Functionalized branched EDOT-terthiophene copolymer films by electropolymerization and post-polymerization “click”-reactions

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# Functionalized branched EDOT-terthiophene copolymer films by electropolymerization and post-polymerization “click”-reactions

Miriam Goll 1, Adrian Ruff 1, Erna Muks 1, Felix Goerigk 1, Beatrice Omiecienski 1,
Ines Ruff 2,§, Rafael C. González-Cano 3, Juan T. Lopez Navarrete 3,
M. Carmen Ruiz Delgado 3 and Sabine Ludwigs *1

Full Research Paper [Open Access](http://www.beilstein-journals.org/bjoc/about/openAccess.htm)

Address:
1IPOC-Functional Polymers, Institute for Polymer Chemistry,

University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany,
2Thermo Fisher Scientific GmbH, Im Steingrund 4-6, 63303 Dreieich,
Germany and 3 Department of Physical Chemistry, University of

Málaga, 29071 Málaga, Spain

Email:
Sabine Ludwigs * [- sabine.ludwigs@ipoc.uni-stuttgart.de](mailto:sabine.ludwigs@ipoc.uni-stuttgart.de)

- Corresponding author

§ née Dreiling

Keywords:

band-gap engineering; “click”-chemistry; conducting polymers;

electropolymerization; Raman spectroscopy; surface functionalization

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

[doi:10.3762/bjoc.11.39](http://dx.doi.org/10.3762%2Fbjoc.11.39)

Received: 19 December 2014

Accepted: 18 February 2015

Published: 11 March 2015

This article is part of the Thematic Series "Electrosynthesis".

Guest Editor: S. R. Waldvogel

License and terms: see end of document.

## Abstract

The electrocopolymerization of 3,4-ethylenedioxythiophene (EDOT) with the branched thiophene building block 2,2′:3′,2″-terthio
phene (3T) is presented as a versatile route to functional polymer films. Comparisons to blend systems of the respective homopoly
mers PEDOT and P3T by in situ spectroelectrochemistry and Raman spectroscopy prove the successful copolymer formation and

the access to tailored redox properties and energy levels. The use of EDOT-N3 as co-monomer furthermore allows modifications of
the films by polymer analogous reactions. Here, we exemplarily describe the post-functionalization with ionic moieties by 1,3
dipolar cycloaddition (“click”-chemistry) which allows to tune the surface polarity of the copolymer films from water contact

angles of 140° down to 40°.

## Introduction

The many different applications of conducting polymers

demand for tailored properties, especially the position of the

HOMO level and the HOMO–LUMO band gap value are

crucial for the applicability in different devices such as organic

photovoltaics, organic field effect transistors, organic light

emitting diodes or organic electrochromic windows [1-6].

There are different ways to tune HOMO–LUMO band gap

values, mostly concerning the modification of the used

monomers, for example by a rigidification of the conjugated

system [7], the introduction of electron-withdrawing [8] or elec
tron-donating groups [9,10] to the monomers or the increase of

the quinoid character [11]. One widely used approach is the

335

introduction of different co-monomers to build up copolymers,

e.g., new donor–acceptor low band gap copolymers [12-14].

Among synthetic approaches electropolymerization has gained

particular attention, because it allows easy tuning of polymer

film properties by modification of the monomers. In addition to

electropolymerization of simple conjugated monomers [15]

more complex monomers which include different building

blocks were presented. Roncali et al. used for example EDOT

containing branched thiophene monomers [16,17]. In some of

the more complex monomer systems the electropolymerization

can be regarded as a crosslinking step [17,18]. Electropolymer
ization of monomer mixtures is another powerful tool to modify

material properties. Among a variety of monomer mixtures

including pyrrole and thiophene [19,20], 2,2’-bithiophene and

pyrrole [21,22] and dicyanovinylene-substituted cyclopentabi
thiophene and EDOT [23], we recently presented the copoly
merization of EDOT and the branched unit 2,2’:3’,2’’-terthio
phene (3T) [24].

Additional functionalities, such as ions, can be introduced either

by direct attachment of the functional moieties to the monomers

or via precursor monomers which give access to post-polymer
ization reactions. Ionic groups on conjugated polymers –

so-called conjugated polyelectrolytes [25] – are discussed in the

context of solubility tuning [26], sensor applications [27],

improvement of solar cell performance by usage as hole injec
tion layers [28] or the modification of the surface polarity

heading for bio-compatible electrodes [29]. The direct elec
tropolymerization of ionically modified monomers was for

example carried out by Reynolds et al. for sulfonic acid func
tionalized pyrrole [30,31]. The groups of Heeger et al. [32-34],

Bäuerle et al. [35] and Visy et al. [36] synthesized sulfonic acid

and carboxylic acid functionalized polythiophenes to study the

so called “self-doping” effect of conducting polymers [37].

Interwoven polymeric composite materials based on polymer

blends were obtained by electrodepositing sulfonic acid modi
fied bithiophene followed by bipyrrole monomers [38].

