Synthesis of oligophenylenevinylene heptamers substituted with fullerene moieties

Article abstract of DOI:10.1002/ejoc.200800312

Oligophenylenevinylene (OPV) derivatives substituted with one or two fullerene subunits have been prepared starting from a fullerene carboxylic acid derivative and OPV heptamers bearing one or two alcohol functions. The electrochemical properties of the resulting C₆₀-OPV derivatives have been investigated by cyclic voltammetry. Whereas the fist reduction of both C₆₀-OPV conjugates is centered on the C₆₀ unit, the oxidation is centered on the OPV rod. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejoc.200800312

FULL PAPER
DOI: 10.1002/ejoc.200800312
Synthesis of Oligophenylenevinylene Heptamers Substituted with Fullerene
Moieties
Aline Gégout,[a] Michel Holler,[a] Teresa M. Figueira-Duarte,[a] and
Jean-François Nierengarten*[a]
Keywords: Conjugated systems / Fullerene / Oligophenylenevinylene
Oligophenylenevinylene (OPV) derivatives substituted with
one or two fullerene subunits have been prepared starting
from a fullerene carboxylic acid derivative and OPV hepta-
mers bearing one or two alcohol functions. The electrochemi-
cal properties of the resulting C60-OPV derivatives have
been investigated by cyclic voltammetry. Whereas the fist re-
duction of both C60–OPV conjugates is centered on the C60
unit, the oxidation is centered on the OPV rod.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
ene moieties.[7] In this paper, we now report in detail the
synthesis of this compound. In addition, we also describe
the preparation of the corresponding system substituted
with one fullerene subunit as well as the electrochemical
properties of the all series of compounds.
Introduction
Following the preparation of the first photovoltaic de-
vices from C60–oligophenylenevinylene (OPV) conjugates,[1]
a great deal of attention has been devoted to hybrid systems
combining C60 with π-conjugated oligomers.[2–3] Among
their potential use as active materials in photovoltaic de-
vices, C60-(π-conjugated oligomer) hybrid systems offers
also interesting perspectives for optical limiting or photody-
namic therapy applications.[4] The photophysical properties
Results and Discussion
The synthesis of the C60-OPV conjugate is based on the
of these C60-(π-conjugated oligomer) dyads have been ex- esterification reaction of a fullerene carboxylic acid building
tensively studied. A characteristic feature in all these dyads block with OPV heptamers bearing one or two hydroxy
is an ultrafast energy transfer from the lowest singlet excited groups. To this end, we have first prepared methanofuller-
state of the conjugated system to populate the fullerene sin- ene derivative 5 (Scheme 1).
glet.[2] This first event can be followed by an electron trans-
N,NЈ-Dicyclohexylcarbodiimide (DCC)-mediated esteri-
fer depending on the donating ability of the oligomer, on fication of tert-butyl 2-hydroxyacetate (2) with carboxylic
structural factors and on the solvent polarity.[2] The pecu- acid 1[8] yielded malonate 3. The functionalization of C60 is
liar electronic properties of C60-(π-conjugated oligomer) dy- based on the Bingel reaction.[9] Nucleophilic addition of a
ads led also to the development of dendritic systems with stabilized α-halocarbanion to the C60 core, followed by in-
interesting light harvesting properties[5] or for evidencing tramolecular nucleophilic substitution, leads to clean cyclo-
original dendritic effects.[6]
propanation of C60. The α-halomalonate derivative is pre-
The C60–OPV conjugates reported so far generally com- pared in situ from the reaction of the malonate with
bine the fullerene accepting unit with relatively short OPV iodine.[10] Treatment of C60 with 3, iodine and 1,8-diazabi-
oligomers.[1,3] However, by increasing the length of the OPV cyclo[5.4.0]undec-7-ene (DBU) in toluene at room tempera-
conjugated backbone, its absorption can be extended to the ture afforded methanofullerene 4 in 52% yield. Subsequent
red thus providing new hybrid materials with improved ab- hydrolysis of the tert-butyl ester group with CF3CO2H gave
sorption properties for photovoltaic applications.[2] In ad- carboxylic acid 5 in 79% yield.
dition, OPV derivatives with longer backbones are better
electron donors, thus allowing electron transfer processes in relies upon reaction of terephthaldicarbaldehyde (benzene-
the corresponding C60-OPV systems. This has been demon- 1,4-dicarbaldehyde) derivatives and phosphonate
The synthetic approach to prepare the OPV heptamers
8
strated with an OPV heptamer derivative bearing two fuller- (Scheme 2). Actually, the Wadsworth–Emmons reaction has
proven to be a powerful tool for the synthesis of OPV deriv-
atives as the trans olefins are selectively produced from ben-
zylic phosphonates.[11] The preparation of phosphonate 8 is
depicted in Scheme 2. Compound 6 was obtained in nine
steps from methyl 3,4,5-trihydroxybenzoate as previously
[a] Laboratoire de Chimie des Matériaux Moléculaires, Université
Louis Pasteur et CNRS (UMR 7509), Ecole Européenne de
Chimie, Polymères et Matériaux (ECPM),
25 rue Becquerel, 67087 Strasbourg Cedex 2, France
E-mail: nierengarten@chimie.u-strasbg.fr
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Scheme 1. Reagents and conditions: a) DCC, DMAP, CH2Cl2, 0 °C to room temp., 24 h (80%); b) C60, DBU, I2, PhMe, room temp., 3 h
(52%); c) CF3CO2H, CH2Cl2, room temp., 4 h (79%).
