Self-assembly behaviour of conjugated terthiophene surfactants in water

Article abstract of DOI:10.1039/c0nj00760a

Conjugated self-assembled systems in water are of great interest because of their potential application in biocompatible supramolecular electronics, but so far their supramolecular chemistry remains almost unexplored. Here we present amphiphilic terthiophenes as a general self-assembling platform for the construction of conjugated aggregates, providing access to aggregates with different morphologies without changing the basic molecular design. We explored the design parameters of these amphiphilic terthiophenes in detail, leading to the selection and synthesis of in total 8 new amphiphilic oligothiophenes. Their aggregation behaviour was investigated by absorbance and fluorescence spectroscopy, dynamic light scattering, and cryo-transmission electron microscopy. Critical micelle concentrations as low as 0.01 mM were found and different sized aggregates ranging from several nanometres up to 200 nm. The aggregate morphology could also be tuned by changing the substitution pattern of hydrophilic and hydrophobic moieties, leading to different types of aggregates ranging from globular- and elongated micelles to bilayers. Remarkably, aggregation had only little effect on the electronic and spectroscopic properties of the oligothiophenes, which will be of interest for their application in supramolecular electronics.

Full text of DOI:10.1039/c0nj00760a

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
Supporting Information
Self-assembly behaviour of conjugated terthiophene surfactants in water
a
a
a
b
Patrick van Rijn, Dainius Janeliunas, Aurélie M. A. Brizard, Marc C. A. Stuart, Ger J.M.
a
Koper, Rienk Eelkema, and Jan H. van Esch*
Experimental Section
General information
Starting materials were commercially available and were used without further purification. Synthesis of compounds 1’-OH,
2
-OH was described in ref. 19, synthesis of 10 and 17 was performed according to literature procedures (ref. 20). Aldrich
silica gel Merck grade 9385 (230-400 mesh) was used for column chromatography, in combination with the Teledyne Isco
CombiFlash Companion with UV-detection. All solvent used for dry reactions were purified with the use of MBRAUN
1
Solvent purification system MB SPS-800, MilliQ-water was used in case of measurements. H NMR-spectra were recorded
on a Bruker Avance-400 spectrometer (at 400MHz) or a Varian Inova-300 spectrometer (at 300MHz), at 25ºC. The splitting
patterns are noted as follows: s (singlet), d (doublet), dd (double doublet), t (triplet), q (quartet), qt (quintet), m (multiplet)
13
and bs (broad singlet). C NMR spectra were recorded on a Bruker Avance-400 spectrometer (at 100 MHz) or a Varian
Inova-300 spectrometer (at 75 MHz). Multiplicity was determined by Attached Proton Test (APT) and chemical shifts are
given in δ (ppm) referenced to the residual protic solvent peaks. Coupling constants J, are given in Hz. LC-MS was
performed on a SHIMADZU Liquid Chromatograph Mass Spectrometer, LCMS-2010, LC-8A pump with a diode-array
detector SPD-M20. The column used here was the Xbridge Shield RP 18.5ꢀm (4.6x150mm) with a 95/5 v/v MeOH-H O
2
mixture as eluent. For UV/Vis measurements an AnalytikJena Specord 250 spectrometer was used equipped with a
deuterium-lamp and a halogen-lamp. Quartz cuvets were used with path-lengths varying from 10mm-0.1mm. Fluorescence
spectroscopy was done on a Jasco J-815 CD-spectrometer equipped with a fluorescence monochromator and detector, and an
L-38 low wavelength filter (cut-off 380nm) placed between the sample and the detector. The cuvet used here was quartz with
dimensions 3x3mm. Dynamic Light Scattering was performed on a ZetaSizer Nano series Nano-ZS by Malvern Instruments.
For cryo-TEM, a few microliter of suspension was deposited on a bare 700 mesh copper grid. After blotting away the excess
of liquid the grids were plunged quickly in liquid ethane. Frozen-hydrated specimens were mounted in a cryo-holder (Gatan,
model 626) and observed in a Philips CM 120 electron microscope, operating at 120 kV. Micrographs were recorded under
low-dose conditions on a slow-scan CCD camera (Gatan, model 794).

