerization
H), 7.32–7.29 (, 2H, arom. H), 7.18 (d, JZ8.7 Hz, 2H, arom.
H), 7.09–7.07 (m, 2H, arom. H), 4.13 (t, JZ7.2 Hz, 2H, CH2),
1
Polymer electrochemistry was carried out on a standard model
galvanostat employing a platinum disk working electrode or
ITO (areaZ1.55 cm ) disk working electrode, and a platinum
plate counter electrode. Spectroelectrochemistry experiments
were carried out on a Cary 100 Bio Varian UV–vis
spectrophotometer. Polymer films were deposited onto ITO-
coated glass plates (9.8!50.0!0.5 mm, 20 U/square, Delta
Technologies). Insoluble polymers were cast onto ITO or
platinum plates (10!70!0.2 mm) from dry acetonitrile.
.75 (q, JZ7.1 Hz, 2H, CH ), 1.25–1.16 (m, 14H, CH ), 0.84
2 2
13
t, JZ6.8 Hz, 3H, CH3). C NMR (CDCl ) d 139.3, 129.0,
3
(
2
1
2
7
26.9, 125.1, 123.4, 123.3, 111.9, 110.4, 43.4, 31.9, 29.5, 29.3,
9.2, 28.8, 27.2, 22.6, 14.1. For C H NS calcd C, 76.41; H,
3
0
33
2
.05; N, 2.97; found C, 76.35; H, 6.95; N, 2.70.
4
.2.4. Compound d. The preparation of N-alkyl-3,6-(2-(3,4-
ethylenedioxythiophene))carbazoles (4a–4b). These com-
pounds were successfully synthesized according to our
method reported for preparation of 3,4-ethylenedioxythio-
1
5
phene derivatives of tetrazines, starting from 1 g of 2a–2d.
Acknowledgements
1
Compound 4a. YZ90% (1.19 g), oil, H NMR (CDCl ) d
3
Financial support from the Polish Science Foundation
(KBN, Grant No. PBZ-KBN-098/T09/2003) is gratefully
acknowledged.
8
7
4
.02 (s, 2H, arom. H), 7.46 (d, JZ6.7 Hz, 2H, arom. H),
.17 (d, JZ8.7 Hz, 2H, arom. H), 6.26 (s, 2H, arom. H),
.12 (t, JZ7.2 Hz, 10H, CH ), 1.72 (q, JZ7.4 Hz, 2H,
2
CH ), 1.27 (sec., JZ7.5 Hz, 2H, CH ), 0.87 (t, JZ7.3 Hz,
2
2
1
H, CH3). C NMR (CDCl ) d 141.8, 139.3, 129.0, 123.4,
3
3
3
1
23.2, 111.9, 110.6, 110.4, 99.7, 64.7, 43.0, 31.0, 20.5, 13.9.
For C H NS O calcd C, 66.77; H, 5.00; N, 2.78, found C,
References and notes
2
8
25
2 4
6
6.20; H, 4.60; N, 2.70.
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1
1
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