Novel soluble and thermally-stable fullerene dyad containing perylene

Article abstract of DOI:10.1039/b316996k

A novel fullerene dyad C₆₀-P1 in which a perylene moiety is attached to C₆₀ through a pyrrolidine ring has been prepared by 1,3-dipolar cycloaddition of the azomethine ylides generated in situ from the corresponding aldehyde and sarcosine. Electrochemical and photophyscial studies of the dyad in solution have revealed that there is no significant ground-state electronic interaction between the covalently bonded perylene moiety and the fullerene. The photophysical investigations have also shown that there exists an effective photoinduced energy transfer from the perylene moiety to C ₆₀. A photovoltaic device made with the dyad has confirmed that photoinduced electron transfer does take place within the dyad; however, the efficiency of the electron transfer is negligible relative to the energy transfer.

Full text of DOI:10.1039/b316996k

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A R T I C L E
Novel soluble and thermally-stable fullerene dyad containing
perylene{
a,b
Jianli Hua, Fanshun Meng, Fang Ding, Fuyou Li and He Tian*
a
a
c
a
a
Lab for Advanced Materials and Institute of Fine Chemicals, East China University of
Science & Technology, Shanghai 200237, P.R. China. E-mail: tianhe@ecust.edu.cn;
Fax: 186-21-64252288; Tel: 186-21-64252756
b
Department of Chemistry, Jiangxi Normal University, Nanchang 330027, P.R. China
Institute of Advanced Materials, Fudan University, Shanghai 200433, P.R. China
c
Received 5th January 2004, Accepted 31st March 2004
First published as an Advance Article on the web 10th May 2004
A novel fullerene dyad C60–P1 in which a perylene moiety is attached to C60 through a pyrrolidine ring has
been prepared by 1,3-dipolar cycloaddition of the azomethine ylides generated in situ from the corresponding
aldehyde and sarcosine. Electrochemical and photophyscial studies of the dyad in solution have revealed that
there is no significant ground-state electronic interaction between the covalently bonded perylene moiety and
the fullerene. The photophysical investigations have also shown that there exists an effective photoinduced
energy transfer from the perylene moiety to C60. A photovoltaic device made with the dyad has confirmed that
photoinduced electron transfer does take place within the dyad; however, the efficiency of the electron transfer
is negligible relative to the energy transfer.
2
6,27
has shifted to more soluble perylenes.
8
Wudl and co-
investigated the excited-state properties of
Introduction
2
workers
a
Since the discovery of a photoinduced electron transfer from a
conjugated oligomer and/or polymer to a fullerene, covalently
linked C60 dyads have attracted great attention due to their
perylene–fulleropyrrolidine dyad with steady-state and femto-
second time-resolved spectroscopy. It was shown that charge
separation and energy transfer occurred in nearly equal pro-
portions after photoexcitation and both processes took place
on a sub-picosecond timescale. Here, we have designed and
synthesized a novel soluble fullerene dyad containing a
perylene moiety (C –P1 in Scheme 1), in which a perylene
1
,2
potential application in photovoltaic devices.
However,
the disordered islands of polymer and fullerene formed in
the actual bulk heterojunction devices limited further improve-
3
ment of their efficiency. To overcome this drawback, fullerene-
6
0
4
–10
based double-cable polymers
dyads
and donor–acceptor
have been synthesized. As shown recently, the
devices made of polythiophene/fullerene blends reached power
moiety is attached to fullerene through a pyrrolidine ring, and
which has been prepared by 1,3-dipolar cycloaddition of the
azomethine ylides generated in situ from the aldehyde and
sarcosine. To our knowledge, few works had been reported on
good soluble fullerene compounds containing a perylene unit.
The structure of the functionalized fullerene dyad was charac-
1
b,11–18
1
9
conversion efficiency values (g) of up to 3.3%. Although such
high efficiency has been achieved, there is large scope for the
further improvement of the solubility for most fullerene
2
0
1
13
compounds.
terized using H-NMR, C-NMR, MS, IR, UV-Vis absorp-
tion, luminescence spectra, CV and TGA data. It was found
that the fullerene dyad containing a perylene moiety has good
solubility in most common organic solvents, high thermal
stability and broad visible-light absorption with high coeffi-
cients. The electrochemical and excited-state properties of the
dyad in solution are discussed using the related perylene
derivatives P1 (see Scheme 1) and fulleropyrrolidine FP (see
Scheme 2) as reference compounds. Finally, the C –P1 dyad
Another factor that limits the efficiency is the narrow
absorption spectra of the polymers. Many efforts have been
devoted to improving the light harvesting ability, but only a
few polymers can achieve near infrared (NIR) absorption.
