The chemo-and electropolymerization of thiophene derivatives containing at the third position of a substituent with a stereogenic phosphorus atom

Article abstract of DOI:10.1080/10426507.2012.740107

Recently, differently functionalized polythiophenes (PTs) have found a broad application in material chemistry. Now, we are working in our laboratories on the synthesis of such derivatives functionalized at the third postion of a thiophene ring with a substituent containing a stereogenic heteroatom. In this paper, we would like to report our preliminary results devoted to the chemo-and electropolymerizations of monomeric thiophene derivatives. The classical three-electrode system used for electropolymerization carried out on platinum (Pt), glassy carbon (GC), and gold (Au) electrodes in acetonitrile with lithium perchlorate as the supporting electrolyte electrolyte will be presented. The chemical polymerization was based on the oxidative coupling using ferric chloride, leading to high molecular weight products.

Full text of DOI:10.1080/10426507.2012.740107

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Phosphorus, Sulfur, and Silicon and the
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The Chemo- and Electropolymerization
of Thiophene Derivatives Containing at
the Third Position of A Substituent with
A Stereogenic Phosphorus Atom
Anna Fenyk a , Dorota Krasowska b c , Paweł Urbaniak a & Józef
Drabowicz b c
a Department of Inorganic and Analytical Chemistry, Faculty of
Chemistry , University of Lodz , Tamka 12, 91-403 , Lodz , Poland
b Department of Heteroorganic Chemistry, Polish Academy of
Sciences , Center of Molecular and Macromolecular Studies ,
Sienkiewicza 112, 90-363 , Lodz , Poland
c Institute of Chemistry Environmental Protection and
Biotechnology , Jan Dlugosz University in Czestochowa , Armii
Krajowej 13/15, 42-200 , Czestochowa , Poland
Accepted author version posted online: 01 Nov 2012.Published
online: 29 May 2013.
To cite this article: Anna Fenyk , Dorota Krasowska , Paweł Urbaniak & Józef Drabowicz (2013) The
Chemo- and Electropolymerization of Thiophene Derivatives Containing at the Third Position of A
Substituent with A Stereogenic Phosphorus Atom, Phosphorus, Sulfur, and Silicon and the Related
Elements, 188:4, 473-482, DOI: 10.1080/10426507.2012.740107
To link to this article: http://dx.doi.org/10.1080/10426507.2012.740107
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Phosphorus, Sulfur, and Silicon, 188:473–482, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.740107
THE CHEMO- AND ELECTROPOLYMERIZATION OF
THIOPHENE DERIVATIVES CONTAINING AT THE THIRD
POSITION OF A SUBSTITUENT WITH A STEREOGENIC
PHOSPHORUS ATOM
Anna Fenyk,1 Dorota Krasowska,2,3 Paweł Urbaniak,1
and Jo´zef Drabowicz2,3
1Department of Inorganic and Analytical Chemistry, Faculty of Chemistry,
University of Lodz, Tamka 12, 91-403 Lodz, Poland
2Department of Heteroorganic Chemistry, Polish Academy of Sciences, Center of
Molecular and Macromolecular Studies, Sienkiewicza 112, 90-363 Lodz, Poland
3Institute of Chemistry Environmental Protection and Biotechnology, Jan Dlugosz
University in Czestochowa, Armii Krajowej 13/15, 42-200 Czestochowa, Poland
GRAPHICAL ABSTRACT
O
P
O
P
S
S
n
(S)- 2a
(S)-4a (99%)
mp=145-146oC
FeCl3
[α]589= -33,89 (0,059, CH2Cl2)
[α]589= -35,6 (2,8, CH2Cl2)
or rac-2b
or rac-4b (93%)
CCl4-CHCl3 (1:1), r.t, 6 hrs
O
P
O
P
O
S
O
n
S
rac-5
rac-3
(64%)
Abstract Recently, differently functionalized polythiophenes (PTs) have found a broad appli-
cation in material chemistry. Now, we are working in our laboratories on the synthesis of such
derivatives functionalized at the third postion of a thiophene ring with a substituent contain-
ing a stereogenic heteroatom. In this paper, we would like to report our preliminary results
devoted to the chemo- and electropolymerizations of monomeric thiophene derivatives. The
classical three-electrode system used for electropolymerization carried out on platinum (Pt),
glassy carbon (GC), and gold (Au) electrodes in acetonitrile with lithium perchlorate as the
supporting electrolyte electrolyte will be presented. The chemical polymerization was based
on the oxidative coupling using ferric chloride, leading to high molecular weight products.
Received 9 October 2012; accepted 10 October 2012.
Address correspondence to Dorota Krasowska, Department of Heteroorganic Chemistry, Polish Academy
of Sciences, Center of Molecular and Macromolecular Studies, Sienkiewicza 112, 90-363, Lodz, Poland. E-mail:
dkras@cbmm.lodz.pl; Paweł Urbaniak, Department of Inorganic and Analytical Chemistry, Faculty of Chemistry,
University of Lodz, Tamka 12. 91-403 Lodz, Poland. E-mail: pawelurb@chemia.uni.lodz.pl
473