Scheme 2. Reagents and conditions: a) TMSBr, CHCl3, 0 °C, 3 h; b) P(OEt)3, 150 °C, 12 h (88% from 6); c) tBuOK, THF, 0 °C to room
temp., 3 h (65%).
reported.[12] Treatment of 6 with trimethylsilyl bromide of 13 with an excess of tBuLi followed by treatment of the
(TMSBr) in CHCl3 yielded bromide 7. It is worth noting resulting organolithium derivative with N,N-dimethylform-
that the choice of the appropriate conditions for the prepa- amide (DMF) gave 14 in 73% yield. The protected OPV
ration of bromide 7 was the key to this synthesis. Actually, heptamer 19 was then obtained from dialdehyde 14 and
this intermediate was found to be unstable. Under bromina-
tion conditions using TMSBr, the volatile by-products can
be eliminated by simple evaporation and no purification
step was required. Therefore, the product could be used in
the next step as received. Treatment of bromide 7 with
P(OEt)3 under Arbuzov conditions then gave phosphonate
8 in 88% yield. Reaction of 8 with dialdehyde 9[13] in the
presence of tBuOK in THF afforded the OPV model com-
pound 10 in 65% yield. All the spectroscopic studies and
elemental analysis results were consistent with the structure
of 10. In particular, coupling constants of ca. 16 Hz for the
AB systems corresponding to the signals of the vinylic pro-
tons in the 1H NMR spectrum confirmed the E stereochem-
istry of all the double bonds in 10.
The preparation of the OPV heptamer substituted with
one methanofullerene subunit is depicted in Schemes 3 and
4. Reduction of ester 11 with lithium aluminum hydride (Li-
Scheme 3. Reagents and conditions: a) LiAlH4, THF, 0 °C (12:
AlH4) in THF gave 12 in 91% yield. Subsequent treatment
91%; 16: 91%); b) TIPSCl, imidazole, DMF, 0 °C, 24 h (13: 90%;
17: 87%); c) tBuLi, THF, –78 °C, 3 h then DMF, –78 to 0 °C, 3 h
ence of imidazole afforded protected derivative 13. Reaction (14: 73%; 18: 84%).
of 12 with triisopropylsilyl chloride (TIPSCl) in the pres-
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Oligophenylenevinylene Heptamers with Fullerene Moieties
phosphonate 8 under Wadsworth–Emmons conditions nally, the C60–OPV conjugate 21 was prepared from 20 and
(Scheme 4). Treatment of 19 with tetra-n-butylammonium carboxylic acid 5 under esterification conditions using DCC
fluoride (TBAF) in THF at 0 °C afforded alcohol 20. Fi- and 4-(dimethylamino)pyridine (DMAP).
Scheme 4. Reagents and conditions: a) 8, tBuOK, THF, 0 °C to room temp., 3 h (40%); b) TBAF, THF, 0 °C, 2 h (93%); c) 5, DCC,
DMAP, CH2Cl2, 0 °C to room temp., 12 h (73%).
Scheme 5. Reagents and conditions: a) 8, tBuOK, THF, 0 °C to room temp., 3 h (46%); b) TBAF, THF, 0 °C, 2 h (47%); c) 5, DCC,
DMAP, CH2Cl2, 0 °C to room temp., 12 h (71%).
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FULL PAPER
Reduction of dialdehyde 15 with LiAlH4 followed by 6.72 ppm for the aromatic protons of the terminal trialkyl-
treatment of the resulting 16 with TIPSCl in the presence oxyphenyl units (Ha), and a singlet at δ = 7.69 ppm for the
1
of imidazole afforded protected derivative 17 (Scheme 3). aromatic protons of the central phenyl ring (Hl). The H
Reaction of 17 with an excess of tBuLi in THF followed by NMR spectrum reveals also two singlets at δ = 5.44 and
quenching with DMF gave 18 in 84% yield. The protected 5.02 ppm corresponding to the resonances of the two dif-
OPV heptamer 22 was then prepared under Wadsworth– ferent benzylic CH2 groups (HA and HC), an A2X system
Emmons conditions from dialdehyde 18 and phosphonate for the aromatic protons of the 3,5-didodecyloxyphenyl
8 (Scheme 5). Diol 23 was finally obtained in 47% yield by moiety (HD and HE) as well as the diagnostic signals of the
treatment with TBAF in THF at 0 °C. The moderate yields alkyloxy groups.
for the two last steps are mainly associated with difficulties
The electrochemical properties of hybrid compounds 21
encountered during the purification of the OPV heptamer and 24 were investigated by cyclic voltammetry (CV). For
derivatives 22 and 23. Reaction of diol 23 with carboxylic the sake of comparison, electrochemical measurements
acid 5 under esterification conditions using DCC and were also carried out with model compounds 4, 19 and 22.
DMAP afforded compound 24 in 71% yield.
All the experiments were performed at room temperature in
The structure and purity of compounds 21 and 24 were CH2Cl2 solutions containing tetra-n-butylammonium tetra-
1
confirmed by H and 13C NMR spectroscopy, mass spec- fluoroborate (0.1 ) as supporting electrolyte, with a Pt wire
trometry and elemental analysis. As a typical example, the as the working electrode and a saturated calomel electrode
1H NMR spectrum of 24 is depicted in Figure 1. Unambig- (SCE) as a reference. Potential data for all of the com-
uous assignment was achieved on the basis of 2D-COSY pounds are collected in Table 1.
and NOESY spectra recorded at room temperature in
In the anodic region, model compound 4 presents an
CDCl3. The spectrum shows the characteristic signals of irreversible peak at ca. +1.7 V vs. SCE which can be likely
the centrosymmetric OPV core. In particular, two sets of attributed to the oxidation of the dialkyloxyphenyl unit.[14]
AB quartets (δ = 7.00 and 7.23 ppm) and a singlet (δ = In the cathodic region, compound 4 revealed the typical
7.08 ppm) are seen for the vinylic protons, a singlet at δ = electrochemical response of methanofullerene derivatives
1
Figure 1. H NMR spectrum (CDCl3, 300 MHz) of compound 24.