Dyes based on 3,4,9,10-perylene tetracarboxylic diimides
2c,21
(
PTCAs) have drawn much attention
for being used as
sensitizers with their outstanding chemical, thermal and photo-
chemical stability. Perylene derivatives are highly absorbing in
6
0
5
21
M
21
cm ) and emit
the visible to NIR region (e # 10
was incorporated into a photovoltaic cell by spin-casting the
compounds onto an ITO glass substrate and depositing an
aluminium film on the top.
2
2
fluorescence with a quantum yield of near unity. On the other
hand, perylene derivatives can be also used as NIR absorber
or luminescent materials, and nowadays the highly photo-
luminescent and environmentally-stable NIR materials are
strongly needed. Besides their conventional uses, perylenes are
one kind of key chromophore for high-tech applications,
spanning from electronic to biological fields, such as optical
Experimental
Materials
2
3
24
25
switches, lasers and DNA/RNA probes, etc. Many
types of PTCAs have been synthesized, but the expected low
solubility of these molecules is a problem for synthesis,
purification and applications in the devices. Therefore, work
2
9
4-(5-Bromopentyloxy)benzaldehyde,
N,N’-di-(n-butyl)-1,6,-
7,12-tetra(4-tert-butylphenoxy)-3,4,9,10-perylenetetracarboxylic
diimide (1), 1,6,7,12-tetra(4-tert-butylphenoxy)-3,4,9,10-peryle-
netetracarboxylic dianhydride (2) and N-(n-butyl)-1,6,7,12-
tetra(4-tert-butylphenoxy)-3,4,9,10-perylenetetracarboxylic
monoimide (3) were prepared following a procedure described
{
Electronic supplementary information (ESI) available: synthesis of
1 13
starting materials and H-NMR, C-NMR, MS spectra and emission
lifetimes of the products. See http://www.rsc.org/suppdata/jm/b3/
b316996k/
2
1,22,26,27,30
in the literature. { 1-Methyl-2-pyrrolidinone (NMP)
was refluxed with calcium hydride and distilled before use. All
T h i s j o u r n a l i s ß T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4
J . M a t e r . C h e m . , 2 0 0 4 , 1 4 , 1 8 4 9 – 1 8 5 3
1 8 4 9

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3
Scheme 1 Synthetic route for fullerene–perylene dyad (C60–P1). Reagents and conditions: (i) KOH/isopropanol, HCl, 80%; (ii) n-butylamine, NH ,
3
5%; (iii) 4-(5-bromopentyloxy)benzaldehyde, NMP/K CO
2
3
, 110 uC, 24h, 70%; (iv) C60, sarcosine, chlorobenzene, reflux 24 h, 25.3%.
Synthesis of C60–P1
A mixture of C60 (0.26 g, 0.36 mmol), compound P1 (0.54 g,
.38 mmol), and sarcosine (0.13 g, 1.44 mmol) in dry
0
chlorobenzene was refluxed for 24 h under an argon atmo-
sphere. The resulting mixture was concentrated and separated
on a silica gel column using toluene/dichloromethane (8:1) to
2
1
give the product (0.18 g, 25.3 %). IR (KBr pellets, cm ): 3059,
961, 2780, 1697, 1660, 1586, 1503, 1261, 1017, 573, 525;
Scheme 2 Synthetic route for FP. Reagents and conditions: (i) C60
sarcosine, chlorobenzene, reflux, 24 h, 21.9%.
,
2
1
H-NMR (500 MHz, CDCl ): d 8.21 (s, 4 H), 7.65 (br, 2 H),
3
7.22 (d, J ~ 12.25 Hz, 8 H), 6.89 (d, J ~ 8.14 Hz, 2 H), 6.83 (d,
J ~ 11.75 Hz, 8 H), 4.95 (d, J ~ 9.36 Hz, 1 H), 4.84 (s, 1 H),
other reagents and solvents were of analytical or chemical
grade, and were purified using standard methods.