474
A. FENYK ET AL.
Keywords Chiral polythiophene derivatives; oxidative coupling; chemical polymerization;
fluorescent properties; random regioisomerism
INTRODUCTION
Among the number of π-conjugated polymers, substituted polythiophenes (PTs) are
one of the most important and widely studied conductive materials that can be used in a
variety of application for field-effect transistors, polymer light-emitting diodes, antistatic
coatings, batteries, electromagnetic shielding materials, solar cells, or bio- or gas sensors.1
Functionalization of an aromatic backbone by a side chain allows an easier processing
of such polymeric materials, but most importantly promotes their electronic properties.
Recently, a lot of efforts have been devoted to the preparation of chiral PTs functionalized
with a substituent containing a stereogenic carbon atom, for example, in amino alcohols,
amino acids, esters, and ethers. It is reasonable to expect that they should show optical
activity when the polymer chains adopt a suitably ordered conformation (or self-assembled
aggregates) in slightly polar solvents, at low temperatures or in a solid state.2,3
Selected functionalized chiral PTs have already found practical applications, for
example, as good candidates for the preparation of enantioselective electrodes, membranes,
electroactive chiral surface, optically active catalysts, or optically active chromatographic
support.4,5 Below we are going to describe part of our recent experiments devoted to the
synthesis and basic structural determinations of new chiral PT systems functionalized at the
third position of a thiophene ring with a substituent containing a stereogenic heteroatom.
Synthesis of Monomers
Enantiomerically pure and racemic tert-butylphenylphosphine oxides [(S)-1a or rac-
1b] were synthesized following the known procedure.6 Racemic and enantiomerically
pure (S)-tert-butylphenyl-2-(3ꢁ-thiophene)ethyl phosphine oxides 2a,b were obtained by
the patented procedure7 via alkylation of the metallated oxides 1a (generated by a di-
rect deprotonation of oxide with sodium hydride in THF at 0◦C) with 2-(3ꢁ-thienyl)ethyl
bromide(chloride). The reaction proceeds with the retention of the configuration at a phos-
phinyl phosphorus atom, giving the expected oxide 2a without detectable racemization
(Scheme 1).
X
X=Cl or Br
O
P
O
P
S
O
1) NaH
Ph
Ph
P
H
Na
THF; 0o
r.t.
THF, 0oC
t-Bu
t-Bu
t-Bu
Ph
S
(S)-1a or rac-1b
(S)-(-)-2a (39%)
mp=145-146oC
rac-2b (85%)
m.p.=113-114 oC
or
Α
[ ]589= -35,6
Scheme 1