In some cases the direct polymerization of ionically modified

monomers remains problematic: this was for example reported

in the case of sulfonic acid modified pyrrole, where film deposi
tion was only possible when a copolymerization with pristine

pyrrole was conducted [30].

Post-polymerization processes on the other hand have to

provide high yields and mild reaction conditions to keep the

formed polymer backbone intact and to reach a considerable

degree of conversion of functional groups. The Cu(I)-mediated

1,3-dipolar cycloaddition between azides and alkynes (“click”
reaction) is a commonly used reaction in post-polymerization

processes [39,40]. In the case of the azidomethyl-modified

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

EDOT (EDOT-N3) building block different approaches of
modifying the corresponding polymer PEDOT-N3 have been
conducted so far, including the modification of electropolymer
ized PEDOT-N3 with different redox functionalities as
employed by Bäuerle et al. [41-43]. The PEDOT relative,

propargyl-substituted chemically synthesized 3,4-propylene
dioxythiophene was used by Kumar et al. to introduce ionic

groups by “click”-chemistry to render the solubility of the

gained polymers from organic solvents to water solubility [44].

“Electro-click” modifications were used for chemically synthe
sized PEDOT-N3 and copolymers of EDOT-N3 and EDOT with
halogens and fluorescent markers [45,46] and of electrochemi
cally synthesized PEDOT-N3 to introduce fluorinated alkyl
chains [47]. In the latter case the water contact angles could be

gradually varied.

We here present the electrocopolymerization of EDOT-N3 with
the branched terthiophene 2,2’:3’,2’’-terthiophene and the post
polymerization into an ionically modified copolymer. Only

recently, we reported on the copolymerization of 3T and EDOT

as a straightforward approach to conducting polymer films with

tailored HOMO levels and therefore band gap values by varying

the monomer ratio during chemical (with FeCl3 as oxidant) and
electrochemical polymerization [24]. Characterization of the
chemically polymerized copolymers by 1 H DOSY NMR and

MALDI–TOF spectroscopy indicated that the EDOT and 3T

units are covalently linked. While comparisons with these

chemically synthesized polymers support our finding, a real

proof of copolymer formation for the electropolymerized films

was still missing in our previous publication. Here, we show

that by comparison of blend films of the homopolymers with

copolymer films obtained by electropolymerizing monomer

mixtures the copolymer formation, i.e., the covalent linkage of

the two co-monomers can be proven also for the electrochemi
cally synthesized films by means of electrochemical and spec
troscopic (in situ and ex situ) techniques.

We further show that the redox properties of the polymers

remain identical when EDOT–N3 is used as a co-monomer
instead of EDOT and that “click”-chemistry is a versatile tool to

largely modify material properties, e.g., by the introduction of

covalently bound ionic groups.

## Results and Discussion

Electropolymerization of monomer mixtures does not necessar
ily lead to copolymers of the two monomers but can also result

in polymer blend structures. This is often a difficult task to

prove [48]. Case one is that both monomers readily react with

each other and the polymerization of a mixture of monomers

leads to a copolymer. In case two, both monomers react with

themselves but not with each other and the polymerization of

336

the monomer mixture leads to a mixture of the two homopoly
mers which can be regarded as a polymer blend. We mimicked

the latter case by consecutive electro-deposition of layers of the

respective homopolymers on the electrode. We have shown in

earlier work [24] that the oxidation potentials of EDOT and 3T
at 1.0 V and 1.1 V vs Fc/Fc +, respectively, do principally allow

for copolymer formation. Scheme 1 highlights the different

polymer constitutions of the electropolymerized films we

discuss in the present article: pure homopolymer films P3T and

PEDOT, the blend film containing both P3T and PEDOT layers

and the copolymer which represents a random combination of

the monomers EDOT and 3T and strongly depends on the ratio

of the monomers used during the electropolymerization. The

nomenclature of the copolymers is in accordance to our

previous publication [24]: P(EDOT- _co_ -3T)-1:1 means for

example that a 1:1 mixture of 3T and EDOT is used during

polymerization.

Figure 1A summarizes representative cyclic voltammograms

(CVs) of PEDOT, P3T, a PEDOT/P3T-blend and the copolymer

P(EDOT- _co_ -3T)-1:1. During the electrochemical oxidation the

Scheme 1: Polymer constitutions of the electropolymerized films.

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

homopolymers PEDOT and P3T both show chemically revers
ible behavior, but they differ significantly in their onset potentials of −0.8 V and 0.3 V vs Fc/Fc +, respectively (blue and red

curves). The cyclic voltammogram (CV) of the PEDOT/P3T
blend has two current maxima located at −0.3 and +0.7 V. Both

values correspond to the oxidation potentials of the respective

homopolymers indicating the combination of the redox prop
erties of PEDOT and P3T. The P(EDOT- _co_ -3T)-1:1 film on the

other hand shows one broad oxidation wave with an onset

potential of −0.6 V. The UV–vis absorption spectra of the

neutral electropolymerized films are shown in Figure 1B: while

the homopolymers exhibit absorption maxima at 630 nm for

PEDOT and 450 nm for P3T, the PEDOT/P3T-blend and the

copolymer P(EDOT- _co_ -3T)-1:1 film show rather broad spectral

shapes with maxima around 530 nm. From the spectra of the

neutral compounds a clear distinction between the copolymer

and the blend is not possible.