4
3
1
.21 (d, J ~ 10.46 Hz, 1 H), 4.10 (m, 4 H), 3.95 (t, 2 H), 2.77 (s,
H), 1.92 (m, 2 H), 1.82 (m, 2 H), 1.66 (m, 2 H), 1.58 (m, 2 H),
Characterization
13
.41 (m, 2 H), 1.29 (s, 36 H), 0.94 (t, 3 H); C-NMR (125 MHz,
1
13
H-NMR and C-NMR spectra were obtained with a Bruker
AM-500 spectrometer. The mass spectra were determined on a
700 Proteomics analyzer spectrometer. FT-IR spectra were
recorded on a Nicolet Magna-IR550 spectrophotometer in the
3
CDCl ): d 164.09, 156.69, 156.61, 153.57, 147.92, 147.42,
147.11, 146.97, 146.66, 146.47, 146.34, 146.10, 145.87, 145.26,
145.14, 144.95, 143.65, 143.53, 143.22, 143.11, 143.06, 142.98,
142.22, 142.83, 142.69, 142.63, 142.55, 142.49, 142.36, 142.24,
142.08, 140.72, 140.49, 140.14, 137.34, 137.19, 136.36, 129.71,
127.33, 123.23, 123.08, 121.31, 121.15, 120.63, 120.58, 120.18,
120.05, 120.01, 83.85, 70.66, 69.59, 68.25, 53.49, 42.66, 41.08,
40.63, 35.04, 32.15, 31.04, 30.89, 30.38, 30.04, 29.49, 28.47,
27.71, 25.32, 24.18, 23.37, 23.22, 21.05, 14.80, 14.48; MALDI-
4
2
1
region of 4000–400 cm using KBr pellets. UV-Visible spectra
were determined with a Varian Cary 500 spectrometer.
Fluorescent spectra were recorded on Varian Cary Eclipse
spectrometer. Thermogravimetric analysis (TGA) was con-
ducted using a Mettler Toledo Thermal Analyzer SDTA 851 at
2
1
1
a heating rate of 10 uC min under a nitrogen atmosphere.
TOF m/z : 1976.71 [M 1 1] . Anal. calc. for C H N O
9
1
42 85
3
(
4
M ~ 1975.71): C, 86.25; H, 4.34; N, 2.13. Found: C, 86.31; H,
.37; N, 2.15%.
Synthesis of compound P1
A mixture of N-(n-butyl)-1,6,7,12-tetra-(4-tert-butylphenoxy)-
3
4
,4,9,10-perylenetetracarboxylic monoimide (0.74 g, 0.61 mmol),
-(5-bromopentyloxy)benzaldehyde (0.33 g, 1.23 mmol), potas-
Synthesis of FP
A mixture of 4-(5-bromopentyloxy)benzaldehyde (0.162 g,
sium carbonate (1.4 g, 10 mmol), and NMP (20 mL) was stirred
at 110 uC under argon for 24 h. The reaction mixture was
cooled, then poured into water (350 mL), extracted with ethyl
acetate, washed with water, dried over anhydrous magnesium
sulfate, and chromatographed on silica gel with a mixture of
CH Cl /CCl (2:1) to give the product (0.6 g, 70%) as a red
0
1
.6 mmol), C60 (0.288 g, 0.4 mmol), and sarcosine (0.143 g,
.6 mmol) in dry chlorobenzene (120 mL) was refluxed under
argon for 24 h. After cooling, the resulting solution was
evaporated to dryness and column chromatography (SiO
petroleum ether/toluene 2:3) gave FP (0.09 g, 21.9%) as a
2
,
2
2
4
1
1
brown solid. H-NMR (500 MHz, CDCl
6
3
): d 7.72 (br, 2 H),
powder. H-NMR (500 MHz, CDCl
3
): d 9.85 (s, 1 H), 8.23 (s,
H), 7.79 (d, J ~ 8.67 Hz, 2 H), 7.24 (d, J ~ 8.23 Hz, 8 H),
.94 (d, J ~ 8.62 Hz, 2 H), 4.97 (d, J ~ 9.94 Hz, 1 H), 4.88 (s,
4
6
4
1
.94 (d, J ~ 8.77 Hz, 2 H), 6.84 (d, J ~ 8.39 Hz, 8 H), 4.14 (m,
H), 4.01 (t, 2 H), 1.85 (m, 2 H), 1.80 (m, 2 H), 1.67 (m, 2 H),
.56 (m, 2 H), 1.39 (m, 2 H), 1.29 (s, 36 H), 0.93 (t, 3 H). Anal.