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Oligophenylenevinylene Heptamers with Fullerene Moieties
Table 1. Electrochemical data of 4, 19, 21, 22 and 24 determined ing the occurrence of intramolecular photo-induced pro-
by CV on a Pt working electrode in CH2Cl2 + 0.1  nBu4NBF4 at
room temperature.
cesses. Detailed photophysical studies are currently under
investigation and special emphasis is placed on the detec-
Oxidation
E1
Reduction
E1
tion of long-lived charge-separated states.
E2
E3
4
1.66[b]
0.96[b]
0.96[b]
1.03[b]
1.14[b]
–0.51 (75)[a]
–1.74[b]
–0.89[b]
–1.12[b]
19
21
22
24
Experimental Section
–0.50 (80)[a]
–1.72[b]
–0.88[b]
–1.10[b]
–1.11[b]
General: Reagents and solvents were purchased as reagent grade
and used without further purification. Compounds 1,[8] 6,[12] and
9[13] were prepared according to the literature. THF was distilled
from sodium benzophenone ketyl. All reactions were performed in
standard glassware under an inert Ar atmosphere. Evaporation and
concentration were done at water aspirator pressure and drying in
vacuo at 10–2 Torr. Column chromatography: silica gel 60 (230–
400 mesh, 0.040–0.063 mm) was purchased from E. Merck. Thin-
layer chromatography (TLC) was performed on glass sheets coated
with silica gel 60 F254 purchased from E. Merck, visualization by
UV light. IR spectra [cm–1] were measured on an ATI Mattson
Genesis Series FTIR instrument. NMR spectra were recorded on
–0.51 (80)[a,c] –0.88[b]
[a] Values for (Epa + Epc)/2 in V vs. SCE and ∆Epc in mV (in paren-
theses) at a scan rate of 100 mVs–1. [b] Peak potential value at a
scan rate of 100 mVs–1, irreversible process. [c] Bielectronic process.
and several reduction steps are seen. Whereas the first one
is reversible, the second is irreversible at low scan rates but
becomes partially reversible upon increasing the scan rate
in accordance with already reported observations on other
C60 derivatives.[15] The third wave gradually disappears
when the second one becomes reversible, so that it probably a Bruker AC 300 with solvent peaks as reference. MALDI-TOF-
mass spectra (m/z; % relative intensity) were carried out on a
Bruker BIFLEXTM matrix-assisted laser desorption time-of-flight
mass spectrometer equipped with SCOUTTM High Resolution Op-
tics, an X-Y multi-sample probe and a gridless reflector. Ionization
is accomplished with the 337 nm beam from a nitrogen laser with
a repetition rate of 3 Hz. All data were acquired at a maximum
accelerating potential of 20 kV in the linear positive ion mode. The
output signal from the detector was digitized at a sampling rate of
implies reduction of the product formed after the second
reduction. OPV heptamers 19 and 22 exhibit an irreversible
one-electron transfer process both in the cathodic and in
the anodic region. The cyclic voltammograms recorded for
hybrid compounds 21 and 24 shows the characteristic elec-
trochemical features of both constitutive units, i.e. meth-
anofullerene and OPV. The comparison of the E1/2 poten-
tials of 21 and 24 with the corresponding model com-
pounds clearly shows that, for both hybrid compounds, the
1 GHz.
A
saturated solution of 1,8,9-trihydroxyanthracene
(dithranol Aldrich EC: 214–538–0) in CH2Cl2 was used as a matrix.
three first reduction waves correspond to fullerene-centered Typically, a 1:1 mixture of the sample solution in CH2Cl2 was
mixed with the matrix solution and 0.5 µL of the resulting mixture
was deposited on the probe tip. Elemental analyses were performed
by the analytical service at the Institut Charles Sadron, Strasbourg.
processes, while the oxidation process is centered on the
OPV unit. Comparison of the redox potentials of 21 with
those of the corresponding model compounds 4 and 19 re-
veals no particular electronic interactions between the ful-
lerene unit and the OPV moiety. In the case of 24, the oxi-
dation potential of the OPV core is shifted to more positive
values. This shift could be a consequence of small electronic
interactions between the OPV core and the C60 units, re-
sulting in a more difficult oxidation for the OPV moiety.
However, the different subunits are separated by rather long
spacers and such effect is not observed for hybrid com-
pound 21. Therefore, it appears more reasonable to ascribe
the observed potential shift to solvation effects resulting
from the presence of the surrounding apolar fullerene
groups.
Compound 3: DCC (8.20 g, 0.04 mol) and DMAP (0.49 g,
4.00 mmol) were added to a solution of 1 (6.00 g, 0.01 mol) and 2
(1.28 g, 0.01 mol) in CH2Cl2 (300 mL) at 0 °C. After 1 h, the mix-
ture was allowed to slowly warm to room temperature. After 24 h
the mixture was filtered and the solvents evaporated. Column
chromatography (SiO2, CH2Cl2/cyclohexane, 1:1) gave 3 (5.42 g,
80%). Colourless glassy product. IR (neat): ν = 1747 (C=O) cm–1
.
˜
1H NMR (CDCl3, 300 MHz): δ = 6.47 (d, J = 2 Hz, 2 H), 6.40 (t,
J = 2 Hz, 1 H), 5.10 (s, 2 H), 4.55 (s, 2 H), 3.92 (t, J = 6 Hz, 4 H),
3.54 (s, 2 H), 1.76 (m, 4 H), 1.49 (s, 9 H), 1.26 (m, 36 H), 0.88 (t,
J = 6 Hz, 6 H) ppm. C40H68O8 (676.98): calcd. C 70.97, H 10.12;
found C 70.99, H 10.38.