THE CHEMO- AND ELECTROPOLYMERIZATION OF THIOPHENE DERIVATIVES
475
Its enantiomeric purity (higher than 99%) was established by NMR spectroscopy
using (S)–(–) –tert–butylphenylphosphinothioic acid as a chiral solvating agent (CSA).
Racemic O-2-(3ꢁ-thienyl)ethyl tert-butylphenylphosphinate 3 was prepared in 93%
yield by the reaction of sodium 2-(3ꢁ-thienyl)ethoxide with tert-butylphenylposhinyl chlo-
ride (Scheme 2).
O
t-Bu
O
P
P Cl
t-Bu
Ph
Ph
O
O
Na
OH
NaH
THF, 0oC
THF (dry); 0oꢀ
r.t.
S
S
S
rac-3 (93%)
Η
D =1.5549
colourless oil
Scheme 2
Chemical Polymerization
The 3-substituted PTs were synthesized by a modification of standard chemical
polymerization based on an oxidative coupling with iron trichloride as oxidative agent.8
Our optimal reaction condition for polymerization are based on the use of a mixture of
CCl4/CHCl3 as a reaction medium (Scheme 3). The resulting polymers were obtained
in good yield as orange solids and were identified by spectroscopic methods. Racemic
polyphosphinic ester 5 was additionally purified by a Soxhlet extraction with methanol.
O
P
O
P
S
S
n
(S)- 2a
(S)-4a (99%)
mp=145-146oC
FeCl3
Α
[ ]589= -33,89 (0,059, CH2Cl2)
[
= -35,6 (2,8, CH2Cl2)
Α]589
or rac-4b (93%)
CCl4-CHCl3 (1:1), r.t, 6 hrs
or rac-2b
O
P
O
P
O
S
O
n
S
rac-5
rac-3
(64%)
Scheme 3

476
A. FENYK ET AL.
Figure 1 1H NMR spectra of O-2-(3ꢁ-thienyl)ethyl tert-butylphenylphosphinate and its polymeric analog in
CDCl3.
Physicochemical and Structural Characterization of Polymeric
Derivatives
The isolated polymeric products 4 and 5 are soluble in dichloromethane, chloroform,
and tetrahydrofuran. Their good solubility should allow an easier processing and potential
application as conductive materials. The structures of the isolated polymeric samples were
confirmed by NMR spectroscopy. 1H-NMR spectra clearly confirmed the presence of α,α‘-
conjugated thiophene system having an irregular structure as can be expected for the
chemical polymerization induced by FeCl3. This conclusion is based on the presence in
the 1H NMR spectrum of polymeric O-2-(3ꢁ-thiophene)ethyl tert-butylphenylphosphinate
recorded in CDCl3 of two resonance peaks (in the range of 2.93 to 3.21 ppm) assigned
to the methylene protons of the CH2 group bonded directly with the thiophene rings
(Figure 1). They indicate the presence of HT and HH (or TT) coupling chains. The HT
coupling percentage in the main chain can be approximately calculated from the ratio of
the intensities of signals of the α-methylene protons. The regioregularity of PT 5 measured
Figure 2 1H NMR spectra of (S)-tert-butylphenyl-2-(3ꢁ-thienyl)ethyl phosphine oxide 4a and its polymeric
analog in CDCl3.

THE CHEMO- AND ELECTROPOLYMERIZATION OF THIOPHENE DERIVATIVES
477
Figure 3 Absorption and emission spectra of (S)-4a in CHCl3 (C = 3 × 10−5 M), λexc = 411 nm (Color figure
available online).
by the head-to-tail content is equal to ca 59%. In the case of the polymeric material derived
from (S)- tert-butylphenyl-2-(3ꢁ-thiophene)ethyl phosphine oxide 4a, determination of the
1
degree of regioregularity from the H NMR spectrum is more difficult. However, it is
evident from the analysis of peak intensities of all the CH2 proton groups that the isolated
PT derivative contains, in fact, the HH or TT defects (Figure 2.).
Optical Properties of Polymers (S)-4a and 5. UV-Visable Aborption
and Fluorescence
The optical properties of the dedoped polymers 4a and 5 were examined as chloroform
solutions by UV-visible and fluorescence spectroscopy. They exhibit the characteristic band
originating from the π-conjugated polymer backbone with a maximum of absorption at 411
and 420 nm, respectively. These bands can be attributed to a coil conformation of the main
PT chain. The UV-VIS absorption maxima for both polymers are blue-shifted, reflecting
a decrease in effective conjugation length. This is consistent with random regioisomerism
of the measured samples. Moreover, photoluminescence spectra of (S)-4a and 5 showed a
maximum emission at 549 nm indicating a yellow fluorescence (Figs. 3, 4).
No
Solvent
λmax (A) [nm]
νA [cm−1
]
λmax (F) [nm]
νF[cm−1
]
Stokes Shift [cm−1
]
4a
5
CHCl3
CHCl3
411
420
24331
23810
549
549
18215
18215
6116
5595
Electrochemical Studies
To characterize the electrochemical properties of isolated thiophenes 2b and 3 the
cyclic voltammetric method was used. Both monomers were oxidized at a potential between
1.16 V (on Au electrode) and at +0.6 V up to +1.95 V vs. Ag/AgCl (on platinum [Pt]