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
Experimentals
Description for synthesis of compounds 1-, 2- 3-OMe and 4-6.
2
-bromo-3-hexadecylthiophene (11): 3-hexadecylthiophene (10) (2.5 g, 8.1 mmol) was dissolved in 10 ml of chloroform. To
this N-bromosuccinimide NBS (2.9 g, 16 mmol) was added at room temperature. It was allowed to react overnight. The
reaction was quenched with 50 ml saturated sodium bicarbonate solution. Then 40 ml of chloroform was added. Organic and
water phases were separated. Organic phase was washed with water and brine and dried over MgSO . Solvent was
4
removed under vacuum. The title compound was obtained as a light yellow solid after precipitation in cold methanol which
was isolated after filtration and drying in vacuum in 90% yield (2.8 g, 7.3 mmol) and was not subdued to further purification.
1
H NMR (400 MHz, CDCl ) δ : 0.88 (t, J = 6.8 Hz, 3H), 1.20-1.38 (m, 26 H), 1.50-1.66 (m, 4H), 2.55 (t, J = 7.8 Hz, 2H),
3
H
3
3
6
.79 (d, J = 5.6 Hz, 1H), 7.18 (d, J = 5.6 Hz, 1H).
3 3
(3-hexadecylthiophen-2-yl)trimethylsilane (12*): 2-bromo-3-hexadecylthiophene (11) (10.0 g, 25.8 mmol) was dissolved in
2
50 ml of dry THF and cooled to -78°C. Then n-butyllithium (21.0 ml, 33.6 mmol, 1.6M in hexane) was added drop wise.
The mixture was allowed to react at -78°C for 2h. Then TMSCl (6.6 ml, 51.6 mmol) was slowly added. The mixture was
allowed to react at -78°C for additional 2h and then left overnight to slowly reach room temperature and was then quenched
with water. The mixture was extracted with THF and diethyl ether. The combined organic layers were then washed with
brine. The organic layer was dried over MgSO and filtered; the solvent was removed under vacuum. The resulting slightly
4
yellowish liquid was identified as the title compound obtained as a colourless oil which solidified when cooled at 4ºC to a
1
soft off-white solid in 89% yield (9.4 g, 23.0 mmol) and was used without further purification. H NMR (400MHz, CDCl )
3
δ : 0.35 (s, 9H), 0.88 (t, J = 6.7 Hz, 3H), 1.26-1.32 (m, 26H), 1.55-1.65 (m, 2H), 2.67 (t, J = 7.8 Hz, 2H), 7.05 (d, J = 4.7
H
3
3
Hz, 1H), 7.45 (d, J = 4.7 Hz 1H).
3
(3-hexadecylthiophen-2-yl)trimethylstannane (12): A solution of 2.0 g (5.2 mmol) of 2-bromo-3-hexadecylthiophene (11) in
1
5 ml of dry THF was cooled to -50˚C. To this 1.05 equivalent of n-butyllithium (3.4 ml, 1.6 M in hexane) was slowly
added and the reaction mixture was stirred for 4 hours. Then 6.3 ml of a 1M solution of trimethyltinchloride in THF was
added slowly to the mixture. After addition the mixture was stirred for 2 hours at -50˚C and was then allowed to slowly warm
to room temperature overnight. The reaction was quenched with water. The organic and aqueous phases were separated and
the organic phase was subsequently washed with water two times, then once with brine and dried over MgSO . After
4
filtration, the solvent was removed in vacuum. The title compound was obtained as a colourless oil which solidifies when
1
cooled at 4ºC to a soft off-white solid in 82% yield (2.5 g, 4.3 mmol) and was not subdued to further purification. H NMR
(
(
400MHz, CDCl ) δ : 0.37 (s, 9H), 0.85-1.00 (s, 3H), 1.20-1.40 (m, 26H), 1.50-1.70 (m, 2H), 2.62 (t, J = 7.8 Hz, 2H), 7.09
3 H 3
d, J = 4.6 Hz, 1H), 7.53 (d, J = 4.7 Hz, 1H).
3
3
2
,5-dibromo-3-hexadecylthiophene (13) : 3-hexadecylthiophene (10) (1.50 g, 4.9 mmol) was dissolved in chloroform. To this
0
Br (1.55 g, 9.7 mmol) (2 equivalent) was added at 0 C. It was allowed to react overnight. The reaction was quenched with a
2
saturated bicarbonate solution. Then chloroform was added. Organic and aqueous phases were separated. The organic phase
was washed with water and brine, dried over MgSO . Solvent was removed and the title compound was obtained after
4
precipitation in cold methanol which was isolated after filtration and drying under vacuum in 94% yield (2.0 g, 4.6 mmol).
1
This was used without any further purification. H NMR (400 MHz, CDCl ) δ : 0.87 (t, J = 6.8 Hz, 3H), 1.22-1.33 (m,
3
H
3
2
5H), 1.42-1.52 (m, 2H), 2.49 (t, J = 7.7 Hz, 2H), 6.77 (s, 1H).
3
(3-hexadecylthiophen-2-yl-trimethylsilyl-5-yl)trimethylstannane (15): To 100ml of THF diisopropylamine (4.2 ml, 29.7
mmol) was added. The mixture was cooled to -78°C. Then n-butyllithium (16.9 ml, 27.0 mmol, 1.6M in hexane) was added
drop wise. The mixture was allowed to react at -78°C for 2h. Then 3-hexadecylthiophen-2-yl)trimethylsilane (12*) (9.4 g,

