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ARTICLE

Lab for Advanced Materials and Institute of Fine Chemicals, East China University of
Science & Technology, Shanghai 200237, P.R. China. E-mail: [email protected];
Fax: 186-21-64252288; Tel: 186-21-64252756
b
Department of Chemistry, Jiangxi Normal University, Nanchang 330027, P.R. China
c
Institute of Advanced Materials, Fudan University, Shanghai 200433, P.R. China

Journal of

Materials
Chemistry

Jianli Hua,a,b Fanshun Meng,a Fang Ding,a Fuyou Lic and He Tian*a

www.rsc.org/materials

Novel soluble and thermally-stable fullerene dyad containing

perylene{

Received 5th January 2004, Accepted 31st March 2004

First published as an Advance Article on the web 10th May 2004

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A novel fullerene dyad C60P1 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.

DOI: 10.1039/b316996k

Introduction
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
potential application in photovoltaic devices.1,2 However,
the disordered islands of polymer and fullerene formed in
the actual bulk heterojunction devices limited further improvement of their efficiency.3 To overcome this drawback, fullerenebased double-cable polymers410 and donoracceptor
dyads1b,1118 have been synthesized. As shown recently, the
devices made of polythiophene/fullerene blends reached power
conversion efficiency values (g) of up to 3.3%.19 Although such
high efficiency has been achieved, there is large scope for the
further improvement of the solubility for most fullerene
compounds.20
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
(PTCAs) have drawn much attention2c,21 for being used as
sensitizers with their outstanding chemical, thermal and photochemical stability. Perylene derivatives are highly absorbing in
the visible to NIR region (e # 105 M21 cm21) and emit
fluorescence with a quantum yield of near unity.22 On the other
hand, perylene derivatives can be also used as NIR absorber
or luminescent materials, and nowadays the highly photoluminescent 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
switches,23 lasers24 and DNA/RNA probes,25 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
{ Electronic supplementary information (ESI) available: synthesis of
starting materials and 1H-NMR, 13C-NMR, MS spectra and emission
lifetimes of the products. See http://www.rsc.org/suppdata/jm/b3/
b316996k/

has shifted to more soluble perylenes.26,27 Wudl and coworkers28 investigated the excited-state properties of a
perylenefulleropyrrolidine dyad with steady-state and femtosecond time-resolved spectroscopy. It was shown that charge
separation and energy transfer occurred in nearly equal proportions 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 (C60P1 in Scheme 1), in which a perylene
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 characterized using 1H-NMR, 13C-NMR, MS, IR, UV-Vis absorption, 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 coefficients. 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 C60P1 dyad
was incorporated into a photovoltaic cell by spin-casting the
compounds onto an ITO glass substrate and depositing an
aluminium film on the top.

Experimental
Materials
4-(5-Bromopentyloxy)benzaldehyde,29 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-perylenetetracarboxylic dianhydride (2) and N-(n-butyl)-1,6,7,12tetra(4-tert-butylphenoxy)-3,4,9,10-perylenetetracarboxylic
monoimide (3) were prepared following a procedure described
in the literature.21,22,26,27,30 { 1-Methyl-2-pyrrolidinone (NMP)
was refluxed with calcium hydride and distilled before use. All

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Scheme 1 Synthetic route for fullereneperylene dyad (C60P1). Reagents and conditions: (i) KOH/isopropanol, HCl, 80%; (ii) n-butylamine, NH3,
35%; (iii) 4-(5-bromopentyloxy)benzaldehyde, NMP/K2CO3, 110 uC, 24h, 70%; (iv) C60, sarcosine, chlorobenzene, reflux 24 h, 25.3%.