Monitoring the optical properties during the electrochemical

oxidation process by in situ spectroelectrochemistry, however,

gives further information about the electronic properties of the

337

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

Figure 1: Cyclic voltammograms in 0.1 M NBu4PF6/MeCN (A) and vis–NIR spectra (B) of electropolymerized films of PEDOT (blue curve), P3T (red
curve), PEDOT/P3T-blend (black curve) and P(EDOT- _co_ -3T)-1:1 (purple curve) deposited on ITO-coated glass substrates. C–F: In situ spectroelectrochemistry of films deposited under potentiostatic control on ITO with oxidative cycles at 50 mV s −1 in 0.1 M NBu4PF6/MeCN (C and E) and vis–NIR
spectra (D and F) recorded during the forward scan in the oxidation process of PEDOT/P3T-blend (C and D) and P(EDOT- _co_ -3T)-1:1 (E and F). The
films were prepared according to [24].

charged species and thus allows to allocate redox states and

absorption bands to certain species. The recorded spectra of the

blend and the copolymer films reveal remarkable differences.

Figure 1C and D show the CVs and the absorption spectra

recorded during the forward scan of the PEDOT/P3T-blend

film. Following the process of the first oxidation wave in the

CV the broad absorption band is decreasing asymmetrically

upon potential increase. The loss of the shoulder of the absorp
tion band at around 630 nm suggests that PEDOT is oxidized

first yielding the charged PEDOT species with an absorption of

338

the radical cation around 890 nm. This is in accordance to

literature where the PEDOT radical cation is described with an

absorption maximum around 880 nm [24]. Only when

approaching the second oxidation wave around +0.9 V the

absorption band at 450 nm is decreasing, revealing a new

absorption at 780 nm which can be attributed to the radical

cation formation of P3T matching the literature value [24]. To

our knowledge this is one of very few examples [48,49], where

a polymer blend provides the separated absorption and redox

properties of the homopolymers which allow for the separated

addressing of the polymers by CV and monitoring thereof by

spectroscopy.

The copolymer P(EDOT- _co_ -3T)-1:1 (Figure 1E and F) shows,

as described above, one broad oxidation wave in the CV and a

broad absorption with a maximum at 530 nm. During the oxi
dation the 530 nm band is decreasing uniformly and steadily

while at 830 nm a single band is ascending, which indicates the

formation of the charged radical cation species. This is in agree
ment with our earlier data where we showed this uniform steady

decrease of the band at 830 nm absorption during the oxidation

for P(EDOT- _co_ -3T) polymer films with different ratios of the

monomers EDOT and 3T [24]. This, with respect to the blend

films, completely opposite behavior is a reliable argument that

indeed a copolymer is formed from the copolymerization of

EDOT and 3T. Table 1 summarizes the characteristic values for

the neutral and charged polymer films.

As a further analytical tool we employed Raman spectroscopy

which addresses the different vibrational modes of the samples.

Figure 2A shows the Raman spectra of the homopolymers

PEDOT and P3T, the blend film PEDOT/P3T-blend and the

copolymer P(EDOT- _co_ -3T)-1:1. Note that the spectra are

recorded at 532 nm in order to be in resonance with the lowest

energy absorption band (HOMO–LUMO transition) of the

neutral polymers and therefore out-of-resonance with the

absorption bands of the oxidized species. In accordance with

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

earlier work [51], the Raman spectrum of PEDOT exhibits a
very intense band at 1428 cm −1 which is associated with a

symmetric Cα=Cβ stretching and two less intense bands at 1519
and 1370 cm −1 which arise from asymmetric Cα=Cβ and Cβ–Cβ
stretching vibrations, respectively. In the branched P3T

polymer, a broadening of the band associated with the collective Cα=Cβ stretching mode (at 1459 cm −1 ) is observed with a
shoulder appearing at 1441 cm −1 while the two less intense
bands appear at 1496 and 1373 cm −1 . The broadening of the

spectra in P3T is related to its branched architecture with

different conjugation paths along their π-conjugated backbones

which also results in a lowering of the molecular symmetry and

an increase of molecular flexibility when compared to the linear

polymers.