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
2
3.0 mmol) was added and the mixture was stirred for 4h. After this trimethyltinchloride (5.9 g, 29.7 mmol, 1M in THF) was
slowly added. The mixture was allowed to react at -78°C for additional 2h and then left overnight to slowly reach room
temperature and was then quenched with water. The mixture was extracted with THF and diethyl ether. The combined
organic layers were then washed with brine. The organic layer was dried over MgSO and filtered; the solvents were removed
4
under vacuum. The resulting slightly yellowish liquid was identified as the title compound and was obtained as a colourless
oil which solidified when cooled at 4ºC to a soft off-white solid in 89% yield (12.4 g, 22.7mmol) and was used without
1
further purification. H NMR (400 MHz, CDCl ) δ : 0.27 (s, 9H), 0.33 (s, 9H), 0.88 (t, J = 6.7 Hz, 3H), 1.26-1.32 (m, 26H),
3
H
3
1
3
1
2
3
.54-1.63 (m, 2H), 2.62 (t, J = 7.8 Hz 2H), 7.03 (s, 1H). C NMR (100 MHz, CDCl ) δ : -8.12 (3*CH ), 0.41 (3*CH ),
3 3 C 3 3
2.54 (2*CH ), 29.35(CH ), 29.39 (CH ), 29.49 (CH ), 29.57 (CH ), 29.60(CH ), 29.65 (CH ), 29.71 (CH ), 30.29 (CH ),
2
2
2
2
2
2
2
2
2
0.58 (CH ), 31.25 (CH ), 31.84 (CH ), 31.94 (2*CH ), 130.01 (CH), 135.25 (C), 142.7 (C).
2
2
2
2
1
2
-(2,5-dibromothiophen-3-yl)-2,5,8,11,14-pentaoxapenta-decane (18): To
a
solution of 1-(2-bromothiophen-3-yl)-
,5,8,11,14-pentaoxapentadecane (17) (0.5 g, 1.3 mmol) in 7 ml of DCM, N-bromosuccinimide (NBS) (0.23 g, 1.3 mmol)
was added. After addition the mixture was stirred for overnight at room temperature and was then quenched with water. The
mixture was extracted with DCM. The combined organic layers were then washed with a 1 M NaOH solution followed by
water and brine. The organic layer was dried over MgSO and filtered; the solvent was removed under vacuum. The resulting
4
1
slightly yellowish liquid was identified as the title compound and obtained in 91% yield (0.55 g, 1.2 mmol). H NMR (400
MHz, CDCl ) δ : 3.37 (s, 3H), 3.56-3.52 (m, 2H), 3.70-3.60 (m, 14H), 4.43 (s, 2H), 6.99 (s, 1H).
3
H
2
-[2-(2-methoxyethoxy)ethoxy]ethyl 2-{[2-(trimethylstannyl)-3-thienyl]methoxy}ethyl ether (19): A solution of 2.0 g (5.2
mmol) of 1-(2-bromothiophen-3-yl)-2,5,8,11,14-pentaoxapentadecane (17) in dry THF was cooled to -78˚C. To this
.05 equivalent of n-butyllithium (3.44 ml, 1.6 M in hexane) was added slowly and the reaction mixture was stirred for 4
1
hours at -78˚C, during this time the colour changed to black. Then 6.37 ml of a 1 M solution of trimethyltinchloride in THF
was added slowly to the mixture. After addition the mixture was stirred for 2 hours at -78˚C and was then allowed to slowly
warm to room temperature overnight. The reaction was quenched with water. The organic and aqueous phases were separated
and the organic phase was subsequently washed with water two times, then once with brine and dried over MgSO . After
4
filtration and removal of solvent in vacuum, the title compound was obtained as a viscous yellow liquid in a 74% yield (1.8 g,
1
3
7
.9 mmol). H NMR (400 MHz, CDCl ) δ : 0.36 (s, 9H), 3.37 (s, 3H), 3.65 (m, 16H), 4.55 (s, 2H), 7.17 (d, J = 4.6 Hz, 1H),
3
H
3
.54 (d, J = 4.7 Hz, 1H).
3
2
-[2-(2-methoxyethoxy)ethoxy]ethyl 2-{[2-(trimethylsilyl)-3-thienyl]methoxy}ethyl ether (20):
A
solution of 1-(2-
bromothiophen-3-yl)-2,5,8,11,14-pentaoxapentadecane (17) (13.0 g, 34 mmol) in 120 ml of dry THF under nitrogen
atmosphere was cooled to -78°C. To this 1.05 equivalent of n-butyllithium (20 ml, 1.6 M in hexane) was added slowly and
the reaction mixture was stirred for 3 hours. Then the reaction was quenched with trimetylsilylchloride (4.0 ml, 35.3 mmol)
and stirred for an additional 3 hours at -78°C. After this the mixture was allowed to warm to room temperature slowly
overnight and then quenched with water. The mixture was washed twice with water and once with brine and dried over
MgSO . After filtration and removal of solvent under vacuum, the title compound was obtained as a yellowish oil in 86%
4
1
yield (11.0 g, 29.3 mmol). The crude compound was used without further purification. H-NMR (400 MHz, CDCl ) δ : 0.34
3
H
(
s, 9H), 3.37 (s, 3H), 3.52-3.56 (m, 2H), 3.60-3.69 (m, 14H), 4.59 (s, 2H), 7.20 (d, 1H, J = 4.9 Hz), 7.48 (d, 1H, J = 4.8Hz).
3 3
2
-[2-(2-methoxyethoxy)ethoxy]ethyl2-{[2-(trimethylsilyl)-5-(trimethylstannyl)-3 thienyl]methoxy}ethyl ether (21): A solution
of 4.0 ml diisopropylamine in 120 ml of dry THF was cooled to -78°C. To this 18.5 ml (29.6 mmol) of n-butyllithium was
added. The mixture was then allowed to reach 0˚C and was stirred at this temperature for 10 minutes. Then it was again
cooled to -78°C and 11.0 g (29.3 mmol) of 20 was added dissolved in 30 ml of dry THF and the mixture was stirred for 4
hours. Then 6 ml of trimethyltinchloride solution (5 M in THF) was added and the mixture was continues to be stirred at -
7
8°C. After 3 hours the reaction mixture was allowed to slowly warm to room temperature overnight. The reaction was

