Synthesis, characterization and surface wettability of polythiophene derivatives containing semi-fluorinated liquid-crystalline segment

Article abstract of DOI:10.1016/j.jfluchem.2011.04.014

In the scope of increasing our knowledge on the elaboration of smart surfaces, the aim of this work was to synthesize monomers as starting materials for the polymerization or copolymerization via electrochemical route. We report the synthesis and characte

Full text of DOI:10.1016/j.jfluchem.2011.04.014

Journal of Fluorine Chemistry 134 (2012) 85–89
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis, characterization and surface wettability of polythiophene derivatives
containing semi-fluorinated liquid-crystalline segment
*
´ ´
Thierry Darmanin, Elisabeth Taffin de Givenchy, Sonia Amigoni, Frederic Guittard
Universite´ de Nice – Sophia Antipolis, Laboratoire Chimie des Mate´riaux Organiques et Me´talliques, Equipe chimie organique aux interfaces, Parc Valrose, 06108 Nice Cedex 2, France
A R T I C L E I N F O
A B S T R A C T
Article history:
In the scope of increasing our knowledge on the elaboration of smart surfaces, the aim of this work was to
synthesize monomers as starting materials for the polymerization or copolymerization via
electrochemical route. We report the synthesis and characterization of original structures containing
a single phenyl unit bound, on one side, to a semi-fluorinated tail via a thioester connector and, on the
other side, to a thiophene moiety. This design approach using cheap raw materials (a single phenyl ring
as mesogenic core) associated to an electropolymerizable unit is of great interest in the development of
liquid crystal low cost materials to build-up non-wetting surfaces based on the fluorophobic effect. The
mesomorphic properties were characterized using differential scanning calorimetry and optical
polarizing microscopy. The effect of the length of the fluorinated tail induced the formation of a smectic
enantiotropic mesophase for F-hexyl and F-octyl tails. The polymerization of the films was performed in
solution of sodium perchlorate in acetonitrile. Hydrophobic surfaces were obtained from the monomers
containing a F-hexyl and F-octyl tail, while superhydrophobic surfaces (contact angle of water of 1588)
were reached from the monomer containing a F-butyl tail.
Received 15 January 2011
Received in revised form 20 April 2011
Accepted 25 April 2011
Available online 6 May 2011
Keywords:
Liquid crystal
Superhydrophobic
Wettability
Electrodeposition
Conductive polymers
ß 2011 Elsevier B.V. All rights reserved.
1. Research topics
surface, changing it from super hydrophobic to superhydrophobic
and superoleophobic properties. If our Group is developing
Our main research prospects concern the conception and
development of new active surfaces like superhydrophobic and
superoleophobic, on one hand, or bioactive surfaces as for example
biocides or biocidal surfaces, on the other hand. Our specific
understanding on highly fluorinated compounds chemistry allows
us to induce new molecular organisation and structuration by
tuning their skeleton. Our results in the field of molecular design
allow, for example, the creation of brain like giant vesicles with
high specific surfaces by the assembly of hybrid fluorocarbon/
hydrocarbon surfactants, the particular liquid crystal orientation
strategies for fluorinated material, one of our strategy is also to
find alternatives of fluorine by the development of biomimetic
surfaces.
2. Introduction
Fluorinated compounds are used in
a wide domain of
applications such as the development of anti-wetting surfaces
[1,2], surfactants [3,4], vesicles [5,6], liquid-crystals [7–8], coating
of nanoparticles [9–10], dendrimers [11–12], membranes [13–14]
or for their barrier [15] or antireflective properties [16]. In anti-
wetting surfaces for example, the introduction of highly fluorinat-
ed compounds is a general approach which confers to the resulting
material a low surface energy [17,18]. The introduction of a
physical parameter, such as surface structuration, in hydrophobic
materials can be sufficient to switch from hydrophobic/oleophobic
surfaces to superhydrophobic/superoleophobic surfaces (contact
angles above 1508) [19,20]. Previously, our group showed that the
electropolymerization of fluorinated monomers such as thiophene
induced by the combination of
a mesogenic group and a
perfluorinated chain in solution as well as in polymer coatings,
the increase of biocidal properties of highly fluorinated surfactants
or polymers. Our most important hot success was induced by this
knowledge that showed us the way to the extraordinary
production of superhydrophobic as well as superoleophobic
surfaces by the electropolymerization of perfluorinated monomers
and/or hydrocarbon homologues. These monomers, depending on
their structures, are able to create special building at the surface
during the polymerization stage and the divergence of just, for
exemple, one methylene unit can induce huge effects on the
and pyrrole derivatives (some examples are given in Fig.