On the other hand, the Raman spectrum of the blend is clearly a

simple superposition of the homopolymer spectra. Note the very

good correlation between the spectral profiles of the experi
mental blend and the calculated spectrum created by adding the

spectra of the two homopolymers PEDOT and P3T in

Figure 2A. A direct comparison between the spectra of the

blend and copolymer, however, reveals a noticeable downshift

of the asymmetric Cα=Cβ stretching modes (from 1514 in
PEDOT/P3T-blend to 1500 cm −1 in P(EDOT _-co-_ 3T)-1:1) and

the Cβ–Cβ Raman bands (from 1368 in PEDOT/P3T-blend to
1364 cm −1 in P(EDOT _-co-_ 3T)-1:1). This frequency downshift

strongly suggests that the copolymer has an improved π-conju
gation because of the better π-electron delocalization through

the covalently connected 3T and EDOT units. A detailed super
position of the spectra of the blend and the copolymer (see

labelled bands in Figure S1 in Supporting Information File 1),

evidences the presence of two new bands in the copolymer at
1204 and 1060 cm −1 which can be assigned to stretchings of

newly formed Cα–Cα bonds [52] between the monomers EDOT
and 3T and to Cβ–H bending modes [51], respectively. This
gives further evidence that the materials formed are copoly
mers rather than polymer blends.

Table 1: Summary of absorption and electrochemical characteristics of polymer films electrochemically deposited on ITO electrodes under potentiostatic control derived from in situ spectroelectrochemical experiments in 0.1 M NBu4PF6/MeCN.

Polymer film _E_ ox onset [V vs. Fc/Fc + ]
(HOMO [eV]) a

λmax (neutral)

[nm] b

λmax (radical cation)

[nm] b,c

P3T d +0.3 (-5.4) 450 780
PEDOT d −0.8 (−4.3) 630 880

PEDOT/P3T-blend −0.7 (−4.4) - ≈780 and ≈890

P(EDOT _-co-_ 3T)-1:1 −0.6 (−4.5) 530 830

aHOMO levels calculated using −5.1 eV as formal potential of the ferrocene/ferrocenium (Fc/Fc+) redox couple in the Fermi scale [50]; bthe error is
estimated to be ±15 nm; c values determined at _E_ = _E_ ox onset +0.5 V as previously described in [24]; d from [24].

339

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

Figure 2: A: Raman spectra of electrodeposited films of the homopolymer P3T and PEDOT, PEDOT/P3T-blend, a simulated spectrum of a blend of
PEDOT and P3T (created by adding the spectra of the two homopolymers) and the copolymer P(EDOT- _co_ -3T)-1:1, λexc = 532 nm. B: Comparison of
Raman spectra between 1300 and 1600 cm −1 for different monomer ratios of the copolymer films (black curve EDOT, broken black curve 1:1, blue
1:3, broken pink curve 1:5, green curve 1:10, red curve P3T), λexc = 532 nm.

The Raman spectra also give valuable information about

different compositions in the copolymers. In a similar manner

as described in our earlier work [24] we prepared copolymer

films with different compositions (ratio of the monomers EDOT

and 3T during polymerization ranging from 1:1 to 1:10).

Figure 2B shows the Raman spectra between 1300 and
1600 cm −1 of the copolymers as well as of the homopolymers

P3T and PEDOT for comparison. The main Raman bands of all

copolymers which are associated with the collective symmetric

Cα=Cβ stretching modes are located between the band maxima
in P3T (1459 cm −1 ) and PEDOT (1428 cm −1 ) and downshift
from 1456 to 1435 cm −1 on passing from P(EDOT- _co_ -3T)-1:10

to -1:1. It is well established in literature that the frequency of

this band shifts downward upon increasing conjugation length

or increasing quinoidization [53,54]. Therefore, the shift

towards lower frequencies (i.e., lower energies) with increasing

EDOT content demonstrates that the incorporation of EDOT in

a branched thiophene polymer improves the conjugation length.

This can be ascribed to the significant participation of the

oxygen atoms in the π-conjugation and a gain in rigidity of the

polymer backbone due to intramolecular sulfur–oxygen interac
tions [55,56]. The asymmetric Cα=Cβ stretching modes upshift
and increase in intensity with increasing EDOT content while

the Cβ–Cβ mode slightly increases in intensity; this is also in
accordance with an improved effective conjugation in going

from P(EDOT- _co_ -3T)-1:10 to -1:1. Note that a similar spectral

evolution is found when the sample is recorded with different

excitation wavelengths (see Figure S2 in Supporting Informa
tion File 1).

Further functionalization

Summarizing the first part of our manuscript the electropoly
merization of monomeric mixtures of 3T and EDOT leads to

copolymers and the HOMO levels of these polymers are

adjustable by varying the ratio of the monomers during the

polymerization process. In a next step we further transferred the

copolymerization approach to the azidomethyl-substituted

EDOT-N3 monomer which allows for the straightforward modification with various alkynes by Cu(I)-catalyzed 1,3-dipolar

cycloaddition (“click”-reaction) [57].