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
quenched with water with water and the layers were separated. The aqueous layer was extracted with diethyl ether. The
combined organic layers were washed with water and then with brine. The organic phase was dried over MgSO . After
4
filtration and removal of solvent under vacuum, the crude compound was obtained in a 98% yield (15.2 g, 28.9 mmol). This
1
compound was used without further purification. H-NMR (400 MHz, CDCl ) δ : 0.34 (s, 9H), 0.35 (t, 9H, J = 29.7 Hz),
3
H
Sn
3
.37 (s, 3H), 3.52-3.56 (m, 2H), 3.62-3.69 (m, 14H), 4.62 (s, 2H), 7.28 (s, 1H).
(4-hexadecyl-3'-2,5,8,11,14-pentaoxapentadecyl-2,2'-bithiophen-5-yl)trimethylsilane
(22):
1-(2-bromothiophen-3-yl)-
2
,5,8,11,14-pentaoxapentadecane (7.0 g, 18.4 mmol) was dissolved in 50 ml of dry DMF. Then
palladium(tetrakis)triphenylphosphine (2.20 g, 1.9 mmol) was added to the solution. The mixture was stirred for 20 min at
room temperature. Then a solution of 15 (10.0 g, 18.4 mmol) solution in 50 ml of toluene was added. The temperature was
raised until 110°C and left overnight. Then the solvents were removed under vacuum. The crude was purified by column
chromatography (silica gel, eluent petroleum ether/EtOAc (gradient 0-100% EtOAc) with 5% TEA) and gave the pure title
1
compound as a yellow oil in 80% yield (8.0 g, 14.7 mmol). H NMR (400 MHz, CDCl ) δ : 0.37 (s, 9H), 0.88 (t, J = 6.7 Hz,
3
H
3
3
4
1
3
1
H), 1.22-1.38 (m, 26H), 1.58-1.68 (m, 2H), 2.65 (t, J = 7.8 Hz, 2H), 3.38 (s, 3H), 3.52-3.58 (m, 2H), 3.72-3.62 (m, 14H),
3
13
.64 (s, 2H), 7.09 (s, 1H), 7.11 (d, J = 5.2 Hz 1H), 7.17 (d, J = 5.2 Hz 1H). C NMR (100 MHz, CDCl ) δ : 0.01 (3*CH ),
3
3
3
C
3
4.00 (CH ), 22.52 (2*CH ), 29.34(CH ), 29.37 (CH ), 29.50 (CH ), 29.55 (CH ), 29.58(CH ), 29.64 (CH ), 29.70 (CH ),
3
2
2
2
2
2
2
2
2
0.27 (CH ), 30.56 (CH ), 58.58 (CH ), 66.58 (CH ), 69.20 (CH ), 70.31(CH ), 70.48 (4*CH ), 70.49 (CH ), 71.30 (CH ),
2
2
3
2
2
2
2
2
2
23.50 (CH), 129.51 (CH), 129.52 (CH), 133.52 (C), 134.25 (C), 134.51 (C), 138.58 (C), 150.58 (C).
4
-hexadecyl-3'-2,5,8,11,14-pentaoxapentadecyl-5'-(trimethylstannyl)-2,2'-bithiophen-5-yl)trimethylsilane (23): To 100ml of
THF diisopropylamine (1.9 ml, 13.5 mmol) was added. The mixture was cooled to -78°C. Then n-butyllithium (8.5 ml, 13.5
mmol, 1.6M in hexane) was added drop wise and the reaction was allowed to warm to room temperature. The mixture was
then cooled to -78°C and 22 (7.3 g, 13.5 mmol) dissolved in THF was added dropwise. The mixture was allowed to react at -
7
8°C for 2h. Then trimethyltinchloride (2.7 g, 13.5 mmol, 1M in THF) was slowly added. The mixture was allowed to react
at -78°C for additional 2h and then left overnight to slowly reach room temperature and was then quenched with water. The
mixture was extracted with THF and diethyl ether. The combined organic layers were then washed with brine. The organic
layer was dried over MgSO and filtered; the solvents were removed under vacuum. The resulting slightly yellowish liquid
4
1
was determined as the title compound obtained in 78% yield (7.0 g, 10.5 mmol) and was used without further purification. H
NMR (400 MHz, CDCl ) δ : 0.36 (s, 9H), 0.38 (s, 9H), 0.88 (t, J = 6.7 Hz, 3H), 1.22-1.38 (m, 26H), 1.58-1.68 (m, 2H), 2.65
3
H
3
13
(
t, J = 7.8 Hz, 2H), 3.38 (s, 3H), 3.52-3.58 (m, 2H), 3.72-3.62 (m, 14H), 4.65 (s, 2H), 7.09 (s, 1H), 7.19 (s, 1H). C NMR
3
(
100 MHz, CDCl ) δ : -8.12 (3*CH ), 0.41 (3*CH ), 14.10 (CH ), 22.52 (2*CH ), 29.42 (CH ), 29.50 (2*CH ),
3
C
3
3
3
2
2
2
2
9.51(4*CH ), 29.53 (5*CH ), 29.54 (CH ), 58.88 (CH ), 66.88 (CH ), 69.30 (CH ), 70.41(CH ), 70.58 (4*CH ), 70.60
2 2 2 3 2 2 2 2
(
CH ), 71.98 (CH ), 129.38 (CH), 133.56 (C), 135.61 (C), 136.52 (C), 138.15 (CH), 139.24 (C), 142.21 (C), 151.00 (C).
2 2
1
-(4'-hexadecyl-2,2'-bithiophen-3-yl)-2,5,8,11,14-pentaoxapentadecane (24): A solution of 7.3 g (19.1 mmol) of 1-(2-
bromothiophen-3-yl)-2,5,8,11,14-pentaoxapentadecane, 2.0 g palladium(tetrakis)triphenylphosphine in 300 ml DMF was
prepared under a nitrogen atmosphere and stirred for 20 minutes. To this, 9.0 g (19.1 mmol) of 14 in 100 ml toluene was
added and heated at 110˚C overnight. The reaction mixture was allowed to cool to room temperature solvent was removed
under vacuum. The crude was purified by column chromatography (silica gel, eluent pentane/EtOAc (1:1), Rf: 0.45) and gave
1
the pure title compound as a yellow oil in 71% yield (8.3 g, 13.6 mmol). H-NMR (300 MHz): 0.87 (t, 3H, J = 6.9Hz), 1.20-
3
1
6
.42 ( m, 26H), 1.63-1.70 (m, 2H), 2.59 (t, 2H, J = 7.7Hz), 3.37 (s, 3H), 3.51-3.57 (m, H), 3.61-3.69 (m, 14H ), 4.61 (s, 2H),
3
.90 (s, 1H), 6.99 (d, 1H, J =1.3Hz), 7.11 (d, 1H, J = 5.2Hz), 7.17 (d, 1H, J = 5.0 Hz).
4
3
3
1
-(5'-bromo-4'-hexadecyl-2,2'-bithiophen-3-yl)-2,5,8,11,14-pentaoxapentadecane (25): To a solution of 8.3 g (13.6 mmol) of
4 in 75 ml DCM, 1.0 equivalent of N-bromosuccinimide was added. The mixture was stirred overnight. After completion
2
the solvent was removed under vacuum. The crude was solubilised in cold heptane and filtered over celite. After evaporation