1
monomers CX), often leads to micro/nanostructured surfaces
displaying exceptional anti-water properties (superhydrophobic)
and sometimes anti-oil properties (superoleophobic) [21,22].
Recently,wehavedemonstratedinfluorinatedpolyacrylatefilms
that the introduction of a mesogenic core between the fluorinated
* Corresponding author.
E-mail address: guittard@unice.fr (F. Guittard).
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.04.014

86
T. Darmanin et al. / Journal of Fluorine Chemistry 134 (2012) 85–89
Fig. 1. Previously reported (A, B, CX, DX for X = NH) and investigated (DX for X = S) monomers.
chains and the polyacrylate backbone (Fig. 1 monomers B) can also
modulate the surface mobility and the dynamic anti-wetting
properties [23].
3.2. Synthesis of 4-(2-F-alkylethylthio)carbonyl)phenyl 2-(thiophen-
3-yl)acetate (DSn)
For the construction of electropolymerized materials,
a
2-F-alkylethyl 4-hydroxythiobenzoate was synthesized in three
steps following a synthesis procedure previously reported [20–22].
Dicyclohexylcarbodiimide (DCC) (1.07 g, 5.2 mmol) was added to a
solution of 3-thiopheneacetic acid (0.74 g, 5.2 mmol) in dichlor-
omethane. After stirring during 30 min at 50 8C, 2-F-alkylethyl 4-
hydroxythiobenzoate (5.2 mmol) was added. After a day, the
solvent was removed and the crude was purified by column
chromatography (silica gel; eluent: dichloromethane) to yield the
products as white solids.
mesogenic core can also be introduced between the semi-
fluorinated chains and the polymer backbone to modulate the
surface properties. Very recently, by comparing the surface
properties of polypyrroles bearing fluorinated segments (Fig.
1
monomers CX for X = NH) and polypyrroles bearing fluorinated
liquid crystalline segments (Fig. 1 monomers DX for X = NH), we
showed that a mesogenic part can modulate the surface properties
but also modify the surface morphology [24].
Using this process, the surface morphology and wettability of
the electrodeposited films are highly depending on the poly-
merizable core (pyrrole, thiophene, fluorene, etc.). Hence, to
study the influence of the polymerizable core, here, we reported
the synthesis, characterization and polymerizability of analo-
gues containing the same liquid crystalline segment than
DS4. Yield 61%. r.t. 21.9 mn. 250 MHz 1H NMR (CDCl3):
2H, 3JHH = 7.8 Hz, 3JHF = 18.2 Hz), 3.28 (t, 2H, 3JHH = 7.8 Hz), 3.93 (s,
d 2.49 (tt,
3
4
2H), 7.13 (dd, 2H, JHH = 4.9 Hz, JHH = 1.3 Hz), 7.20 (d, 2H,
3JHH = 8.7 Hz), 7.27 (m, 1H), 7.35 (dd, 2H, JHH = 4.9 Hz,
4JHH = 2.9 Hz), 7.98 (d, 2H, 3JHH = 8.7 Hz). 50 MHz 13C NMR (CDCl3):
3
3
2
d
20.14 (t, JCF = 4.8 Hz), 31.62 (t, JCF = 21.8 Hz), 35.87, 121.87,
123.41, 126.19, 128.27, 128.83, 132.35, 134.02, 154.86, 168.84
(OC = O), 189.61 (SC = O). 19F NMR (CDCl3):
ꢀ126.45 (m, 2F),
max (cmꢀ1):
previously (Fig.
1 monomers DX for X = NH) linked to a
thiophene heterocycle as polymerizable unit (Fig. 1 monomers
DX for X = S).
d
ꢀ124.77 (m, 2F), ꢀ115.17 (m, 2F), ꢀ81.42 (m, 3F). IR
n
3105, 2942, 1759 (OC = O), 1664 (SC = O), 1596, 1500, 1238, 1215,
1130 cmꢀ1. MS (70 eV, m/z): 524 (M+, 1%), 245 (C13H9O3S+, 100%),
121 (C7H5O2+, 97%), 97 (C5H5S+, 95%).