For the functionalization experiments we chose the copolymer

prepared with the highest EDOT-N3 content namely the 1:1copolymer. The functionalization was first conducted with

1-hexyne as a model system. The successful modification had

been displayed earlier by Bäuerle et al. who could show, that

the cycloaddition takes place with high conversion rates both

with EDOT-N3 and when the reaction was performed in electropolymerized films of PEDOT-N3 [41]. As functional moiety
we introduced an ionic alkyne sulfonate (SO3Na–alkyne). As
the cycloaddition-reaction with SO3Na–alkyne is not known in
literature we first made tests on the reaction with the monomer

EDOT-N3 and obtained the product EDOT-clickSO3Na in high
yield. For 1 H NMR and IR-spectra we refer to Figure S3 and

Figure S4 in Supporting Information File 1. Figure 3A depicts

the synthesis of the cycloaddition-reactions of the copolymer

films P(EDOT-N3 _-co-_ 3T)-1:1 with 1-hexyne and SO3Na-alkyne
(yielding a butyl end group or a sulfonate end group, respective
ly). DMSO was chosen as solvent as the degree of swelling is

very high [58] and allows modification of the bulk of the film

and not just of the surface.

The modified films were analyzed by IR spectroscopy in a

combined reflection/absorption mode (RAS) (Figure 3B). The
disappearance of the characteristic azide-band at 2100 cm −1

indicates that the cycloaddition-reaction takes place almost

340

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

Figure 3: A: Modification of the copolymer films P(EDOT-N3 _-co-_ 3T) with 1-hexyne and alkyne sulfonate with [Cu(NCMe)4]PF6 and copper powder as
catalyst in DMSO, reaction time 3 days at room temperature (rt). B: IR spectra of copolymer films P(EDOT-N3 _-co-_ 3T) (black line), P(EDOT-clickHex _-_
_co-_ 3T)-1:1 (red line, hexyl modification) and P(EDOT-clickSO3Na _-co-_ 3T)-1:1 (green line, sulfonate modification); spectra were rescaled (y-offset) for
comparison reasons. C, D: Microscope images (top) and IR mappings (bottom) of the azide band intensity at 2100 cm −1 of copolymer films deposited
under potentiostatic control on gold in 0.1 M NBu4PF6/MeCN. P(EDOT-N3 _-co-_ 3T)-1:1 (C, before modification) and P(EDOT-clickSO3Na _-co-_ 3T) (D,
after sulfonate modification). Spectra of the IR microscopy were normalized and plotted with identical colour ranges for comparison reasons.

quantitatively (within the detection limit of IR spectroscopy).

For the butyl-modified film P(EDOT-clickHex _-co-_ 3T)-1:1 (red
line) one can also observe new sp 3 -C–H-vibrations at
2800–3000 cm −1, which also confirm the successful incorpor
ation of the alkyl moieties. The characteristic bands of the

sulfonic acid at 1190 and 1030 cm −1 (see Figure S4 in

Supporting Information File 1) overlap with other bands of the

polymer P(EDOT-clickSO3Na _-co-_ 3T) (green line) in the fingerprint region and therfore a proper assignment is difficult.

Further information was gained by a mapping of the polymer

341

films with IR-microspectroscopic measurements. Figure 3

shows the microscope images of the polymer films P(EDOT
N3 _-co-_ 3T)-1:1 (C, top, before modification) and P(EDOTclickSO3Na _-co-_ 3T)-1:1 (D, top, after sulfonate-modification)
and the corresponding maps (bottom) of the intensity of the
azide-band at 2100 cm −1 wherein the highest azide band inten
sities (transmission of 10%) are displayed in red, and the lowest

intensities (transmission of 100%) are displayed in blue. For

comparison and to limit the influence of the film thickness all

transmission spectra were normalized. While for P(EDOT-N3 _-_
_co-_ 3T)-1:1 the high intensity and a homogeneous distribution of

the azide band is observed for the whole film unless the bare

gold electrode is visible (light areas in the microscope images;

green and blue spots in the IR map. Note that the background of

the single IR spectra is about 70–80%), for the modified

P(EDOT-clickSO3Na _-co-_ 3T)-1:1 nearly no azide band intensity can be observed. This provides information about the

integrity of the modification over the whole film.

The integrity of the redox and optical behavior upon modifica
tion of the P(EDOT-N3 _-co-_ 3T)-1:1 with sulfonic acid with
regard to the parent copolymer was further proven by cyclic

voltammetry and in situ spectroelectrochemistry. It was recently

demonstrated that the azide group does not change the oxi
dation potentials and that the redox behavior of EDOT-N3
resembles pristine EDOT [41]. The copolymerization of

mixtures of the monomers EDOT-N3 and 3T in different ratios
(1:1, 1:3, 1:5 and 1:10) was performed in analogy to the copoly
merization of EDOT and 3T. The cyclic voltammograms of the

respective copolymers show broad oxidation waves with onset

potentials ranging in between the onset potentials of the

homopolymers P3T and PEDOT-N3 (see Figure 4A). The
cathodic cycles of the copolymers reveal identical onset poten
tial values and therefore LUMO levels for P3T and the P3T-rich

copolymers (1:3, 1:5 and 1:10), while PEDOT-N3 and the
PEDOT-N3-rich 1:1 copolymers show a chemically irreversible
electron transfer reaction under our conditions. These data are

consistent with those obtained for P(EDOT- _co_ -3T) films.