1 H), 4.24 (d, J ~ 9.53 Hz, 1 H), 3.96 (t, J ~ 6.43 Hz, 2 H),
3.43 (t, J ~ 6.74 Hz, 2 H), 2.79 (s, 3 H), 1.93 (m, 2 H), 1.81 (m,
2 H), 1.62 (m, 2 H). Anal. calc. for C74H20BrNO (M ~
calc. for C H N O (M ~ 1229.51): C, 78.15; H, 6.56; N,
8
1018.88): C, 87.23; H, 1.98; N, 1.37. Found: C, 87.32; H, 2.04;
N, 1.39%.
0
80
2
10
2
.28. Found: C, 78.21; H, 6.48; N, 2.23%.
1
8 5 0
J . M a t e r . C h e m . , 2 0 0 4 , 1 4 , 1 8 4 9 – 1 8 5 3

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Results and discussion
The synthetic route of functionalized fullerene C60–P1 is shown
in Scheme 1. The synthetic approach to prepare those com-
pounds relies upon the 1,3-dipolar cycloaddition of azomethine
3
1
ylides to C60. This method has been proven to be very efficient
for the functionalization of C60 due to its versatility and the
3
1
ready availability of the starting materials. The 1,3-dipolar
cycloaddition of the azomethine ylides generated in situ from
P1 and sarcosine in refluxing chlorobenzene with C60 leads to
the fulleropyrrolidine C –P1 in 25.3% yield. Owing to the
6
0
presence of the branched tert-butyl phenyl substitute on the
bay of the perylene moiety, compound C60–P1 is highly soluble
in common solvents such as toluene, CH Cl , CHCl , THF, or
2 2 3
NMP, and its complete spectroscopic characterization was
easily achieved. The IR spectrum of C60–P1 shows a charac-
2
teristic absorption band of C60 at around 525 cm , and the
1
2 2
Fig. 2 Cyclic voltammogram of C60–P1, P1, and FP in CH Cl
1
21
containing tetrabutylammonium perchlorate at the scan of 100 mV s
.
H-NMR spectrum of C –P1 in CDCl solution also shows
6
0
3
all the expected signals, such as those corresponding to the
pyrrolidine ring at d ~ 4.95, 4.84, and 4.21 ppm. Interestingly,
the signals (d ~ 7.65 ppm) corresponding to some of the
protons of the phenyl group directly attached to the pyrrolidine
ring are broad (for details, see ESI{), which indicates restricted
with one-electron in the cathodic region (Table 1 and Fig. 2).
The first and second reduction potentials of C60–P1 are very
close to those of P1, which indicates that both reduction peaks
of fullerene in C60–P1 are hidden. The third reversible
reduction wave is C60-based. The observed C60-based reduction
potential (E1/2) of C60–P1 is shifted to a more negative value
compared with the model compound FP. This is typical for
most C60 adducts which show small shifts due to the partial loss
3
2
rotation of the phenyl substitute on the pyrrolidine ring. This
result is in good accordance with the data previously reported
9
by Eckert et al. The structure of C –P1 is also characterized
by MALDI-TOF mass spectroscopy with a molecular isotopic
6
0
1
peak at m/z ~ 1976.71 ([M 1 1] , calculated for C142
33
H
85
N
3
O
975.71). The fragment showing the peak at 1256.71, corres-
9
:
of conjugation upon derivation. In the anodic region, C60–P1
1
presents one, reversible oxidation peak characterized with one-
electron corresponding to the P1 model compound. The
electrochemical data indicate that there is no distinct ground-
state electronic interaction between the electron-donating
perylene and the electron-accepting fullerene.
The ground-state electronic absorption spectra of the com-
2 2
pounds C60–P1, P1, and FP in CH Cl are shown in Fig. 3.