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
of the solvent, purification was done by column chromatography (silica gel, pentane/EtOAc (1:1)) and gave the pure title
1
compound as a yellow oil in 95% yield (8.9 g, 12.9 mmol). H-NMR (300 MHz): 0.87 (t, 3H, J = 6.9 Hz), 1.20-1.42 ( m,
3
2
1
6H), 1.63-1.70 (m, 2H), 2.55 (t, 2H, J =7.5 Hz), 3.37 (s, 3H), 3.51-3.57 (m, H), 3.61-3.69 (m, 14H), 4.56 (s, 2H), 6.86 (s,
3
H), 7.10 (d, 1H, J =5.4 Hz), 7.19 (d, 1H, J = 5.1 Hz).
3
3
(
1-OMe): A solution of 0.9 g (1.9 mmol) of 13, 0.1 g palladium(tetrakis)triphenylphosphine in 5 ml DMF was prepared and
stirred for 20 minutes. To this, 1.8 g (4.3 mmol) of 19 was added and heated at 110˚C overnight. The reaction mixture was
allowed to cool to room temperature and filtrated to remove any solids. To the filtrate an excess of water was added and this
was then extracted with di-ethyl ether. The obtained organic phase was washed with brine and then dried over Na SO . After
2
4
filtration and removal of solvent in vacuum the crude was purified by column chromatography (silica gel, eluent
pentane/EtOAc (gradient 0-100% EtOAc)) and gave the pure title compound as a yellow oil in a 38% yield (0.66 g, 0.72
1
mmol). H NMR (400 MHz, CDCl ) δ : 0.873 (t, J = 6,7 Hz, 3H), 1.30-1.180 (m, 28 H), 2.48 (t, J = 7.7 Hz, 2H), 3.36 (s,
3
H
3
3
6
3
H), 3.70-3.60 (m, 32H), 4.47 (s, 2H), 4.63 (s, 2H), 7.03 (s, 1H), 7,13 (d, J = 5.2 Hz, 1H) 7.18 (d, J = 3.7, 1H), 7.19 (d, J =
3 3 3
13
.7 Hz, 1H), 7.34 (d, J = 5.3 Hz, 1H). C NMR (100 MHz, CDCl ) δ : 14.15 (CH ), 22.62 (2*CH ), 28.99 (CH ), 29.43
3
3
C
3
2
2
(
CH ), 29.49 (2*CH ), 29.69(7*CH ), 30.69 (CH ), 31.89 (CH ), 58.98 (2*CH ), 66.28 (2*CH ), 69.35 (2*CH ), 70.50
2 2 2 2 2 3 2 2
(
2*CH ), 70.55 (2*CH ), 70.59 (8*CH ), 71.89 (2*CH ), 123.91 (CH), 126.05 (CH), 128.02 (CH), 128.17 (C), 128.59 (CH),
2 2 2 2
1
30.51 (CH), 131.11 (C), 135.12 (C), 135.21 (C), 138.25 (2*C), 143.26 (C). (ESI-MS) M/z-calc: 912.5; M/z-found: 935.5
+
(
M+Na ).
(
(
2-OMe-TMS): A solution of 5.1 g (7.4 mmol) of 25, 0.32 g palladium(tetrakis)triphenylphosphine in 80 ml DMF/toluene
50/50) was prepared under a nitrogen atmosphere and stirred for 20 minutes. To this, 12.2 g (17.8 mmol) of 21 in 20 ml
DMF/toluene (50/50) was added and heated at 110˚C overnight. The solvents were removed under vacuum and the crude was
purified by column chromatography (silica gel, eluent heptane/EtOAc gradient 0-100% EtOAc). This gave the pure title
1
compound in 80% yield (5.9 g, 5.9 mmol). H-NMR (400 MHz, CDCl ) δ : 0.37 (s, 9H), 0.88 (t, 3H, J =7.4 Hz), 1.20-1.44
3
H
3
(
(
m, 26H), 1.60-1.70 (m, 2H), 2.74 (t, 2H, J =7.8 Hz), 3.37 (s, 6H), 3.54-3.63 (m, 4H), 3.66-3.76 (m, 28H), 4.56 (s, 2H), 4.62
3
s, 2H), 6.99 (s, 1H), 7.12 (d, 1H, J =5.2 Hz), 7.18 (d, 1H, J =5.6 Hz), 7.21 (s, 1H).
3
3
(
2-OMe): 2-OMe-TMS (2.4 g, 2.3 mmol) was stirred overnight in a TBAF solution in THF. After removal of the solvent the
yellow oil was dissolved in water and 100 g of a cationic ion-exchange resin (DOWEX MAC-3) was added and the
suspension was stirred until the water became colourless and the resin yellow. This was then filtrated and washed several
times with water to remove the TBAF. After extensive rinsing, the product was released from the resin by washing with
1
methanol to obtain the pure title compound in quantitative yield as a yellow oil (2.6 g, 2.3 mmol). H-NMR (400 MHz,
CDCl ) δ : 0.87 (t, 3H, J = 7.4Hz), 1.15-1.40 (m, 26H), 1.60-1.68 (m, 2H), 2.73 (t, 2H, J = 7.8 Hz), 3.37 (s, 6H), 3.54-3.63
3
H
3
3
(
(
(
(
(
m, 4H), 3.66-3.76 (m, 28H), 4.55 (s, 2H), 4.64 (s, 2H), 6.99 (s, 1H), 7.08 (d, 1H, J =1.3 Hz), 7.12 (d, 1H, J = 5.2Hz), 7.19
4 3
13
d, 1H, J =5.6Hz), 7.20 (d, 1H, J = 1.3Hz); C-NMR (100 MHz, CDCl ) δ : 13.99 (CH ), 22.50 (CH ), 29.10 (CH ), 29.17
3
4
3
C
3
2
2
CH ), 30.45 (CH ), 31.53 (CH ), 61.56 (CH ), 66.77 (CH ), 68.42 (CH ), 69.30 (CH ), 69.33 (CH ), 70.18 (CH ), 70.44
2
2
2
2
2
2
2
2
2
CH ), 70.47 (CH ), 70.50 (CH ), 72.45 (CH ), 122.84 (CH), 123.85 (CH), 126.04 (CH), 129.20 (CH), 130.03 (CH), 132.98
2
2
2
2
+
C), 134.99 (C), 136.13 (C), 139.64 (C), 140.06 (C). (ESI-MS) M/z-calc: 912.5; M/z-found: 935.5 (M+Na ).
(
3-OMe). A solution of 1.1 g (2.5 mmol) of 13 and palladium(tetrakis)triphenylphosphine in 5ml DMF was prepared and
stirred for 20 minutes. To this, 2.6 g (5.0 mmol) of 21 was added and heated at 110˚C overnight. The solvent was removed
under vacuum and redissolved in 10% HCl methanol solution and stirred for 4h. After removal of all volatile compounds
under vacuum, crude was purified by column chromatography (silica gel, eluent PET 40-60/EtOAc in a gradient 0-100%
1
EtOAc) and gave the pure title compound as a yellow oil in a 40% yield (900 mg, 1.0 mmol). H NMR (400 MHz, CDCl )
3
δ : 0.88 (t, J = 6.7 Hz, 3H), 1.22-1.38 (m, 26H), 1.58-1.68 (m, 2H), 2.70 (t, J = 8.0 Hz, 2H), 3.37 (s, 6H), 3.51-3.56 (m, 4H),
H
3
3
13
3
.62-3.70 (m, 28H), 4.52 (s, 2H), 4.55 (s, 2H), 6.98 (s, 1H), 7.07 (s, 1H), 7.09 (s, 1H), 7.11 (s, 1H), 7.18 (s, 1H). C NMR