The in situ spectroelectrochemistry data in Figure 4B–E reveals

that the ionic modification with sulfonic acid has no influence

on the oxidation onset and therefore HOMO level of the

polymer film. We attribute this finding to the absence of conju
gation between the attached N3 groups and the π-system of the
polymer backbone. The absorption development upon electro
chemical charging shows the characteristic steady decrease of

the neutral band and the increase of the absorption at lower

energy accounting for the generation of delocalized charges in

both the parent polymer and the ionically modified one. The

preparation of a conjugated polyelectrolyte with tunable HOMO

level is therefore accessible via this modification process.

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

While no changes of the electronic properties were detected

between P(EDOT-N3 _-co-_ 3T)-1:1 and P(EDOT-clickSO3Na _-co-_
3T)-1:1, the introduction of ions into the polymers can drasti
cally alter the surface properties. Water contact angle measure
ments are a convenient tool to study the surface polarity. Inter
estingly, we found in the context of this study that the water

contact angle of as polymerized P(EDOT-N3 _-co-_ 3T)-1:1 is
quite high with a value of 137 ± 2° (Figure 5, left). Similar

values were found for P(EDOT _-co-_ 3T)-1:1 (137 ± 1°). The

corresponding homopolymers PEDOT and PEDOT-N3 have
lower values with a contact angle of 71 ± 3° and 91 ± 6°, res
pectively, whereas P3T gives an even larger value of 147 ± 6°

(see Figure S5 in Supporting Information File 1). This highly

hydrophobic surface of the polymers containing branched 3T

units may be explained by a high porosity based on a 3-dimen
sional growth of these polymer films during the electropolymer
ization process [59,60].

After butyl modification the hydrophobic character remains

constant (135 ± 2° after modification, Figure 5, middle), while

we changed the surface polarity of the polymer from highly

hydrophobic to hydrophilic in the case of the sulfonate modifi
cation. A water contact angle of 42 ± 4° is obtained for

P(EDOT-clickSO3Na _-co-_ 3T)-1:1 after modification (Figure 5,
right), i.e., 100° lower than in the case of the parent polymer

P(EDOT-N3 _-co-_ 3T)-1:1. In the case of the analogue modification of PEDOT-N3 similar trends were observed (see Figure S6
in Supporting Information File 1).

## Conclusion

We showed that the monomers 3T and EDOT are suited for

blend formation by sequential electropolymerization, where

both polymers maintain their pristine redox features and are

both addressable in electrochemical devices. We used in situ

spectroelectrochemistry and Raman spectroscopy to prove that

copolymer formation from mixtures of the two monomers takes

place and that by variation of the feed ratio polymers with

adjustable optical and redox properties are accessible. We

successfully transferred the copolymerization route to the func
tional EDOT derivative EDOT-N3. As an example we showed
the potential of surface polarity adjustment by the introduction

of ionic moieties to the hydrophobic polymer films. A decrease

of the water contact angle of ≈100° could be achieved which

evoked a complete change of the polymer surface nature from

hydrophobic to hydrophilic. This opens the way to a library of

polymers which carry tailored redox properties as well as addi
tional functionalities through a manifold of different functional
ization possibilities by “click”-chemistry by leaving the redox

properties unchanged. Such an orthogonal functionalization

may further be used to control the properties in new materials

for organic photovoltaics where low oxidation potentials are

342

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

Figure 4: Cyclic voltammograms of films deposited under potentiostatic control on gold-coated glass substrates (1 cm 2 ) from different monomer
mixtures: (A) Ratio of EDOT-N3:3T = 1:0 (black), 1:1 (dark green), 1:3 (light green), 1:5 (orange), 1:10 (red) and 0:1 (brown curve) recorded in 0.1 M
NBu4PF6/MeCN, 20 mV/s. B–E: In situ spectroelectrochemistry of films deposited under potentiostatic control on ITO in 0.1 M NBu4PF6/MeCN. Cyclic
voltammograms (B and D) and corresponding vis–NIR spectra (C and E) recorded during the forward scan of the oxidation of the P(EDOT-N3 _-co-_ 3T)1:1 (B and C) and P(EDOT-clickSO3Na _-co-_ 3T)-1:1 (D and E) at 50 mV s −1 .

343

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

Figure 5: Water contact angle (CA) of the films of P(EDOT-N3 _-co-_ 3T) (left), P(EDOT-clickHex _-co-_ 3T)-1:1 (middle) and P(EDOT-clickSO3Na _-co-_ 3T)1:1 (right).

needed (monomer ratio) and a good processability from envi
ronmental solvents (e.g., water) is desired (introduction of

polar/ionic groups).

## Experimental

Materials

All chemicals and solvents were purchased from Sigma-Aldrich

or Alfa-Aesar. Solvents were at least of HPLC grade and were

used as received except otherwise noted. NBu4PF6 (SigmaAldrich, electrochemical grade) was stored in a desiccator over

silica beads (activated in an oven at 80 °C for several days).