Compound 4: DBU (0.26 mL, 1.74 mmol) was added to a stirred
solution of C60 (500 mg, 0.69 mmol), I2 (194 mg, 0.76 mmol) and
3 (331 mg, 0.69 mmol) in toluene (500 mL) at room temperature.
The solution was stirred for 12 h, filtered through a short plug of
SiO2 (CH2Cl2) and the solvents evaporated. Column chromatog-
raphy (SiO2, CH2Cl2/Hexane, 1:9) yielded 4 (503 mg, 52%). Dark
Conclusions
In conclusion, we have developed novel OPV heptamers
substituted with one or two alcohol groups allowing their
further functionalization with fullerene subunits. The elec-
trochemical properties of the resulting hybrid compounds
have been investigated. Whereas the fist reduction of both
C60–OPV conjugates is centered on the C60 unit, the oxi-
dation is centered on the OPV rod. Preliminary lumines-
cence measurements reveal no emission from the OPV core
in 21 or 24 indicating a strong quenching of the OPV fluo-
red glassy product. IR (neat): ν = 1747 (C=O) cm–1 1H NMR
.
˜
(CDCl3, 300 MHz): δ = 6.61 (d, J = 2 Hz, 2 H), 6.39 (t, J = 2 Hz,
1 H), 5.47 (s, 2 H), 4.84 (s, 2 H), 3.89 (t, J = 6 Hz, 4 H), 1.73 (m,
4 H), 1.56 (s, 9 H), 1.28 (m, 36 H), 0.88 (t, J = 6 Hz, 6 H) ppm.
C100H66O8 (1395.62): calcd. C 86.06, H 4.77; found C 85.90, H
4.98.
Compound 5: A solution of 4 (667 mg, 0.48 mmol) and trifluoro-
acetic acid (25 mL) in CH2Cl2 (100 mL) was stirred at room tem-
rescence by the fullerene moiety in both 21 and 24 suggest- perature for 12 h. The mixture was then washed with water, dried
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A. Gégout, M. Holler, T. M. Figueira-Duarte, J.-F. Nierengarten
FULL PAPER
(MgSO4), filtered and the solvents evaporated. Recrystallization
rated. The residue was taken up with Et2O, washed with brine,
dried (MgSO4), filtered and the solvents evaporated. Column
chromatography (SiO2, hexane) yielded 13 (7.14 g, 90%). Colour-
from CH2Cl2/hexane yielded 5 (510 mg, 79%). Dark red solid. IR
(neat): ν = 1747 (C=O) cm–1 1H NMR (CDCl3, 300 MHz): δ =
.
˜
1
6.59 (d, J = 2 Hz, 2 H), 6.39 (t, J = 2 Hz, 1 H), 5.45 (s, 2 H), 5.00
(s, 2 H), 3.89 (t, J = 6 Hz, 4 H), 1.73 (m, 4 H), 1.28 (m, 36 H),
0.88 (t, J = 6 Hz, 6 H) ppm. 13C NMR (CDCl3, 75 MHz): δ =
163.0, 162.9, 160.5, 145.3, 145.2, 145.1, 145.0, 144.9, 144.7, 144.5,
144.4, 143.9, 143.8, 143.1, 143.0, 142.95, 142.9, 142.2, 142.1, 141.9,
141.8, 140.9, 140.8, 139.7, 138.6, 136.5, 107.4, 101.7, 71.1, 69.2,
68.2, 62.0, 51.2, 31.9, 31.4, 31.0, 30.2, 29.7, 29.6, 29.5, 29.4, 29.3,
26.1, 25.7, 22.7, 14.1 ppm. C96H58O8 (1339.51): calcd. C 86.08, H
4.36; found C 86.20, H 4.74.
less oil. H NMR (CDCl3, 300 MHz): δ = 7.70 (d, J = 2 Hz, 1 H),
7.34 (d, J = 8 Hz, 1 H), 7.25 (dd, J = 8 and 2 Hz, 1 H), 4.78 (s, 2
H), 1.13 (m, 21 H) ppm. 13C NMR (CDCl3, 75 MHz): δ = 142.6,
134.5, 133.3, 132.7, 131.0, 130.5, 121.7, 119.2, 64.4, 17.7, 12.2 ppm.
C
16H26Br2OSi (422.28): calcd. C 45.51, H 6.21; found C 44.98, H
5.82.