C60–P1 matches the profile obtained by summation of the
1
ponding to [M 2 C60
85 3 9
] (calculated for C82H N O : 1255.71),
is also consistent with the structure of C60–P1. Thermal pro-
perties of compounds P1 and C –P1 are investigated by
means of thermogravimetric analysis (TGA) at a heating rate
6
0
2
1
of 10 uC min under a nitrogen atmosphere, which shows that
60–P1 has better thermal stability than P1 with its decom-
C
position temperature up to 432 uC as shown in Fig. 1.
The model fulleropyrrolidine FP was obtained in 21.9% yield
by treatment of C60 with 4-(5-bromopentyloxy)benzaldehyde
and sarcosine in refluxing chlorobenzene (Scheme 2). The
spectra of component units FP and P1 (Fig. 3) within experi-
mental error. This result is in agreement with previous studies
3
4
on donor–acceptor dyads in solution and suggests that there
is no significant ground-state interaction between the perylene
moiety and the fullerene. Interestingly, the absorption spec-
1
H-NMR spectra of FP shows all the expected signals, and
restricted rotation of the phenyl substitute on the pyrrolidine
ring is also observed for compound FP.{
2 2
trum of FP in CH Cl displays two very intense bands in the
The electrochemistry of the compounds C60–P1, and FP
were studied by cyclic voltammetry (CV). All the experiments
were performed in dichloromethane solution using tetrabutyl-
ammonium perchlorate as the supporting electrolyte, glassy
carbon as the working electrode, Pt as the counter electrode
and Ag/AgCl as the reference electrode. The scan rate was
UV and much weaker features in the visible spectral region
(Table 2). In particular, two band maxima attributed to the
lowest (lmax: 702 nm) and lowest allowed (lmax: 430 nm) singlet
transitions are observed. The absorption spectrum of FP is very
similar to that of the simple N-methylfulleropyrrolidine
reported by Prato and Maggini, thus showing modest
perturbations induced by the phenylene fragment bound to
the pyrrolidine ring.
3
1
2
1
100 mV s . The voltammetric results are presented in Fig. 2
and the data are collected in Table 1.
C –P1 shows three reversible reduction peaks characterized
60
The absorption and fluorescence data of C –P1, P1, and FP
60
are listed in Table 2. In the UV-Vis spectra, C60–P1 and P1
show three typical perylene absorption peaks at 451, 537, and
5
78 nm with high coefficients. P1 in CH
displays a fluorescence maximum at 610 nm. Also, dyad C –
2 2
Cl excited at 560 nm
6
0
P1 has emission spectra with characteristic features of the
a
Table 1 Electrochemical data for C60–P1, P1, and FP
E
1/2
(1st red.)
E
1/2
(2nd red.)
E
1/2
(3rd red.)
Compound
60–P1
P1
FP
a
E
1/2 (ox.)
C
11.32
11.34
20.67
20.70
20.62
20.83
20.84
21.00
21.01
CV measurements in dichloromethane solution using tetrabutylam-
monium perchlorate as supporting electrolyte, glassy carbon as
working electrode, Pt as counter electrode and Ag/AgCl as reference
2
1
electrode. The scan rate is 100 mV s
(
and half-wave potentials
E
1/2) are expressed in volts relative to SCE.
Fig. 1 TGA spectrum of C60–P1 and P1.
J . M a t e r . C h e m . , 2 0 0 4 , 1 4 , 1 8 4 9 – 1 8 5 3
1 8 5 1

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Fig. 4 Current–voltage characteristics of the ITO/C60–P1/Al device
under different white light intensities.
Fig. 3 (a) UV-Vis absorption spectra of
P1 (solid curve), and FP (dotted curve) in CH
C60–P1 (dashed curve),
25 21
Cl (1 6 10 mol L ).
2
2
In the inset, their absorption spectrum is multiplied by a factor of 40
above 650 nm. The corrected excitation spectrum of C60–P1 (dash dot
curve) is taken at lem ~ 710 nm (maximum of the fullerene moiety
fluorescence). (b) Fluorescence spectra of C60–P1 (dashed curve) and
P1 (solid curve) excited at 560 nm in CH Cl (1 6 10 mol L ).
2 2
Fluorescence intensity for FP (dotted curve) is multiplied by a factor
of 10.