478
A. FENYK ET AL.
Figure 4 Absorption and emission spectra of rac-5 in CHCl3 (C = 1,6 × 10−5 M), λexc = 420 nm (Color figure
available online).
electrode). The cyclic voltammograms showed three types of behavior.9 The peaks height
of compound 3 decreases and the cyclic voltammogram approximates the base line in the
cycles thereafter. No reduction peaks were obtained at a studied potential range. From
the decreasing current it was concluded that a thin nonconductive film was deposited on
the surface of the electrode (Fig. 6). The racemic phosphine oxide 2b showed another
characteristic behavior on gold (Au) and glassy carbon (GC) electrodes. The oxidation
current decreased after the first cycle but increased in the cycles thereafter. These results
mean that no deposition of a redoxidizable polymer films on the electrodes surfaces were
observed. The resulting polymer formed a colloidal greenish glow at the bottom of the cell.
2b Showed on a Pt electrode another different behavior (Fig. 5). The cyclic voltammograms
of this system showed a little decreasing of the oxidation current in contrast to the case for
3. This result is not clear and requires further study.
Figure 5 Cyclic voltammograms of polymerization of tert-butylphenyl-2-(3ꢁ-thienyl)ethyl phosphine oxide rac-
2b in CH3CN + LiClO4 on Pt, Gc, and Au electrodes, respectively. Repetitive sweeps between 0.6–2 V vs.
Ag/AgCl electrode. The red lines indicate the 1st scan (Color figure available online).

THE CHEMO- AND ELECTROPOLYMERIZATION OF THIOPHENE DERIVATIVES
479
Figure 6 Cyclic voltammograms of polymerization of O-2-(3ꢁ-thienyl)ethyl tert-butylphenylphosphinate rac 3
in CH3CN + LiClO4 on Pt, Gc, and Au electrodes, respectively. Repetitive sweeps between 0.6–2 V vs. Ag/AgCl
electrode. The red lines indicate the 1st scan (Color figure available online).
Experimental
The NMR spectra were recorded on a Bruker spectrometer Avance AV 200 (Bruker,
Karlsruhe, Germany) (200.16 MHz (1H), 50.30 MHz (13C), 81,03 MHz (31P)) in CDCl3.
Mass spectral data were collected on MAT95-Finnigan spectrometer (Finnigan MAT, Bre-
men, Germany). Optical rotation was determined on 241 MC-Perkin Elmer polarimeter
(Perkin Elmer,Vienna, Austria) at room temperature. Melting point was determined on
Betius apparatus (PHMK VEB Analytik, Dresden, Germany) and was uncorrected. Tetrahy-
drofuran (THF) and diethyl ether were dried and distilled over sodium in the presence of
benzophenone under argon atmosphere. CHCl3 was purified by distillation over P2O5.
CH2Cl2 was dried with CaH2 before use. The reactions were carried out under dry argon.
Column chromatography was performed on Merk Silica Gel (F254 60, 270–400 mesh).
Merk Silica F254 plates were used for thin layer chromatography and visualization was
effected with UV light (254 nm). UV/Vis absorption spectra were recorded at room tem-
perature with resolution increment 1 nm using a Nicolet Evolution 300 spectrophotometer.
The fluorescence spectra were recorded at room temperature with resolution increment
1 nm, slit 3 using a FluoroMax-4 spectrophotometer. The source of light was a 150 W
continuous ozone-free xenon lamp. IR spectra were recorded as KBr pellets using FT IR
60 instrument. ATI Mattson, Mass spectral data were collected on a MAT95–Finnigan
spectrometer (Finnigan MAT, Bremen, Germany). Microanalyses were performed with a
CHNSO-EA1108 analyzer.
The electropolymerization of thiophene derivatives has been studied with cyclic
voltammetry. Potential sweeps were controlled by a AUTOLAB PGSTAT 128N potentio-
stat/galvanostat (Metrohm Autolab B.V., Utrecht, Netherlands). The measurements were
carried out in typical three-electrode system: a platinum gauze as the counter electrode,
Ag/AgCl electrode as reference and Pt, GC, or Au electrodes as the working ones. The
experiments were conducted in 0.1 M solutions of lithium perchlorate as the supporting
electrolyte in acetonitrile. The solution was deareated for 15 min. by dry argon bubbling
and electropolymerization took place under argon atmosphere. The measurements have
been recordered with the potential scan rate of 50 mV/s at 298 K. Potentials were cycled