Compound 14: A 1.7  tBuLi solution in THF (11 mL, 18.7 mmol)
was added dropwise within 0.5 h to a solution of 13 (2.0 g,
4.73 mmol) in dry THF (80 mL) at –78 °C under Ar. The resulting
mixture was stirred at –78 °C for 2 h, then warmed slowly to 0 °C
(1 h) and cooled to –78 °C. DMF (2.2 mL, 28.38 mmol) was added
and after 1 h at –78 °C, the mixture was warmed slowly to 0 °C. A
2  aqueous HCl solution was then added. The THF was evapo-
rated and Et2O added. The organic layer was washed with a 2 
aqueous HCl solution, then with water, dried (MgSO4) and the
solvents evaporated. Column chromatography (SiO2, hexane/
CH2Cl2, 2:1) yielded 14 (1.11 g, 73%). Compound 14 was found to
be quite unstable and was used as received in the next step. Colour-
Compound 8: TMSBr (0.1 mL, 0.69 mmol) was added to a stirred
solution of 6 (500 mg, 0.58 mmol) in CHCl3 (3 mL) at 0 °C. After
1 h, the mixture was warmed to room temperature (within 1 h),
then stirred for 3 h, filtered and evaporated to give compound 7 as
a yellow solid that was used as received in the next step. A solution
of 7 in P(OEt)3 (1 mL) was stirred at 150 °C for 12 h. After cooling,
the resulting mixture was evaporated. Column chromatography
(SiO2, CH2Cl2/MeOH, 49:1) yielded 8 (502 mg, 88%). Yellow
glassy product. 1H NMR (CDCl3, 300 MHz): δ = 7.49 (s, 4 H),
7.46 (d, J = 3 Hz, 2 H), 7.31 (dd, J = 2, J = 6.5 Hz, 2 H), 7.10 (s,
2 H), 7.10 (d, J = 16,5 Hz, 1 H), 6.99 (d, J = 16.5 Hz, 1 H), 6.72
(s, 2 H), 4.03 (t, J = 6.5 Hz, 6 H), 3.99 (t, J = 6.5 Hz, 4 H), 3.17
(d, J = 22 Hz, 2 H), 1.80 (m, 6 H), 1.32 (m, 60 H), 0.88 (t, J =
6 Hz, 9 H) ppm. 13C{1H} {31P} NMR (CDCl3, 75 MHz): δ = 153.3,
132.5, 131.0, 130.1, 128.8, 128.2, 128.0, 127.2, 126.8, 126.7, 126.6,
105.3, 73.5, 69.2, 62.2, 31.9, 30.4, 29.8, 29.75, 29.7, 29.65, 29.6,
29.5, 29.4, 29.35, 26.1, 22.7, 16.4, 14.1 ppm. 31P{1H} {13C} NMR
(CDCl3, 162 MHz): δ = 27.4 ppm. C63H101O6P (985.47): calcd. C
76.79, H 10.33; found C 76.69, H 10.38.
1
less oil. H NMR (CDCl3, 300 MHz): δ = 10.23 (s, 1 H), 10.14 (s,
1 H), 8.36 (br. s, 1 H), 7.98 (m, 2 H), 5.27 (s, 2 H), 1.19 (m, 21 H)
ppm. 13C NMR (CDCl3, 75 MHz): δ = 192.7, 191.8, 145.5, 139.4,
136.2, 133.5, 128.4, 128.2, 127.3, 62.9, 18.04, 12.2 ppm.
Compound 16: A 2  LiAlH4 solution in THF (10 mL) was added
to a stirred solution of 15 (1.00 g, 3.40 mmol) in dry THF (50 mL)
at 0 °C under argon. After 2 h, MeOH was added, then water. The
resulting mixture was filtered through celite and evaporated to yield
1
16 (0.92 g, 91%). Colourless solid. H NMR (CD3OD, 300 MHz):
δ = 7.70 (s, 2 H), 4.63 (s, 4 H) ppm. C8H8Br2O2 (295.96): calcd. C
32.47, H 2.72; found C 32.56, H 2.71.
Compound 10: tBuOK (73 mg, 0.65 mmol) was added to a stirred
solution of 8 (600 mg, 0.56 mmol) and 9 (100 mg, 0.26 mmol) in
THF (10 mL) at 0 °C. After 1 h, the mixture was allowed to slowly
warm to room temperature (within 1 h), then stirred for 2 h, filtered
and the solvents evaporated. Column chromatography (SiO2, hex-
ane/CH2Cl2, 3:1) followed by gel permeation chromatography (Bi-
orad, Biobeads SX1, CH2Cl2) yielded 10 (350 mg, 65%). Orange
glassy product. 1H NMR (CDCl3, 300 MHz): δ = 7.53 (s, 8 H),
7.50 (s, 8 H), 7.46 (d, J = 16 Hz, 2 H), 7.18 (d, J = 16 Hz, 2 H),
7.14 (AB, J = 16 Hz, 4 H), 7.05 (AB, J = 16 Hz, 4 H), 6.73 (s, 4
H), 4.03 (m, 12 H), 3.98 (t, J = 6.5 Hz, 4 H), 1.83 (m, 16 H), 1.27
(m, 128 H), 0.89 (t, J = 6 Hz, 24 H) ppm. 13C NMR (CDCl3,
75 MHz): δ = 153.3, 151.2, 138.4, 137.4, 136.8, 136.6, 136.5, 132.5,
128.8, 128.4, 128.2, 128.0, 127.3, 127.0, 126.9, 126.8, 126.7, 123.4,
110.6, 105.3, 73.5, 69.6, 69.2, 31.9, 31.8, 30.3, 29.8, 29.75, 29.7,
29.6, 29.5, 29.45, 29.4, 29.35, 29.3, 26.3, 26.1, 22.7, 14.1 ppm.
C142H218O8 (2053.29): calcd. C 83.06, H 10.66; found C 83.28, H
10.52.
Compound 17: A mixture of TIPSCl (2.4 mL, 11.40 mmol), imid-
azole (1.55 g, 22.80 mmol) and 16 (1.40 g, 4.73 mmol) in DMF
(20 mL) was stirred at room temperature for 12 h and the solvents
evaporated. The residue was taken up with Et2O, washed with
brine, dried (MgSO4), filtered and the solvents evaporated. Column
chromatography (SiO2, hexane) yielded 17 (2.50 g, 87%). Colour-
1
less oil. H NMR (CDCl3, 300 MHz): δ = 7.73 (s, 2 H), 4.77 (s, 4
H), 1.12 (s, 36 H), 1.09 (s, 6 H) ppm. 13C NMR (CDCl3, 75 MHz):
δ = 140.4, 130.7, 119.6, 64.3, 18.0, 12.0 ppm. C26H48Br2O2Si2
(608.64): calcd. C 51.31, H 7.95; found C 51.47, H 8.08.