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
(
(
(
100 MHz, CDCl3) δ : 14.09 (CH ), 22.65 (CH ), 29.29(CH ), 29.32 (CH ), 29.44 (CH ), 29.53 (CH ), 29.57 (CH ), 29.66
C
3
2
2
2
2
2
2
CH ), 30.52 (CH ), 31.88 (CH ), 68.48 (CH ), 68.53 (CH ), 69.40 (CH ), 70.47 (CH ), 70.57 (CH ), 70.61 (CH ), 71.89
2
2
2
2
2
2
2
2
2
CH ), 121.70 (CH), 122.74 (CH), 123.72 (CH), 125.98 (CH), 126.45 (CH), 129.59 (C), 135.01 (C), 136.37 (C), 137.67 (C),
2
+
1
39.75 (C), 140.22 (C), 140.27 (C). (ESI-MS) M/z-calc: 912.5; M/z-found: 930.7 (M+NH ).
4
(
4): A solution of 0.6 g (1.3 mmol) of 18, 0.1 g (0.1 mmol) palladium(tetrakis)triphenylphosphine in 5 ml DMF was prepared
and stirred for 20 minutes. To this, 1.2 g (2.6 mmol) of 12 was added and heated at 110˚C overnight. The reaction mixture
was allowed to cool to room temperature and filtrated to remove any solids. To the residue an excess of water was added and
this was then extracted with di-ethyl ether. The obtained organic phase was washed with brine and then dried over Na SO .
2
4
After filtration and removal of solvent in vacuum the crude was purified by column chromatography (silica gel, eluent PET
4
0-60/EtOAc in a gradient 0-100% EtOAc) and gave the pure title compound as a yellow oil in a 40% yield (0.85 g, 0.9
1
mmol). H NMR (400 MHz, CDCl ) δ : 0.82-0.94 (m, 6H), 1.16-1.40 (m, 52H), 1.50-1.70 (m, 4H), 2.55 (t, J = 7.8 Hz, 2H),
3
H
3
2
.77 (t, J = 7.75 Hz, 2H), 3.37 (s, 3H), 3.5-3.6 (m, 2H), 3.6-3.74 (m, 14H), 4.42 (s, 2H), 6.92 (d, J = 5.20 Hz, 1H ), 6.97 (d,
3 3
13
J = 5.2 Hz, 1H), 7.16 (d, J = 5.2 Hz, 1H), 7.17 (s, 1H), 7.31 (d, J = 5.2 Hz, 1H). C NMR (100 MHz, CDCl ) δ : 14.11
3
3
3
3
C
(
(
(
2*CH ), 22.52 (2*CH ), 29.33(CH ), 29.35 (CH ), 29.50 (CH ), 29.49 (CH ), 29.69(11*CH ), 29.71 (10*CH ), 30.71
3 2 2 2 2 2 2 2
CH ), 30.83 (CH ), 31.92 (CH ), 59.03 (CH ), 66.75 (CH ), 69.40 (CH ), 70.50 (CH ), 70.55 (CH ), 70.61 (4*CH ), 71.62
2
2
2
3
2
2
2
2
2
CH ), 123.70 (CH), 125.81 (CH), 126.99 (CH), 128.85 (CH), 130.01 (CH), 131.12 (C), 132.15 (C), 133.52 (C), 134.41 (C),
2
+
1
38.02 (C), 139.72 (C), 144.01 (C). (ESI-MS) M/z-calc: 916.6; M/z-found: 939.6 (M+Na ).
(
5-TMS) 2-Bromo-3-hexadecylthiophene (11) (3.85 g, 9.9 mmol) was dissolved in 20 ml of toluene. Then
palladium(tetrakis)triphenylphosphine (2.20 g, 1.9 mmol) was added to the solution. The mixture was stirred for 20 min at
room temperature. Then 23 (7.0 g, 8.3 mmol) solution in 20 ml of toluene was added. The temperature was raised to 110°C
and left overnight. Then the solvents were removed under vacuum. The crude was purified by column chromatography
(
silica gel, eluent petroleum ether 40-60/EtOAc (gradient0-100% EtOAc)) with 5% TEA) and gave the pure title compound
1
as a yellow oil in a 50% yield (4.0 g, 5.0 mmol). H NMR (400 MHz, CDCl ) δ : 0.36 (s, 9H), 0.88 (t, J = 6.7 Hz, 6H), 1.34-
3
H
3
1
3
.22 (m, 52H), 1.69-1.62 (m, 4H), 2.64 (t, J = 7.8 Hz, 2H), 2.77 (t, J = 7.8 Hz, 2H), 3.36 (s, 3H), 3.54-3.52 (m, 2H), 3.68-
3 3
.61 (m, 14H), 4.63 (s, 2H), 6.92 (d, J = 5.2 Hz, 1H), 7.10 (s, 1H), 7.12 (s, 1H), 7.15 (d, J = 5.2Hz, 1H).
3
3
(
5): To 20 ml of 10% HCl solution in methanol 5-TMS (300 mg, 0.3 mmol) was added. The mixture was allowed to react
overnight at room temperature. Then solvent and HCl were removed under vacuum. The crude was purified by column
chromatography (silica gel, petroleum ether 40-60/EtOAc (gradient0-100% EtOAc)) and gave the pure title compound in an
1
8
4
5% yield (250 mg, 0.26 mmol). H NMR (400 MHz, CDCl ) δ : 0.88 (t, J = 6.7 Hz, 6H), 1.34-1.22 (m, 52H), 1.69-1.62 (m,
3
H
3
H), 2.60 (t, J = 7.6 Hz, 2H), 2.77 (t, J = 7.6 Hz, 2H), 3.37 (s, 3H), 3.54-3.52 (m, 2H), 3.69-3.61 (m, 14H), 4.61 (s, 2H), 6.92
3
3
13
(
s, 1H), 6.92 (d, J = 5.2 Hz, 1H), 7.02 (d, J = 1.0 Hz, 1H), 7.12 (s, 1H), 7.16 (d, J = 5.2 Hz, 1H). C NMR (100MHz,
3 4 3
CDCl3) δ : 14.21 (2*CH ), 22.75 (2*CH ), 29.13(CH ), 29.17 (CH ), 29.45 (CH ), 29.47 (CH ), 29.68(11*CH ), 29.70
H
3
2
2
2
2
2
2
(
10*CH ), 30.49 (CH ), 30.71 (CH ), 31.98 (CH ), 59.00 (CH ), 66.80 (CH ), 69.40 (CH ), 70.50 (CH ), 70.55 (CH ), 70.61
2 2 2 2 3 2 2 2 2
(
4*CH ), 71.91 (CH ), 120.71 (CH), 127.81 (CH), 127.91 (CH), 128.51 (CH), 130.01 (CH), 134.09 (2*C), 134.49 (C),
2 2
+
1
34.99 (2*C), 139.71 (C), 143.95 (C). (ESI-MS) M/z-calc: 916.6; M/z-found: 939.5 (M+Na ).
(
6): A solution of 18 (432 mg, 0.93 mmol), palladium(tetrakis)triphenylphosphine (50 mg, 0.04 mmol) and CuO (77 mg, 0.97
mmol) in 5 ml of dry DMF was prepared. To this 14 (964 mg, 1.90 mmol) was added. The mixture was stirred overnight at
10°C. After this, the reaction was cooled to room temperature. Formed solids were filtered off and water was added to the
1
reaction mixture. The mixture was extracted with diethylether. The combined organic layers were then washed with brine.
The organic layer was dried over MgSO and filtered; the solvent was removed under vacuum. The crude was subsequently
4
purified by column chromatography (silica gel, petroleum ether 40-60/EtOAc (gradient 0-100% EtOAc)) and gave the pure
1
title compound in a 45% yield (368 mg, 0.42 mmol). H NMR (400 MHz, CDCl ) δ : 0.88 (t, J = 6.7 Hz, 6H), 1.22-1.38 (m,
3
H
3