Acetonitrile (Alfa Aesar, supergradient HPLC grade (far-UV),

+99.9%) was stored over neutral Al2O3 (activated under
vacuum at 120 °C for 24 h) under an argon atmosphere. DMSO

was distilled in vacuum, crystallized at 4 °C and the mother

liquor was removed. After melting of the crystals the crystal
lization procedure was repeated once. DMSO was stored over

3 Å molecular sieves (activated in an oven at 80 °C for several

days) under argon atmosphere. All reactions were carried out

under argon atmosphere unless otherwise noted. The synthesis

of 3T was published elsewhere [61].

Methods
1H (250 MHz) and 13C{1H} (63 MHz) NMR spectra were

recorded on a Bruker Avance 250 spectrometer. vis-NIR spectra

of the polymer films deposited on ITO-coated glass substrates

were recorded with a Lambda 35 spectrometer (Bruker).

IR spectroscopy was performed on a Bruker FTIR spectrometer
IFS 66/S in a wavelength region of 600–3500 cm −1 . Liquids

and oils were measured on a diamond-ATR-device (golden
gate). Polymer films were measured with a VeeMAX TM II

Variable Angle Specular Reflectance Accessory (Pike Tech
nologies) with an incidence angle differing 35° from the orthog
onal plane. IR-microscopy experiments (ultra-fast mappings) of

deposited films were performed with a Thermo Fisher Scien
tific Nicolet iN10 MX spectrometer equipped with a nitrogen

cooled MCT/A detector. The sampling interval was 0.10 s, with

a step size of 25 µm or 50 µm. The spectral resolution was
16 cm −1, the aperture was set to 80 µm or 150 µm. Spectra are

corrected for background. Modified electrodes were directly

placed under the microscope. Data acquisition was performed

with Thermo Fisher Scientific Omnic Picta software. Raman

344

spectra with 532 laser excitation were recorded using a Bruker

Senterra dispersive Raman microscope equipped with a

neon lamp and using a Nd:YAG laser with excitation at

λexc = 532 nm. Raman spectra with excitation at λexc = 488 nm
were recorded by using a Microscope Invia ReflexRaman

RENISHAW. Fourier Transform (FT) Raman spectra with

1064 nm laser excitation were recorded using a Bruker FRA

106/S instrument and a Nd:YAG laser source with excitation at

λexc = 1064 nm, operating in a back-scattering configuration.
Water contact angle measurements were carried out on a

Contact Angle System OCA 20 by dataphysics using water

droplets of 1–2 µL volume ( _R_ - 18.2 MΩ). Calculations of the

contact angles were done with the software SCA20 using ellipse

fitting. Mean values were calculated using at least 4 different

measurements. Deviations given are the mean values of al

obtained single deviations.

Electrochemical experiments

All electrochemical experiments were performed with an

Autolab PGSTAT101 potentiostat (Metrohm, Germany) in a

three-electrode glass cell under argon atmosphere at room

temperature. The counter electrode was a Pt plate. The

pseudoreference electrode consisted of AgCl-coated silver wire

that was directly immersed into the electrolyte. As working

electrodes, gold (50 nm layer)-coated Si wafers (with a 5 nm Cr

adhesion layer between the Si wafer and the Au layer) or ITO
coated glass (≤50 Ω/sq, PGO, Germany) slides (approximately
1 cm 2 ) were used. The gold working electrodes were fabricated

by the physical vapor deposition of Cr and Au on rotating Si

wafers. The gold-coated Si wafers and the ITO substrates were

thoroughly washed with acetone prior to use. Additionally, the

electrodes were treated with oxygen plasma for at least 5 min

before electrodepositions. NBu4PF6 was used as the supporting
electrolyte at a concentration of 0.1 M. Electrolyte solutions

were deaerated by argon bubbling. All potentials are referenced
to the formal potential of the Fc/Fc + external redox standard

[62]. To avoid charge-trapping effects during cyclic voltam
metric experiments, the oxidation and reduction cycles were

performed separately.

Visible–NIR spectroelectrochemical measurements were made

in situ with transparent ITO electrodes (on glass, ≤50 Ω/sq,

PGO, Germany) and 0.1 M NBu4PF6/MeCN as the electrolyte.
The electrodeposited films were used directly for the measure
ments. The vis–NIR spectra were recorded with a diode array

spectrometer from the Zeiss MCS 600 series (equipped with a

Zeiss CLH600 halogen lamp and two MCS 611 NIR 2.2 and

MCS 621 VIS II spectrometer cassettes).

Electropolymerization of PEDOT, PEDOT-N3, P3T and
copolymers: In a similar manner as described in reference [24]

_Beilstein J. Org. Chem._ 2015, _11,_ 335–347.

electropolymerization of the monomers 3T, EDOT and EDOT
N3 on gold or ITO was performed under potentiostatic control
(deposition time = 200 s) with an overall monomer or

comonomer concentration of 2 mM in 0.1 M NBu4PF6/MeCN
at 0.9–1.1 V vs Fc/Fc +, followed by a discharging step
(200–205 s, −1.4 V vs Fc/Fc + ). The deposition potentials

correspond to the peak potential of the overlapping signal of the

oxidation of both comonomers in the corresponding electrolyte.