Synthesis of C60P1

Scheme 2 Synthetic route for FP. Reagents and conditions: (i) C60,
sarcosine, chlorobenzene, reflux, 24 h, 21.9%.

other reagents and solvents were of analytical or chemical

grade, and were purified using standard methods.
Characterization
1

H-NMR and 13C-NMR spectra were obtained with a Bruker

AM-500 spectrometer. The mass spectra were determined on a
4700 Proteomics analyzer spectrometer. FT-IR spectra were
recorded on a Nicolet Magna-IR550 spectrophotometer in the
region of 4000400 cm21 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 conducted using a Mettler Toledo Thermal Analyzer SDTA 851 at
a heating rate of 10 uC min21 under a nitrogen atmosphere.
Synthesis of compound P1
A mixture of N-(n-butyl)-1,6,7,12-tetra-(4-tert-butylphenoxy)3,4,9,10-perylenetetracarboxylic monoimide (0.74 g, 0.61 mmol),
4-(5-bromopentyloxy)benzaldehyde (0.33 g, 1.23 mmol), potassium 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
CH2Cl2/CCl4 (2:1) to give the product (0.6 g, 70%) as a red
powder. 1H-NMR (500 MHz, CDCl3 ): d 9.85 (s, 1 H), 8.23 (s,
4 H), 7.79 (d, J ~ 8.67 Hz, 2 H), 7.24 (d, J ~ 8.23 Hz, 8 H),
6.94 (d, J ~ 8.77 Hz, 2 H), 6.84 (d, J ~ 8.39 Hz, 8 H), 4.14 (m,
4 H), 4.01 (t, 2 H), 1.85 (m, 2 H), 1.80 (m, 2 H), 1.67 (m, 2 H),
1.56 (m, 2 H), 1.39 (m, 2 H), 1.29 (s, 36 H), 0.93 (t, 3 H). Anal.
calc. for C80H80N2O10 (M ~ 1229.51): C, 78.15; H, 6.56; N,
2.28. Found: C, 78.21; H, 6.48; N, 2.23%.

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J. Mater. Chem., 2004, 14, 18491853

A mixture of C60 (0.26 g, 0.36 mmol), compound P1 (0.54 g,

0.38 mmol), and sarcosine (0.13 g, 1.44 mmol) in dry
chlorobenzene was refluxed for 24 h under an argon atmosphere. The resulting mixture was concentrated and separated
on a silica gel column using toluene/dichloromethane (8:1) to
give the product (0.18 g, 25.3 %). IR (KBr pellets, cm21): 3059,
2961, 2780, 1697, 1660, 1586, 1503, 1261, 1017, 573, 525;
1
H-NMR (500 MHz, CDCl3): d 8.21 (s, 4 H), 7.65 (br, 2 H),
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),
4.21 (d, J ~ 10.46 Hz, 1 H), 4.10 (m, 4 H), 3.95 (t, 2 H), 2.77 (s,
3 H), 1.92 (m, 2 H), 1.82 (m, 2 H), 1.66 (m, 2 H), 1.58 (m, 2 H),
1.41 (m, 2 H), 1.29 (s, 36 H), 0.94 (t, 3 H); 13C-NMR (125 MHz,
CDCl3): 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; MALDITOF m/z : 1976.71 [M 1 1]1. Anal. calc. for C142H85N3O9
(M ~ 1975.71): C, 86.25; H, 4.34; N, 2.13. Found: C, 86.31; H,
4.37; N, 2.15%.

Synthesis of FP
A mixture of 4-(5-bromopentyloxy)benzaldehyde (0.162 g,
0.6 mmol), C60 (0.288 g, 0.4 mmol), and sarcosine (0.143 g,
1.6 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 (SiO2,
petroleum ether/toluene 2:3) gave FP (0.09 g, 21.9%) as a
brown solid. 1H-NMR (500 MHz, CDCl3): d 7.72 (br, 2 H),
6.94 (d, J ~ 8.62 Hz, 2 H), 4.97 (d, J ~ 9.94 Hz, 1 H), 4.88 (s,
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 ~
1018.88): C, 87.23; H, 1.98; N, 1.37. Found: C, 87.32; H, 2.04;
N, 1.39%.