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
5
6
2
2H), 1.58-1.68 (m, 4H), 2.64-2.54 (m, 4H), 3.36 (s, 3H), 3.55-3.51 (m, 2H), 3.72-3.61 (m, 14H), 4.59 (s, 2H), 6.79 (s, 1H),
13
.9 (s, 1H), 6.99 (s, 1H), 7.00 (s, 1H), 7.15 (s, 1H). C NMR (100 MHz, CDCl3) δ : 14.11 (2*CH ), 22.52 (2*CH ),
C
3
2
9.23(CH ), 29.25 (CH ), 29.50 (CH ), 29.51 (CH ), 29.69(11*CH ), 29.71 (10*CH ), 30.49 (CH ), 30.71 (CH ), 31.92
2
2
2
2
2
2
2
2
(
(
CH ), 66.89 (CH ), 69.41 (CH ), 70.50 (CH ), 70.55 (CH ), 70.61 (4*CH ), 71.91 (CH ), 120.71 (CH), 123.71 (CH), 127.81
2 2 2 2 2 2 2
CH), 128.51 (CH), 130.01 (CH), 134.29 (2*C), 134.49 (2*C), 134.59 (C), 139.71 (C), 143.95 (C). (ESI-MS) M/z-calc:
+
9
16.6; M/z-found: 939.5 (M+Na ).