Compound 18: A 1.7  tBuLi solution in THF (12 mL, 20.4 mmol)
was added dropwise within 0.5 h to a solution of 17 (3.0 g,
4.90 mmol) in dry THF (80 mL) at –78 °C under Ar. The resulting
mixture was stirred at –78 °C for 2 h, then warmed slowly to 0 °C
(1 h) and cooled to –78 °C. DMF (2.2 mL, 28.38 mmol) was added
and after 1 h at –78 °C, the mixture was warmed slowly to 0 °C. A
2  aqueous HCl solution was then added. The THF was evapo-
rated and Et2O added. The organic layer was washed with a 2 
aqueous HCl solution, then with water, dried (MgSO4) and the
solvents evaporated. Column chromatography (SiO2, hexane/
Compound 12: A 1  LiAlH4 solution in THF (33 mL) was added
to a stirred solution of 11 (8.04 g, 27.0 mmol) in dry THF (400 mL)
at 0 °C under argon. After 2 h, MeOH was added, then water.
The resulting mixture was filtered through celite and the solvents
evaporated. Column chromatography (SiO2, CH2Cl2/hexane, 1:1)
yielded 12 (6.50 g, 91%). Colourless solid. 1H NMR (CDCl3,
300 MHz): δ = 7.66 (d, J = 2 Hz, 1 H), 7.40 (d, J = 8 Hz, 1 H),
7.29 (dd, J = 8 and 2 Hz, 1 H), 4.72 (d, J = 6 Hz, 2 H), 2.00 (t, J
= 6 Hz, 1 H) ppm. C7H6Br2O (265.93): calcd. C 31.62, H 2.27;
found C 31.70, H 2.28.
1
CH2Cl2, 7:3) yielded 18 (2.10 g, 84%). Colourless solid. H NMR
(CDCl3, 300 MHz): δ = 10.26 (s, 2 H), 8.35 (s, 2 H), 5.28 (s, 4 H),
1.13 (s, 36 H), 1.11 (s, 6 H) ppm. 13C NMR (CDCl3, 75 MHz):
δ = 193.3, 143.0, 135.2, 131.9, 62.7, 18.0, 12.0 ppm. C28H50O4Si2
(506.87): calcd. C 66.35, H 9.94; found C 66.41, H 10.09.
Compound 19: tBuOK (170 mg, 1.55 mmol) was added to a stirred
solution of 8 (1.40 g, 1.37 mmol) and 14 (200 mg, 0.62 mmol) in
THF (10 mL) at 0 °C. After 1 h, the mixture was allowed to slowly
warm to room temperature (within 1 h), then stirred for 2 h, filtered
and the solvents evaporated. Column chromatography (SiO2, hex-
Compound 13: A mixture of TIPSCl (5 mL, 22.56 mmol), imidazole
(3.10 g, 45.12 mmol) and 12 (5.00 g, 18.80 mmol) in DMF (50 mL)
was stirred at room temperature for 12 h and the solvents evapo-
3632
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2008, 3627–3634

Oligophenylenevinylene Heptamers with Fullerene Moieties
ane/CH2Cl2, 1:1) followed by gel permeation chromatography (Bi-
THF (20 mL) at 0 °C. After 1 h, the mixture was allowed to slowly
warm to room temperature (within 1 h), then stirred for 2 h, filtered
and the solvents evaporated. Column chromatography (SiO2, hex-
ane/CH2Cl2, 1:1) followed by gel permeation chromatography (Bio-
rad, Biobeads SX1, CH2Cl2) yielded 22 (800 mg, 46%). Orange
glassy product. 1H NMR (CDCl3, 300 MHz): δ = 7.82 (s, 2 H),
7.52 (s, 8 H), 7.51 (s, 8 H), 7.40 (d, J = 16 Hz, 2 H), 7.13 (s, 4 H),
7.08 (d, J = 16 Hz, 2 H), 7.05 (d, J = 16 Hz, 2 H), 6.96 (d, J =
16 Hz, 2 H), 6.72 (s, 4 H), 5.00 (s, 4 H), 4.04 (t, J = 6 Hz, 8 H),
3.98 (t, J = 6 Hz, 4 H), 1.80 (m, 12 H), 1.32 (m, 108 H), 1.15 (m,
42 H), 0.89 (t, J = 6 Hz, 18 H) ppm. 13C NMR (CDCl3, 75 MHz):
δ = 153.3, 138.4, 137.4, 136.5, 132.5, 128.8, 128.1, 127.3, 126.9,
126.7, 124.2, 105.3, 73.6, 69.2, 63.5, 31.9, 30.4, 29.7, 29.5, 29.4,
26.2, 22.7, 18.2, 17.7, 14.1, 12.2 ppm. C146H230O8Si2·0.5CH2Cl2
(2212.06): calcd. C 79.55, H 10.53; found C 79.55, H 10.40.
orad, Biobeads SX1, CH2Cl2) yielded 19 (480 mg, 40%). Orange
1
glassy product. H NMR (CDCl3, 300 MHz): δ = 7.70 (br. s, 1 H),
7.65 (d, J = 8 Hz, 1 H), 7.52 (br. s, 8 H), 7.51 (br. s, 8 H), 7.43 (s,
1 H), 7.40 (d, J = 16 Hz, 2 H), 7.15–7.07 (m, 6 H), 7.05 (d, J =
16 Hz, 2 H), 6.97 (d, J = 16 Hz, 2 H), 6.72 (s, 4 H), 4.99 (s, 2 H),
4.03 (t, J = 6 Hz, 8 H), 3.98 (t, J = 6 Hz, 4 H), 1.81 (m, 12 H),
1.27 (m, 108 H), 1.14 (m, 21 H), 0.89 (t, J = 6 Hz, 18 H) ppm. 13C
NMR (CDCl3, 75 MHz): δ = 153.3, 138.9, 138.4, 137.0, 136.9,
136.8, 136.7, 136.6, 136.5, 134.6, 132.5, 129.7, 128.8, 128.6, 128.5,
128.2, 128.2, 128.15, 128.1, 128.0, 127.2, 126.9, 126.8, 126.7, 125.6,
125.4, 125.3, 125.0, 105.2, 73.5, 69.2, 63.6, 63.5, 31.9, 30.4, 29.8,
29.75, 29.7, 29.6, 29.45, 29.4, 29.3, 26.1, 22.7, 18.1 ppm.