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Results and discussion

The synthetic route of functionalized fullerene C60P1 is shown
in Scheme 1. The synthetic approach to prepare those compounds relies upon the 1,3-dipolar cycloaddition of azomethine
ylides to C60.31 This method has been proven to be very efficient
for the functionalization of C60 due to its versatility and the
ready availability of the starting materials.31 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 C60P1 in 25.3% yield. Owing to the
presence of the branched tert-butyl phenyl substitute on the
bay of the perylene moiety, compound C60P1 is highly soluble
in common solvents such as toluene, CH2Cl2, CHCl3, THF, or
NMP, and its complete spectroscopic characterization was
easily achieved. The IR spectrum of C60P1 shows a characteristic absorption band of C60 at around 525 cm21, and the
1
H-NMR spectrum of C60P1 in CDCl3 solution also shows
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
rotation of the phenyl substitute on the pyrrolidine ring.32 This
result is in good accordance with the data previously reported
by Eckert et al.9 The structure of C60P1 is also characterized
by MALDI-TOF mass spectroscopy with a molecular isotopic
peak at m/z ~ 1976.71 ([M 1 1]1, calculated for C142H85N3O9:
1975.71). The fragment showing the peak at 1256.71, corresponding to [M 2 C60]1 (calculated for C82H85N3O9: 1255.71),
is also consistent with the structure of C60P1. Thermal properties of compounds P1 and C60P1 are investigated by
means of thermogravimetric analysis (TGA) at a heating rate
of 10 uC min21 under a nitrogen atmosphere, which shows that
C60P1 has better thermal stability than P1 with its decomposition 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
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.{
The electrochemistry of the compounds C60P1, and FP
were studied by cyclic voltammetry (CV). All the experiments
were performed in dichloromethane solution using tetrabutylammonium 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
100 mV s21. The voltammetric results are presented in Fig. 2
and the data are collected in Table 1.
C60P1 shows three reversible reduction peaks characterized

Fig. 2 Cyclic voltammogram of C60P1, P1, and FP in CH2Cl2

containing tetrabutylammonium perchlorate at the scan of 100 mV s21.

with one-electron in the cathodic region (Table 1 and Fig. 2).

The first and second reduction potentials of C60P1 are very
close to those of P1, which indicates that both reduction peaks
of fullerene in C60P1 are hidden. The third reversible
reduction wave is C60-based. The observed C60-based reduction
potential (E1/2) of C60P1 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
of conjugation upon derivation.33 In the anodic region, C60P1
presents one, reversible oxidation peak characterized with oneelectron corresponding to the P1 model compound. The
electrochemical data indicate that there is no distinct groundstate electronic interaction between the electron-donating
perylene and the electron-accepting fullerene.
The ground-state electronic absorption spectra of the compounds C60P1, P1, and FP in CH2Cl2 are shown in Fig. 3.
C60P1 matches the profile obtained by summation of the
spectra of component units FP and P1 (Fig. 3) within experimental error. This result is in agreement with previous studies
on donoracceptor dyads in solution34 and suggests that there
is no significant ground-state interaction between the perylene
moiety and the fullerene. Interestingly, the absorption spectrum of FP in CH2Cl2 displays two very intense bands in the
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,31 thus showing modest
perturbations induced by the phenylene fragment bound to
the pyrrolidine ring.
The absorption and fluorescence data of C60P1, P1, and FP
are listed in Table 2. In the UV-Vis spectra, C60P1 and P1
show three typical perylene absorption peaks at 451, 537, and
578 nm with high coefficients. P1 in CH2Cl2 excited at 560 nm
displays a fluorescence maximum at 610 nm. Also, dyad C60
P1 has emission spectra with characteristic features of the
Table 1 Electrochemical dataa for C60P1, P1, and FP

Fig. 1 TGA spectrum of C60P1 and P1.

Compound

E1/2 (ox.)

C60P1
P1
FP

11.32
11.34

E1/2
(1st red.)

E1/2
(2nd red.)