3. Experimental
3.1. Techniques and materials
DS6. Yield 35%. r.t. 23.1 mn. 250 MHz 1H NMR (CDCl3):
d
2.49 (tt,
2H, 3JHH = 7.8 Hz, 3JHF = 18.2 Hz), 3.28 (t, 2H, 3JHH = 7.8 Hz), 3.93 (s,
3
4
All chemical products were purchased from Sigma–Aldrich.
The retention time (r.t.) of the compounds were determined
with a 5890 series II gas chromatography from Hewlett Packard
equipped with a capillary column HP5 (30 m, 0.32 mm) and with
this following programming: heating from 60 8C to 250 8C at
10 8C minꢀ1 and 30 min at 250 8C. The onset temperatures and
the enthalpies of transition of the monomers were investigated
with a Jade DSC of PerkinElmer at a rate of 10 8C minꢀ1. The
polarizing optical microscopy (POM) images were obtained with
an Olympus BX60 microscope. Electrochemical experiments
were performed with an Autolab PGSTAT 30 potentiostat from
Eco Chemie B.V. equipped with General Purpose Electrochemical
System (GPES) software. A three-electrode cell was used with a
platinum disk working electrode, a glassy carbon rod counter-
electrode and a saturated calomel reference electrode (SCE). The
electrochemical polymerization of these monomers was per-
formed in anhydrous acetonitrile solutions containing
0.01 M of the monomer and 0.1 M of tetrabutylammonium
hexafluorophosphate or sodium perchlorate (electrochemical
grade). The solutions were degassed with argon before each
experiment.
2H), 7.13 (dd, 2H, JHH = 4.9 Hz, JHH = 1.3 Hz), 7.20 (d, 2H,
3JHH = 8.7 Hz), 7.27 (m, 1H), 7.35 (dd, 2H, JHH = 4.9 Hz,
3
4JHH = 2.9 Hz), 7.98 (d, 2H, 3JHH = 8.7 Hz). 50 MHz 13C NMR (CDCl3):
3
2
d
20.17 (t, JCF = 4.8 Hz), 31.71 (t, JCF = 21.8 Hz), 35.87, 121.88,
123.41, 126.19, 128.28, 128.83, 132.35, 134.03, 154.86, 168.85
(OC = O), 189.61 (SC = O). 19F NMR (CDCl3):
d
ꢀ126.57 (m, 2F),
ꢀ123.82 (m, 2F), ꢀ123.29 (m, 2F), ꢀ122.32 (m, 2F), ꢀ114.94 (m,
2F), ꢀ81.19 (m, 3F). IR nmax (cmꢀ1): 3092, 2948, 1755 (OC = O),
1657 (SC = O), 1599, 1500, 1238, 1212, 1144 cmꢀ1. MS (70 eV, m/z):
624 (M+, 1%), 245 (C13H9O3S+, 68%), 121 (C7H5O2+, 100%), 97
(C5H5S+, 87%).
DS8. Yield 38%. r.t. 25.1 mn. 250 MHz 1H NMR (CDCl3):
2H, 3JHH = 7.8 Hz, 3JHF = 18.2 Hz), 3.28 (t, 2H, 3JHH = 7.8 Hz), 3.93 (s,
d 2.49 (tt,
3
4
2H), 7.13 (dd, 2H, JHH = 4.9 Hz, JHH = 1.3 Hz), 7.20 (d, 2H,
3JHH = 8.7 Hz), 7.27 (m, 1H), 7.35 (dd, 2H, JHH = 4.9 Hz,
3
4JHH = 2.9 Hz), 7.98 (d, 2H, 3JHH = 8.7 Hz). 50 MHz 13C NMR (CDCl3):
3
2
d
20.17 (t, JCF = 4.8 Hz), 31.72 (t, JCF = 21.8 Hz), 35.87, 121.87,
123.41, 126.19, 128.28, 128.83, 132.35, 134.03, 154.86, 168.85
(OC = O), 189.61 (SC = O). 19F NMR (CDCl3):
d
ꢀ126.53 (m, 2F),
ꢀ123.76 (m, 2F), ꢀ123.13 (m, 2F), ꢀ122.29 (m, 6F), ꢀ114.91 (m,
2F), ꢀ81.16 (m, 3F). IR nmax (cmꢀ1): 3092, 2948, 1755 (OC = O),

T. Darmanin et al. / Journal of Fluorine Chemistry 134 (2012) 85–89
87
O
O
S
S
O
CnF2n+1
DCC / CH2Cl2
24h at 50°C
OH
+
HO
CnF2n+1
O
S
O
n = 4, 6, 8
S
(DSn)
Fig. 2. Reaction pathway for the synthesis of DS4–8 (n = 4, 6 and 8).