The desired concentrations were achieved by taking appro
priate aliquots from stock solutions ( _c_ = 10 or 20 mM). For

blend formation, four consecutive potentiostatic polymerizations (each for 50 s at 0.9–1.1 V vs Fc/Fc +, followed by a
discharging step of 50 s at −1.4 V vs Fc/Fc + ) were conducted

alternating the used monomer in each step. For this purpose,

two identical cells, one loaded with EDOT and one with 3T

( _c_ = 2 mM) were used. Between the steps, the polymer films

were rinsed thoroughly with pure acetonitrile.

Synthesis

2-(Azidomethyl)-2,3-dihydrothieno[3,4- _b_ ][1,4]dioxine

(PEDOT-N 3 ) [42,63] and sodium 3-(prop-2-yn-1yloxy)propane-1-sulfonate (SO3Na–alkyne) [64] were synthesized based on literature.

Synthesis of sodium 3-((1-((2,3-dihydrothieno[3,4-

_b_ ][1,4]dioxin-2-yl)methyl)-1 _H_ -1,2,3-triazol-4-

yl)methoxy)propane-1-sulfonate (EDOT-clickSO3Na):
Sodium 3-(prop-2-yn-1-yloxy)propane-1-sulfonate

(SO3Na–alkyne, 0.1 mmol, 20.0 mg), 2-(azidomethyl)-2,3-dihydrothieno[3,4- _b_ ][1,4]dioxine (PEDOT-N3, 0.1 mmol, 19.5 mg)
and tetrakis(acetonitrile) copper(I) hexafluorophosphate

(0.005 mmol, 2.0 mg) were dissolved in DMSO (2.5 mL).

Copper powder (0.1 mmol, 6.9 mg) was added and the reaction

mixture was stirred for 3 days at room temperature. The reac
tion mixture was filtered, the filtrate was concentrated in

vacuum and poured in methanol which was then decanted.

Residual solvent was removed under reduced pressure to yield

the raw product as a greenish highly viscous oil (37 mg, 93%).
1H NMR (250 MHz, DMSO- _d_ 6) δ 8.13 (s, 1H), 6.61 (s, 2H),
4.66 (m, 3H), 4.47 (s, 2H), 4.31 (m, 1H), 3.95 (m, 1H) 3.48 (t, _J_

= 6.6 Hz, 2H), 2.4 (t, _J_ = 7.5 Hz, 2H), 1.78 (m, 2H) ppm;
13C{1H} NMR (63 MHz, DMSO- _d_ 6) δ 141.1, 140.8, 125.1,
100.9, 100.6, 72.2, 69.5, 65.7, 63.7, 50.35, 49.6, 26.1 ppm; IR
(ATR): 3107, 3006, 2916, 2870, 2484, 2424, 1192, 1035 cm −1 .

Synthesis of P(EDOT-clickHex-co-3T) and P(EDOT-

clickSO3Na-co-3T): For the polymer analogue “click”-modification of P(EDOT-N3 _-co-_ 3T) polymer films on gold or ITO
electrodes were placed in flasks containing DMSO (10 mL),

tetrakis(acetonitrile) copper(I) hexafluorophosphate

(0.005 mmol, 1.9 mg) and copper powder (0.1 mmol, 6.4 mg).

345

Alkyne (sodium 3-(prop-2-yn-1-yloxy)propane-1-sulfonate,

0.1 mmol, 20.0 mg or 1-hexyne, 0.1 mmol, 8.2 mg) was added.

The films were allowed to react for three days, while the solu
tion was gently agitated from time to time. The films were thor
oughly rinsed with DMSO (2×) and methanol (3×) and dried in

vacuum. The success of the reaction was confirmed by IR spec
troscopy.

## Supporting Information

Supporting Information File 1

Additional Raman data of PEDOT, P3T, copolymers and
blends; 1 H NMR and IR spectra of EDOT-ClickSO3Na;
contact angles of P3T; PEDOT-N3, PEDOT-clickHex and
PEDOT-clickSO3Na.

[[http://www.beilstein-journals.org/bjoc/content/](http://www.beilstein-journals.org/bjoc/content/supplementary/1860-5397-11-39-S1.pdf)

[supplementary/1860-5397-11-39-S1.pdf]](http://www.beilstein-journals.org/bjoc/content/supplementary/1860-5397-11-39-S1.pdf)

## Acknowledgements

The authors thank K. Dirnberger and M. Scheuble for the

helpful discussions. This work was financially supported by the

DFG within the Emmy Noether program. The work at the

University of Malaga was supported by MINECO project refer
ence CTQ2012-33733 and Junta Andalucía (P09_FQM-4708).

R.C.G.C. acknowledges the Junta de Andalucía for a personal

doctoral grant. M.C.R.D. thanks the MICINN for a “Ramón y

Cajal” research contract.

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