Fig. 5 Photocurrent spectra of the ITO/C60–P1/Al device.
matches the absorption profile throughout the UV-Vis spectral
region of P1 [Fig. 3(a)]. These findings are consistent with
quantitative occurrence of singlet–singlet energy transfer from
the P1 unit to the fullerene in the dyad C –P1. The
2
6
21
6
0
fluorescence of the perylene moiety in the dyad is strongly
quenched by the intramolecular energy transfer (ca. 88.4%).
The photovoltaic device consists of a metal (Al) contact on
the surface of an organic film of the C60–P1 on a partially
coated ITO glass. The organic layer was prepared by spin
coating from chlorobenzene solution. The current–voltage
characteristics of the ITO/C60–P1/Al device under different
white light intensities are depicted in Fig. 4. Under an intensity
perylene unit; however, its luminescence was largely quenched
Fig. 3). The fluorescence lifetimes (t) of P1 and C60–P1 were
determined by a time-correlated single photon counting
spectrometer with excitation at 370 nm. The fluorescence
decay at lem ~ 610 nm is mono-exponential for P1 (t ~
(
1
5.4 ns). C60–P1 exhibits dual-exponential decay characteristics
~ 6.69 ns, 94% and t ~ 2.6 ns, 6%),{ and the relative
short-lived fluorescent component is attributed to the interac-
(t
1
2
3
6
22
tion between the perylene and the fullerene. It seems to be
common sense that the solvent effect of the fluorescence
quenching can be observed if intramolecular charge transfer
of 31 mW cm , the short-circuit current density and the open-
2
2
circuit voltage of the device are about 3.76 mA cm and 0.67 V,
respectively. The IPCE (incident photo-to-current conversion
efficiency) of the ITO/C60–P1/Al device is equal to 0.01%. The
performance of the ITO/C60–P1/Al device is not as good as that
3
7
occurs in a system. In this system, solvent polarity neither led
to the shifts of the fluorescence emission band nor influenced
the excited-state lifetime, although the emission intensity of
1
3
observed for some fullerene–azothiophene-based solar cells.
C60–P1 increased a little with increasing solvent polarity. This
evidence disallows the possibility of the intramolecular charge
It is well known that the photocurrent is the result of
photoinduced electron transfer from the donor to the acceptor.
As shown in Fig. 5, the photocurrent spectrum of the ITO/C60–
transfer process in C –P1 at room temperature. FP exhibits a
0
6
fluorescence band with lmax ~ 710 nm, and a emission
quantum yield of 0.0022 and an excited-state lifetime of 1.2 ns.
The excitation spectrum of C60–P1 taken at lem ~ 710 nm
P1/Al device matches the absorption spectrum of the dyad.
This indicates that the characteristic electron transportation of
the perylene moiety in the dyad dominates the performance of
a
2 2
Table 2 Absorption and fluorescence data for C60–P1, P1, and FP in CH Cl
abs.
lmax /nm (log e)
fl.
max /nm
b
Compound
l
W
em
C
60–P1
702 (0.3)
579 (4.76)
578 (4.73)
430 (0.72)
541 (4.56)
537 (4.52)
302 (4.62)
451 (4.41)
451 (4.32)
610
610
710
0.115
1
0.0022
P1
FP
a
702 (0.3)
For C60–P1 and P1 the fluorescence spectra and quantum yields were obtained upon excitation at their absorption maxima (lex: 560 nm); for
b
FP the fluorescence spectra and quantum yield values are independent of the excitation wavelength. Fluorescence quantum yields Wem were
measured with the method using perylene as a standard.
35
1
8 5 2
J . M a t e r . C h e m . , 2 0 0 4 , 1 4 , 1 8 4 9 – 1 8 5 3

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the device. We believe that the low efficiency of the device could
result from the fact that hole transportation in the device is
poor since the perylene moiety and the fullerene unit are both
electron transporting domain species. Secondly, it is possible
that the introduction of the pentyl group between the fullerene
and the perylene may reduce charge transfer. On the other
hand, the lower IPCE value is due to the fact that the device has
not been optimized for layer thickness and device architectures.