C
136H208O7Si (1983.23): calcd. C 82.37, H 10.57; found C 82.45, H
10.61.
Compound 20: A 1  TBAF solution in THF (0.5 mL) was added
to a stirred solution of 19 (300 mg, 0.15 mmol) in dry THF (6 mL)
at 0 °C under argon. After 2 h, H2O (10 mL) was added. The THF
was evaporated and CH2Cl2 added. The organic layer was washed
with water, dried (MgSO4) and the solvents evaporated. Column
chromatography (SiO2, CH2Cl2/hexane, 1:1) followed by gel perme-
ation chromatography (Biorad, Biobeads SX1, CH2Cl2) yielded 20
(250 mg, 93%). Orange glassy product. 1H NMR (CDCl3,
Compound 23: A 1  TBAF solution in THF (1.1 mL) was added
to a stirred solution of 22 (740 mg, 0.34 mmol) in dry THF (15 mL)
at 0 °C under argon. After 2 h, H2O (10 mL) was added. The THF
was evaporated and CH2Cl2 added. The organic layer was washed
with water, dried (MgSO4) and the solvents evaporated. Column
chromatography (SiO2, CH2Cl2/hexane, 1:1) followed by gel perme-
ation chromatography (Biorad, Biobeads SX1, CH2Cl2) yielded 23
(303 mg, 47%). Orange glassy product. 1H NMR (CDCl3,
300 MHz): δ = 7.70 (s, 1 H), 7.65 (d, J = 8 Hz, 1 H), 7.52 (br. s, 8 300 MHz): δ = 7.73 (s, 2 H), 7.53 (br. s, 8 H), 7.50 (br. s, 8 H), 7.40
H), 7.51 (br. s, 8 H), 7.43 (s, 1 H), 7.40 (d, J = 16 Hz, 2 H), 7.15–
7.07 (m, 6 H), 7.05 (d, J = 16 Hz, 2 H), 6.97 (d, J = 16 Hz, 2 H),
6.73 (br. s, 4 H), 4.89 (s, 2 H), 4.03 (t, J = 6 Hz, 8 H), 3.98 (t, J =
(d, J = 16 Hz, 2 H), 7.13 (s, 4 H), 7.12 (d, J = 16 Hz, 2 H), 7.04
(d, J = 16 Hz, 2 H), 6.97 (d, J = 16 Hz, 2 H), 6.72 (s, 4 H), 4.91
(s, 4 H), 4.03 (t, J = 6 Hz, 8 H), 3.98 (t, J = 6 Hz, 4 H), 1.83 (m,
6 Hz, 4 H), 1.81 (m, 12 H), 1.27 (m, 108 H), 0.89 (t, J = 6 Hz, 18 12 H), 1.32 (m, 108 H), 0.88 (t, J = 6 Hz, 18 H) ppm. 13C NMR
H) ppm. 13C NMR (CDCl3, 75 MHz): δ = 153.3, 138.4, 138.1,
137.0, 136.9, 136.7, 136.6, 136.5, 135.4, 132.5, 130.4, 128.9, 128.4,
128.3, 128.3, 128.2, 128.0, 127.95, 127.9, 127.2, 127.1, 127.0, 126.9,
126.8, 126.7, 126.5, 126.3, 126.1, 124.6, 116.1, 105.3, 73.6, 69.2,
63.7, 31.9, 30.3, 29.8, 29.75, 29.7, 29.6, 29.45, 29.4, 29.3, 26.1, 22.7,
14.13 ppm. C127H188O7 (1826.89): calcd. C 83.50, H 10.37; found
C 82.95, H 10.37.
(CDCl3, 75 MHz): δ = 153.7, 138.9, 137.3, 136.8, 131.0, 129.3,
128.8, 128.4, 127.7, 127.5, 127.2, 127.1, 126.4, 124.8, 105.7, 73.9,
69.6, 63.9, 32.3, 30.7, 30.15, 30.1, 30.0, 29.9, 29.85, 29.8, 29.7, 26.5,
23.1, 14.5 ppm. C128H190O8·0.5CH2Cl2 (1899.38): calcd. C 81.26,
H 10.14; found C 81.60, H 10.10.