480
A. FENYK ET AL.
between +0.6 V and +2.0 V or +2.25 V vs. the Ag/AgCl electrode. The concentration of
thiophenes that were examined were 0.01 mol L-1.
TERT-BUTYLPHENYL-2-(3ꢀ-THIENYL)ETHYL PHOSPHINE OXIDE–racemic
Mixture. To a stirred suspension of 50%-NaH (0.763 g, 15.90 mmol) in THF (50 mL)
at 0◦C under argon atmosphere secondary tert-butylphenylphosphine oxide 1b (2.633 g,
14.45 mmol) dissolved in THF (50 mL) was slowly dropped. After stirring at 0◦C for
1 h, freshly distilled 2-(3ꢁ- thienyl)ethyl chloride (2.120 g, 14.45 mmol) was added to the
reaction mixture. The reaction mixture was stirred at 0◦C for 3 h, and then was allowed to
reach room temperature and stirred at RT for additional 21 h. The reaction was monitored
by 31 P NMR spectroscopy. After 24 h, when the presence of substrate was not observed,
the reaction mixture was treated with 50 mL of saturated ammonium chloride solution
and extracted with 50 mL CH2Cl2 (3 × 50 mL). The combined organic phases were dried
over anhydrous MgSO4, filtered and evaporated in vacuo. The crude product (3.690 g) was
purified by washing with cold hexane to give 3.584 g (yield 84.9%) of tert-butylphenyl-2-
(3ꢁ-thiophene)ethyl phosphine oxide as a white solid. mp = 113◦C –114◦C
3
1H NMR [ppm] (200 MHz, CDCl3) δ = 1.14 (d, JP-H = 14.50 Hz, 9H, Me3C),
2.23–2.43 (m, 2H, CH2--C3ꢁTiof), 2.48–2.72 (m, 1H, CH2–P), 2.97–3.16 (m, 1H, CH2–P),
6.91–6.95 (m, 2H, ArTiof), 7.21–7.24 (m, 1H, ArTiof), 7.45–7.58 (m, 3H, Ar), 7.69–7.78 (m,
2H, Ar);
31P NMR [ppm] (81 MHz, CDCl3) δ = 48.93;
13C NMR [ppm] (50 MHz, CDCl3) δ = 20.99 (d, J = 3.22 Hz, CH2–C3ꢁTiof), 23.05
(d, J = 62.02 Hz, CH2–P), 23.19 (s, (CH3)3C), 31.46 (d, J = 68.90 Hz, CH3C), 119.30
(s, C2’ Tiof), 124.52 (s, C5’ Tiof), 126.50 (s, C4’ Tiof), 127.03 (d, J = 10.56 Hz, o-CArx2),
128.51 (d, J = 86.05 Hz, ipso-CAr), 130.19 (s, p-CAr), 130.56 (d, J = 7.8 Hz, m-CArx2),
140.62 (d, J = 14.44 Hz, C3ꢁ Tiof).
MS (CI/izobutan): m/z (%): 293.2 (100) [M + 1], 585.3 (72,5) [2M + 1].
HRMS (EI) dla C16H21OPS: calcd.: 292.10507, found: 292.10488.
Elem. Anal. for C16H21OPS: calcd.: C (65.73%), H (7.24%), S(10.97%); found: C
(65.82%), H (7.08%), S (10.95%).
IR (KBr) [ν/cm−1]: 3074; 3048 (C–Haryl); 2979; 2933; 2911; 2865 (C–Halif); 1464,
1435; 1169; 1156 (s) (P O).
TERT-BUTYLPHENYL-2-(3ꢀ-THIENYL)ETHYL PHOSPHINE OXIDE-optica-
lly Active Form. To a stirred suspension of 50%-NaH (0.082g, 1.71 mmol) in THF
(5 mL) at 0◦C under argon atmosphere dissolved in tetrahydrofuran (10 mL) secondary
(S)-tert-butylphenylphosphine oxide (0.282g, 1.55 mmol) was slowly dropped. After stir-
ring at 0◦C for 1 h, freshly distilled 2-(3ꢁ- thienyl)ethyl bromide (0.296 g, 1.55 mmol)) was
added to the reaction mixture. The reaction mixture was stirred at 0◦C for 3 h, and then
was allowed to reach room temperature and stirred for the next 24 h. The reaction was
monitored by 31 P NMR spectroscopy. After 27 h, when the presence of substrate was not
observed, the reaction mixture was treated with 15 mL of saturated ammonium chloride
solution and extracted with CH2Cl2 (3 × 15 mL). The combined organic phases were
washed with brine and dried over anhydrous MgSO4, filtered and evaporated in vacuo. The
crude product (0.439 g) was purified by crystallization from CH2Cl2: hexane solution to
give 0.176 g (yield: 39%) of enantiomarically pure (S)-tert-butylphenyl-2-(3ꢁ-thienyl)ethyl
phosphine oxide as white solid.