E. Menna, G. Scorrano, M. Svensson, M. R. Andersson and
N. S. Sariciftc, Synth. Met., 2001, 121, 1555.
7
8
9
F. Zhang, M. Svensson, M. R. Andersson, M. Maggini, S. Bucella,
E. Menna and O. Ingan a¨ s, Adv. Mater., 2001, 13, 1871.
A. M. Ramos, M. T. Rispens, J. K. J. van Duren, J. C. Hummelen
and R. A. J. Janssen, J. Am. Chem. Soc., 2001, 123, 6714.
J.-F. Eckert, J.-F. Nicoud, J.-F. Nierengarten, S.-G. Liu,
L. Echegoyen, F. Barigelletti, N. Armaroli, L. Ouali,
V. Krasnikov and G. Hadziioannou, J. Am. Chem. Soc., 2000,
122, 7467.
E. Peeters, P. A. van Hal, J. Knol, C. J. Brabec, N. S. Sariciftci,
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1
0
Summary
1
0 174.
N. Martin, L. Sanchez, B. Illescas and I. Perez, Chem. Rev., 1998,
8, 2527.
1
1
2
In summary, a novel soluble and high thermally-stable
fullerene dyad containing perylene as electronic donor has
been synthesized. The electrochemical and photophysical
studies in solution have revealed that there is no significant
ground-state electronic interaction between the covalently
bonded perylene and the fullerene sphere in C60–P1. The
photophysical study in dichloromethane solution has also
shown that singlet–singlet energy transfer from the perylene
9
1
D. Hirayama, K. Takimiya, Y. Aso, T. Otsubo, T. Hasobe,
H. Yamada, H. Imahori, S. Fukuzumi and Y. Sakata, J. Am.
Chem. Soc., 2002, 124, 532.
13 M. Maggini, G. Possamai, E. Menna, G. Scorrano, N. Camaioni,
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1
4
N. Armaroli, G. Accorsi, J.-P. Gisselbrecht, M. Gross,
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unit to the fullerene in the dyad C –P1 takes place whereas
6
0
electron transfer is a minor process. A photocurrent observed
for ITO/C –P1/Al photovoltaic devices has shown that
15 H. Yamada, H. Imahori, Y. Nishimura, I. Yamazaki, T. K. Ahn,
S. K. Kim, D. Kim and S. Fukuzumi, J. Am. Chem. Soc., 2003,
6
0
photoinduced electron transfer from the perylene moiety to
C60 does occur, but the efficiencies of the photovoltaic devices
are low, namely 0.01%. We believe that the main part of the
light energy absorbed by the perylene fragment is promptly
conveyed to the fullerene lowest singlet excited-state, and only
a small part of absorbed light is able to contribute effectively
to the photocurrent. The use of new donor-linked fullerenes
that absorb in the visible range will be important for a broad
absorption of the sunlight and as models for the study of
charge mobility and transportation.
1
25, 9129.
1
6
G. Possamai, N. Camaioni, G. Ridolfi, L. Franco, M. Ruzzi,
E. Menna, G. Casalbore-Miceli, A. M. Fichera, G. Scorrano,
C. Corvaja and M. Maggini, Synth. Met., 2003, 139, 585.
17 M. A. Loi, P. Denk, H. Hoppe, H. Neugebauer, D. Meissner,
C. Winder, C. J. Brabec, N. S. Sariciftci, A. Gouloumis, P. Vazquez
and T. Torres, Synth. Met., 2003, 137, 1491.
18
19
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A. Dhanabalan, J. K. J. van Duren, J. L. J. van Dongen and
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R. C. Haddon, A. S. Perel, R. C. Morris, T. T. M. Palstra,
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Acknowledgements
21 H. Quante, P. Schlichting, U. Rohr, Y. Geerts and K. M u¨ llen,
Macromol. Chem. Phys., 1996, 197, 4029.
This work was supported by National Science Foundation of
China and Education Committee of Shanghai. The photo-
voltaic devices were made in the lab in the Swiss Federal
Institute of Technology in Lausanne/Switzerland and Dr
F. N u¨ esch and Professor L. Zuppiroli would be appreciated
for their assistance. J. L. H. thanks the grant support from
Postdoctoral Science Foundation of China and Science
Committee of Shanghai (No.03dz12034).
22 H. Langhals and W. Jona, Angew. Chem., Int. Ed., 1998, 37, 952.
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