Compound 24: DCC (26 mg, 0.13 mmol) and DMAP (3 mg,
0.02 mmol) were added to a solution of 23 (98 mg, 0.05 mmol) and
5 (156 mg, 0.12 mmol) in CH2Cl2 (10 mL) at 0 °C. After 1 h, the
mixture was allowed to slowly warm to room temperature. After
24 h the mixture was filtered and the solvents evaporated. Column
chromatography (SiO2, CH2Cl2/cyclohexane, 1:1) followed by gel
permeation chromatography (Biorad, Biobeads SX1, CH2Cl2) gave
Compound 21: DCC (54 mg, 0.26 mmol) and DMAP (5 mg,
0.04 mmol) were added to a solution of 20 (161 mg, 0.12 mmol)
and 5 (200 mg, 0.11 mmol) in CH2Cl2 (15 mL) at 0 °C. After 1 h,
the mixture was allowed to slowly warm to room temperature. Af-
ter 24 h the mixture was filtered and the solvents evaporated. Col-
umn chromatography (SiO2, CH2Cl2/cyclohexane, 1:1) followed by
gel permeation chromatography (Biorad, Biobeads SX1, CH2Cl2)
24 (160 mg, 71%). Dark brown glassy product. IR (neat): ν = 1747
˜
1
(C=O) cm–1. H NMR (CDCl3, 300 MHz): δ = 7.69 (s, 2 H), 7.48
gave 21 (250 mg, 73%). Dark brown glassy product. IR (neat): ν =
(m, 16 H), 7.32 (d, J = 16 Hz, 2 H), 7.15 (d, J = 16 Hz, 2 H), 7.08
(s, 4 H), 7.04 (d, J = 16 Hz, 2 H), 6.94 (d, J = 16 Hz, 2 H), 6.72
(s, 4 H), 6.57 (d, J = 1.5 Hz, 4 H), 6.38 (t, J = 1.5 Hz, 2 H), 5.44
(s, 4 H), 5.39 (s, 4 H), 5.02 (s, 4 H), 4.03 (t, J = 6 Hz, 8 H), 3.98
(t, J = 6 Hz, 4 H), 3.85 (t, J = 6 Hz, 8 H), 1.80 (m, 20 H), 1.32 (m,
180 H), 0.87 (m, 30 H) ppm. 13C NMR (CDCl3, 75 MHz): δ =
166.9, 163.4, 163.3, 160.9, 153.7, 145.6, 145.55, 145.5, 145.4,
˜
1747 (C=O) cm–1 1H NMR (CDCl3, 300 MHz): δ = 7.69 (d, J =
.
7 Hz, 1 H), 7.48 (m, 18 H), 7.32 (d, J = 16 Hz, 2 H), 7.15 (m, 6
H), 7.04 (d, J = 16 Hz, 2 H), 6.94 (d, J = 16 Hz, 2 H), 6.73 (br. s,
4 H), 6.57 (d, J = 2 Hz, 2 H), 6.38 (t, J = 2 Hz, 1 H), 5.47 (s, 2 H),
5.38 (s, 2 H), 5.04 (s, 2 H), 4.03 (t, J = 6 Hz, 8 H), 3.98 (t, J =
6 Hz, 4 H), 3.85 (t, J = 6 Hz, 4 H), 1.83 (m, 12 H), 1.70 (m, 4 H),
1.28 (m, 144 H), 0.88 (m, 24 H) ppm. 13C NMR (CDCl3, 75 MHz): 145.35, 145.3, 145.0, 144.9, 144.85, 144.2, 143.4, 143.3, 142.5,
δ = 166.4, 163.0, 160.4, 153.3, 145.2, 145.15, 145.1, 145.05, 144.95,
144.9, 144.6, 144.55, 144.5, 144.4, 143.8, 143.7, 143.0, 142.9, 142.8,
142.2, 142.1, 141.8, 141.7, 140.9, 140.8, 139.7, 138.4, 137.2, 136.9,
136.8, 136.6, 136.5, 136.45, 136.4, 136.35, 136.2, 132.5, 132.2,
131.1, 128.9, 128.8, 128.6, 128.4, 128.3, 128.0, 127.6, 127.3, 127.2,
127.1, 127.05, 127.0, 126.95, 126.9, 126.8, 126.7, 123.9, 107.3,
105.2, 101.6, 73.5, 71.1, 69.2, 68.1, 65.7, 62.7, 31.9, 30.3, 29.8, 29.7,
29.6, 29.5, 29.45, 29.4, 26.1, 22.7, 14.1 ppm. MALDI-TOF-MS:
141.25, 141.2, 127.8, 127.4, 127.3, 127.1, 107.7, 105.7, 102.0, 73.9,
71.6, 69.6, 69.5, 68.6, 63.1, 51.7, 32.4, 30.8, 30.15, 30.1, 29.9, 29.8,
29.7, 26.6, 23.1, 14.6, 14.5 ppm. MALDI-TOF-MS: 4501 (MH+,
calcd. for C320H303O22: 4500.91). C320H302O22 (4499.90): calcd. C
85.41, H 6.76; found C 85.68, H 6.73.
Electrochemistry: The cyclic voltammetric measurements were car-
ried out with a potentiostat Autolab PGSTAT100. Experiments
were performed at room temperature in a homemade airtight
three–electrode cell connected to a vacuum/argon line. The refer-
ence electrode consisted of a saturated calomel electrode (SCE) sep-
arated from the solution by a bridge compartment. The counter
electrode was a platinum wire of ca 1 cm2 apparent surface. The
3148.8 (M+, calcd. for C223H244O14
: 3148.38). C223H244O14
(3148.38): calcd. C 85.07, H 7.81; found C 84.61, H 7.58.
Compound 22: tBuOK (220 mg, 2.00 mmol) was added to a stirred
solution of 8 (1.72 g, 1.75 mmol) and 18 (410 mg, 0.8 mmol) in
Eur. J. Org. Chem. 2008, 3627–3634
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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3633

A. Gégout, M. Holler, T. M. Figueira-Duarte, J.-F. Nierengarten
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Acknowledgments
This research was supported by the Centre National de la Recher-
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de la Recherche (Solaire Photovoltaïque – Nanorgysol). A. G.
thanks the Agence de l’Environnement et de la Maîtrise de l’Ener-
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[15]
Received: March 25, 2008
Published Online: May 6, 2008
3634
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Eur. J. Org. Chem. 2008, 3627–3634