THE CHEMO- AND ELECTROPOLYMERIZATION OF THIOPHENE DERIVATIVES
481
[α]D = –35,57 (2,8, CH2Cl2)
mp = 145–146◦C
3
1H NMR [ppm] (200 MHz, CDCl3) δ = 1.15 (d, JP-H = 14.47 Hz, 9H, Me3C),
2.23–2.49 (m, 2H, CH2--C3ꢁTiof), 2.54–2.72 (m, 1H, CH2–P), 2.97–3.16 (m, 1H, CH2–P),
6.91–6.95 (m, 2H, ArTiof), 7.21–7.24 (m, 1H, ArTiof), 7.49–7.52 (m, 3H, Ar), 7.70–7.78 (m,
2H, Ar);
31P NMR [ppm] (81 MHz, CDCl3) δ = 48.92;
MS (CI/isobutane): m/z (%): 293.2 (100) [M+1], 585.3 (72.5) [2M+1]
Elemental analysis: dla C16H21OPS: calcd.: C(65.73%), H (7.24%), S (10.97%);
found: C (65.64%), H (7.11%), S (10.99%);
IR (KBr) [ν/cm−1]: 3075, 3049 (C–Haryl); 2979; 2933; 2912; 2866 (C–Halif), 1464;
1435; 1169; 1156 (s) (P = O).
O-2-(3ꢀ-THIENYL)ETHYL TERT-BUTYLPHENYLPHOSPHINATE rac-3. To a
stirred suspension of 50%-NaH (0.824g, 34.32 mmol, 1.1 equiv) in THF (20 mL) at 0◦C
under argon atmosphere 3-thiopheneethanol (2 g, 15.6 mmol) was added. After stirring
at 0◦C for 2 h, a solution of tert-butylphenylphosphinyl chloride (3.337g, 15.36 mmol)
in THF (10 mL) was added to the reaction mixture. The reaction was monitored by 31
P NMR spectroscopy. After 6 h the reaction mixture was treated with 30 mL of satu-
rated ammonium chloride solution and extracted with CH2Cl2 (3 × 30 mL). The com-
bined organic phases were washed with brine and dried over anhydrous MgSO4, filtered
and evaporated in vacuo. The product (4.474 g) was obtained in 93% yield as colorless
oil.
1H NMR (200 MHz, CDCl3): δ 1.09 (d, J = 15.67 Hz, 9H, (CH3)3C); 3.03 (t, J =
6.66 Hz, 2H, CH2–Tiof); 3.87–3.98 (m, 1H, CH2–O–P); 4.02–4.35 (m, 1H, CH2–O–P);
6.96 (dd, J = 0.84; 4.66 Hz, 1H, Tiof); 7.04 (d, J = 1.84 Hz; 1H, Tiof); 7.24–7.28 (m, 1H,
Tiof); 7.35–7.65 (m, 5 H, Ph).
13C NMR (125 MHz, CDCl3): δ 24.04 ((CH3)3C); 31.46 (d, J = 6.7 Hz; CH2–O–P);
32.44 (d, J = 100.4 Hz, (CH3)3C); 64.43 (d, J = 7.2 Hz, CH2–Tiof); 121.77; 125.41;
127.45; 128.16 (d, J = 11.56 Hz, Corto × 2); 128.36; 131.94 (d, J = 2.49 Hz); 133.03 (d, J
= 8.86 Hz, Cmeta × 2); 137.91.
31 P NMR (81 MHz, CDCl3): δ 51.51(s).
MS (CI/isobutane): m/z:111; 309 [M + 1].
HRMS (EI) dla C16H21O2PS: calcd.: 308.0996, found: 308.0999.
Chemical Polymerization
General procedure: Iron trichloride (4 equiv) was suspended in a CHCl3/CCl4 (1:1)
mixture (c = 0.08 M). The studied monomer was dissolved in CHCl3/CCl4 (1:1) (c = 0.08
M) and the solution was added dropwise to the reaction mixture at room temperature under
argon atmosphere. The mixture was stirred for 6 h under a flow of argon. The reaction
mixture was treated with 1M HCl and diluted with CHCl3. The organic phase was washed
with HCl solution untill the Fe(III) ions were present in the inorganic phase. The chloroform
phase was dried over anhydrous MgSO4 and filtered. Evaporation of the solvent gave the
crude polymers. The polyester 5 was additionally purified by a Soxhlet extraction with
methanol.