1657 (SC = O), 1599, 1497, 1242, 1208, 1147 cmꢀ1. MS (70 eV, m/
z): 724 (M+, 1%), 245 (C13H9O3S+, 82%), 121 (C7H5O2+, 100%), 97
(C5H5S+, 75%).
4. Synthesis and discussion
The studied monomers DSn incorporating a liquid-crystal
segment, which consists in a rigid single phenyl group bound to
a pro-mesogenic fluorinated tail (which can induce liquid crystal
behaviour by phase microsegregation) by a thioester connector,
were prepared following the chemical pathway represented in
Fig. 2. The ability to have LC behaviour with a single phenyl unit is
based on microphasic separation from fluorophobic effect [25,26].
This is remarkable because such behaviour would not be expected
for hydrocarbon series without additional hydrogen bonding. The
choice of a thioester connector (structure C) is related to previous
work showing its ability to form LC properties over a wide range
[27]. So, to synthesize structure DSn, the first step is the protection
of the acid function of 4-hydroxybenzoic acid with methyl
chloroformate. The reaction proceeds in an aqueous solution of
sodium hydroxide and during 18 h at ꢀ7 8C. The obtained product
was coupled with 2-F-alkylethanethiol using dicyclohexylcarbo-
diimide (DCC) in dichloromethane. After purification on a silica-gel
column, the hydroxyl function was released with a mixture of
ammonium hydroxide, dichloromethane and ethanol (1:1:1).
Afterwards, the incorporation of the LC segment on the thiophene
backbone was performed from commercially available 3-thiophe-
neacetic acid and via an esterification reaction with DCC as
coupling agent in dichloromethane. After purification by column
chromatography, the monomers DS4–8 were obtained as white
powders and in 35–61% isolated yields.
Fig. 3. DSC curves for DS8 (scan rate = 10 8C minꢀ1).
100
90
80
70
60
50
40
I
Sm
Cr
4
6
8
F
Length of the -alkyl tail
Fig. 4. Phase diagram for the monomers as a function of the fluorinated chain
length.
5. Mesomorphic behaviour
The phase behaviour of these original fluorinated monomers
was studied by combining differential scanning calorimetry (DSC)
and optical polarizing microscopy. The phase transition tempera-
tures and enthalpies of the monomers are gathered in Table 1.
These observations revealed an enantiotropic behaviour depen-
dent on the fluorinated tail length. The presence of a mesomorphic
behaviour was detected for the monomers DS6 and DS8 but no
evidence of mesomorphism was detected for DS4. Indeed, the
higher mobility of the F-butyl tail [28] can, in this case, destabilize
the arrangement of the molecules, which has a high influence on
the liquid crystal behaviour. An example of a DSC curve obtained
Table 1
Phase transition temperatures and enthalpies obtained for the monomers on
heating.
Compound
n
Yield, %
Transition temperatures (onset), 8C
Cr
Sm
I
DS4
DS6
DS8
4
6
8
61
35
38
ꢁ
ꢁ
ꢁ
41.6 [48.98]a
59.3 [32.58]
90.5 [26.21]
ꢁ
ꢁ
63.2 [2.20]
98.9 [2.60]
ꢁ
ꢁ
Fig. 5. Optical polarizing micrograph of DS8 (ꢂ66): T = 96 8C on cooling.
a
Figures in square brackets denote enthalpies of transition (J/g).

88
T. Darmanin et al. / Journal of Fluorine Chemistry 134 (2012) 85–89
0.30
0.25
0.20
0.15
0.10
0.05
0.00
-0.05
Table 2
ox
peak, m
E
Static contact angles.
Compound
Static contact angles,8
Water
Diiodomethane
Hexadecane
PolyDS4
PolyDS6
PolyDS8
158.0
115.0
113.9
131.4
101.1
94.1
84.2
72.4
72.2
6. Polymerizability study
The study of the polymerizability of the monomers was
performed in anhydrous acetonitrile and tetrabutylammonium
hexafluorophosphate (Bu4NPF6) (0.1 M). After determination of
the oxidation potential of the monomers (Fig. 6) by single
voltammetric scan (E
0.0
0.5
1.0
1.5
2.0
2.5
3.0
E / V vs SCE
Fig. 6. Cyclic voltammogram of DS4 in Bu4NPF6/MeCN: 1 scan.