E1/2
(3rd red.)

20.67
20.70
20.62

20.83
20.84
21.00

21.01

a
CV measurements in dichloromethane solution using tetrabutylammonium perchlorate as supporting electrolyte, glassy carbon as
working electrode, Pt as counter electrode and Ag/AgCl as reference
electrode. The scan rate is 100 mV s21 and half-wave potentials
(E1/2) are expressed in volts relative to SCE.

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Fig. 4 Currentvoltage characteristics of the ITO/C60P1/Al device

under different white light intensities.

Fig. 3 (a) UV-Vis absorption spectra of C60P1 (dashed curve),

P1 (solid curve), and FP (dotted curve) in CH2Cl2 (1 6 1025 mol L21).
In the inset, their absorption spectrum is multiplied by a factor of 40
above 650 nm. The corrected excitation spectrum of C60P1 (dash dot
curve) is taken at lem ~ 710 nm (maximum of the fullerene moiety
fluorescence). (b) Fluorescence spectra of C60P1 (dashed curve) and
P1 (solid curve) excited at 560 nm in CH2Cl2 (1 6 1026 mol L21).
Fluorescence intensity for FP (dotted curve) is multiplied by a factor
of 10.

perylene unit; however, its luminescence was largely quenched

(Fig. 3). The fluorescence lifetimes (t) of P1 and C60P1 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 ~
15.4 ns). C60P1 exhibits dual-exponential decay characteristics
(t1 ~ 6.69 ns, 94% and t2 ~ 2.6 ns, 6%),{ and the relative
short-lived fluorescent component is attributed to the interaction between the perylene and the fullerene.36 It seems to be
common sense that the solvent effect of the fluorescence
quenching can be observed if intramolecular charge transfer
occurs in a system.37 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
C60P1 increased a little with increasing solvent polarity. This
evidence disallows the possibility of the intramolecular charge
transfer process in C60P1 at room temperature. FP exhibits a
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 C60P1 taken at lem ~ 710 nm

Fig. 5 Photocurrent spectra of the ITO/C60P1/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 singletsinglet energy transfer from
the P1 unit to the fullerene in the dyad C60P1. The
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 C60P1 on a partially
coated ITO glass. The organic layer was prepared by spin
coating from chlorobenzene solution. The currentvoltage
characteristics of the ITO/C60P1/Al device under different
white light intensities are depicted in Fig. 4. Under an intensity
of 31 mW cm22, the short-circuit current density and the opencircuit voltage of the device are about 3.76 mA cm22 and 0.67 V,
respectively. The IPCE (incident photo-to-current conversion
efficiency) of the ITO/C60P1/Al device is equal to 0.01%. The
performance of the ITO/C60P1/Al device is not as good as that
observed for some fullereneazothiophene-based solar cells.13
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
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

Table 2 Absorption and fluorescence data for C60P1, P1, and FP in CH2Cl2 a
Compound

lmaxabs./nm (log e)

C60P1
P1
FP

702 (0.3)
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)

lmaxfl./nm

Wem b

610
610
710

0.115
1
0.0022

For C60P1 and P1 the fluorescence spectra and quantum yields were obtained upon excitation at their absorption maxima (lex: 560 nm); for
FP the fluorescence spectra and quantum yield values are independent of the excitation wavelength. b Fluorescence quantum yields Wem were
measured with the method using perylene as a standard.35
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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.

7
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Summary
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 C60P1. The
photophysical study in dichloromethane solution has also
shown that singletsinglet energy transfer from the perylene
unit to the fullerene in the dyad C60P1 takes place whereas
electron transfer is a minor process. A photocurrent observed
for ITO/C60P1/Al photovoltaic devices has shown that
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.

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Acknowledgements

21

This work was supported by National Science Foundation of

China and Education Committee of Shanghai. The photovoltaic devices were made in the lab in the Swiss Federal
Institute of Technology in Lausanne/Switzerland and Dr
F. Nuesch 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
23

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