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
a
ESI-1 : Isomer 1-OMe
HPLC trace (UV)
UV-Vis of main signal
ESI-MS of main signal

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
b
ESI-1 : Isomer 2-OMe
HPLC trace (UV)
UV-Vis of main signal
ESI-MS of main signal

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
c
ESI-1 : Isomer 3-OMe
UV-Vis of main signal
HPLC trace (UV)
ESI-MS of main signal

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
d
ESI-1 : Isomer 4
HPLC trace (UV)
UV-Vis of main signal
ESI-MS of main signal

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
e
ESI-1 : Isomer 5
C15H31
C15H31
S
S
S
MeO(EO )O
4
HPLC trace (UV)
UV-Vis of main signal
ESI-MS of main signal

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
f
ESI-1 : Isomer 6
HPLC trace (UV)
UV-Vis of main signal
Event#: 1 Scan(E+) Ret. Time: 15.95
ESI-MS of main signal

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
ESI 2
1
2
1
2
'-OH
-OH
-OMe
-OMe
-OMe
4
5
6
1.0
1.00
0.8
3
0.75
0.6
0.50
0.4
0.25
0.2
0
.0
1
0.00
1E-4
E-3
0.01
0.1
1
1E-3
0.01
0.1
1
conc. (mM)
log conc. (mM)
Concentration dependent scattering measurements of the different terthiophene amphiphiles in
water at 20°C.
ESI 3
1
1
2
2
-OMe
'-OH
-OMe
-OH
-OMe
660
50
40
30
20
10
00
90
80
1
2-OH
1
,0
6
3
6
0,8
4
5
6
6
0,6
6
6
0,4
6
0,2
5
5
0,0
1
E-4
1E-3
0,01
0,1
1
10
1
E-4
1E-3
0,01
0,1
1
10
A
B
conc. mM
conc. mM
4
5
6
6
60
50
40
30
20
10
00
1-OMe
2
3-OMe
6
60
50
40
630
20
10
00
90
6
6
6
6
6
6
6
6
6
6
6
5
1E-5
1E-4
1E-3
0,01
0,1
1
10
1E-4
1E-3
0,01
0,1
1
conc. mM
conc. mM
C
D
A) Emission intensity of Nile Red in combination with different concentrations of
thiophene amphiphiles to determine the cmc of isomers 1-6 at 20°C and B-D) the
shift in emission wavelength, displaying also a transition at lower concentrations
which are attributed to premicellar aggregates.

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
ESI 4
DSC of the different thiophene surfactants that display a temperature effect. Concentrations
used were 1.0 mM for compounds 1-OMe and 2-OMe, for 3-OMe 10 mM was used and
corrected for this to 1.0mM.
Normalized plot for the self-quenching of the concentration corrected emission with
increasing concentration. The declining concentration corrected emission with increasing
concentration depicts aggregation due to the electronic coupling between chomophores.

Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2010
ESI 6
2
-OMe in different solvent (polarity, dielectric const.)
1,00
0,75
0,50
0,25
water (80)
ethanol (30)
2-propanol (18)
THF (7,5)
choloform (5)
300
350
400
450
500
wavelength (nm)
Normalized absorption-spectra of 2-OMe in different solvents with different polarity in order
to illustrate that the absorption maxima did not change with solvent polarity upon going from
moderately polar (ethanol) to an apolar solvent (chloroform). Therefore, the different
absorption maxima of the oligothiophenes in chloroform and water are most likely due to
aggregation in the later.