ox
peak;m
¼ 2:23 V vs SCE for DS4 and 2.24 V for
DS6 and DS8), the polymerizability of the monomers were studied
for DS8 on heating and on cooling is given in Fig. 3. It follows from
Fig. 4 that the mesophase range and the transition temperatures
(both melting and clearing temperatures) increase with the F-alkyl
tail length. The mesophase range of DS8 was about 10 8C during the
heating or the cooling and a decrease of about 5 8C was observed
for a diminution of the F-alkyl tail length of two fluoromethylene
units. The transition temperatures and mesophase ranges of the
thiophene derivatives were much lower than the previously
reported pyrrole analogues [24], which was probably due to the
presence of hydrogen bonding with the hydrogen bound by the
nitrogen of pyrrole and the oxygen of the carbon groups.
by consecutive voltammetric scan from ꢀ1 V and until a potential
ox
slightly lower than
E
. The polymer electrodeposits if
peak;m
oxidation and reductions peaks of the electroactive polymer
ox
peak;m
appear before E
and with intensities increasing at each scan.
However, no redox system was observed for the three monomers
contrary to the previously reported pyrrole analogues [24]. Other
experiments were also performed by imposed potential on gold
substrates but no films were also obtained with this condition.
These molecules did not give electrodeposited films probably
because of the high spatial volume of the substituents and the high
oxidation potential of thiophene in comparison to that of pyrrole.
To form electrodeposited films with that series, Bu4NPF6 was
replaced by sodium perchlorate, a more powerful salt for the
electrodeposition. With that salt, polymer films were obtained by
imposed potential with the three monomers but a high decrease of
By optical microscopic observation and on cooling from isotropic
melt, the mesophases of DS8 and DS6 appeared as rods and after
coalescence gave rise to fan-shaped textures with focal-conic
domains (Fig. 5), which are characteristic of smectic mesophases.
Fig. 7. SEM images of polyDS4 with a magnification of (A) ꢂ2500 and (B) ꢂ10,000, polyDS6 with a magnification of (C) ꢂ10,000 and polyDS8 with a magnification of (D)
ꢂ10,000.

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89
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7. Surface characterization
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The polymer films were characterized by contact angle
measurements. Surprisingly, superhydrophobic films with static
contact angle of water (CAwater) of 1588 were obtained with the
monomer containing the shortest fluorinated chains (DS4), as
shown in Table 2. Using the tilted-drop method, water droplets did
not roll off the surfaces after inclination, which means that the
surfaces were sticky. Hence, these surfaces were more hydropho-
bic than that previously obtained from pyrrole analogues [24]. In
contrast, polyDS6 and polyDS8 were only hydrophobic with quite
the same value for the two polymers (CAwater ꢃ 114–1158). The
static contact angles of diiodomethane and hexadecane were also
higher for polyDS4. The very high contact of polyDS4 being
probably due to surface morphology, the polymer was analyzed by
scanning electron microscopy (SEM).
SEM images of the polymer are given in Fig. 7. On one hand,
polyDS4 was extremely structured and the surface morphology
consisted in an assembly of sub-micronic needles (Fig. 7A and B),
which confirms their exceptional surface anti-wetting properties.
On the other hand, polyDS6 surfaces were composed of well-
ordered (in two dimensions) nanoparticles (Fig. 7C) and polyDS8
was relatively smooth (Fig. 7D). The low roughness of these two
films explains their low anti-wetting properties.
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8. Conclusion
Wehavereported the synthesisof a series of monomers bearing a
single phenyl unit as mesogenic group between the heterocyclic
core(thiophene)and thehighly fluorinatedtailwithfour, six oreight
fluoromethyleneunits(DS4, DS6, DS8). These compounds exhibiteda
liquid crystal behaviour of smecticA type which can be used to avoid
or limit the surface reconstructions of the corresponding polymers
in the presence of polar media. Polymer films were obtained using
sodium perchlorate as salt for the electrodeposition. Superhydro-
phobicfilmswithstaticcontactangleof1588wereobtainedfromthe
monomer containing a F-butyl chain. The surface morphology of
these films consisted in an assembly of sub-micronic needles.
[22] (a) T. Darmanin, E. Taffin de Givenchy, S. Amigoni, F. Guittard, Langmuir 26
(2010) 17596–17602;
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Kofman, F. Celestini, Soft Matter 7 (2011) 1053–1057;
(c) T. Darmanin, F. Guittard, Langmuir 25 (2009) 5463–5466.
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