482
A. FENYK ET AL.
POLYMER 4a
1H NMR (200 MHz, CDCl3): δ 1.13–1.21 (bm, 9H, C(CH3)3), 2.42 (bm, 2H, CH2);
2.83, 2.19 (2bm, 2H, CH2); 7.04 (bm, 1H, 4-Thioph); 7.45, 7.76 (2bm, 5 H, Ph);
31 P NMR (81 MHz, CDCl3): δ 48.75 49.12 (bm)
POLYMER 4b
1H NMR (200 MHz, CDCl3): δ 1.12 (bm, 9H, C(CH3)3), 2.38, 2.83, 3.16 (3xbm, 4H,
2 × CH2); 7.00 (bs, 1H), 7.44, 7.71 (2 × bm, 5 H, Ph).
31 P NMR (81 MHz, CDCl3): δ 48.93 (bm)
POLYMER 5
1H NMR (500 MHz, CDCl3): δ 1.08–1.10 (bm, 9H, C(CH3)3), 2.92, 3.21 (2 × bm,
2H, CH2); 3.99, 4.03, 4.23, 4.35 (4 × bm, 2H, CH2–OP); 7.08, 7.12 (2 × bm, 1H); 7.40,
7.47, 7.62 (3 × bm, 5 H, Ph)
31 P NMR (81 MHz, CDCl3): δ 52.86 (bm)
REFERENCES
1. Fichou, D. (Ed.), Handbook of Oligo- and Polythiophenes; Vol. 10; Wiley-VCH: Weinheim, 1999;
pp. 491-515.
2. Bouman, M. M.; Meijer, E. W. Adv. Mater. 1995, 7, 385-387.
3. Bouman, M. M.; Havinga, E. E.; Janssen, R. A. J.; Meijer, E. W. Mol. Cryst. Liq. Cryst. 1994,
256, 439-448.
4. Andreani, F.; Angiolini, L.; Caretta, D.; Salatelli, E. J. Mater. Chem. 1998, 8, 1109-1111.
5. Cagnoli, R.; Lanzi, M.; Mucci, A.; Parenti, F.; Schenetti, L. Polymer 2005, 46, 3588-3596.
6. Drabowicz, J.; Łyz˙wa, P.; Omelan´czuk, J.; Pietrusiewicz, K. M.; Mikołajczyk, M. Tetrahedron:
Asymmetry 1999, 10, 2757-2763.
7. Drabowicz, J.; Krasowska, D. Polish Patent pending, P398421.
8. Sugimoto, R.; Takeda, S.; Gu, H. B.; Yoshino, K. Chem. Express 1986, 1, 635-638.
9. Welzel, H.-P.; Kossmehl, G.; Boettcher, H.; Engelmann, G.; Hunnius, W.-D. Macromolecules
1997, 30, 7419-7426.