Formation of [60]fullerene nanoclusters with controlled size and morphology through the aid of supramolecular rod-coil diblock copolymers

Article abstract of DOI:10.1002/anie.200461174

On the starting block: Polystyrene-block-poly(4-vinylpyridine) and a [60]fullerene carboxylic acid combine to form spherical supramolecular aggregates (see picture), the size and morphology of which can be controlled by changing the block composition rati

Full text of DOI:10.1002/anie.200461174

Angewandte
Chemie
Supramolecular Chemistry
Formation of [60]Fullerene Nanoclusters with
Controlled Size and Morphology through the Aid
of Supramolecular Rod–Coil Diblock
Copolymers**
Norifumi Fujita, Taketomo Yamashita, Masayoshi Asai,
and Seiji Shinkai*
It is known that block copolymers can self-organize into a
large number of phase-separated superlattices with character-
istic dimensions that range from a few nanometers up to
[
1]
several micrometers.
The interplay of supramolecular
physics and chemistry has opened up several new approaches
to the production of inorganic, organic, and biological super-
[
2]
structures and to their integration into functional units.
Amphiphilic compounds are frequently utilized as functional
[
3]
matrices in the preparation of these superstructures. In the
study of their applications, the importance of controlling the
size of nanoparticles has been described; such control was
successful particularly in the field of inorganic materials such
[
1,4]
as metal colloids, quantum dots, and cluster catalysts.
Examples of controlling the size of their organic counterparts,
[
5]
however, are very limited so far, in spite of their wide range
of applications in materials science.
When a solution of diblock copolymer PS(21400)-b-
P4VP(20700) (A; PS = polystyrene, b = block, P4VP =
poly(4-vinylpyridine)) is cast on a surface under appropriate
conditions, a periodic lamellar structure about 20 nm in
diameter is formed as a result of the amphiphilic nature of the
[
6]
copolymer. The very different surface basicities of the PS
and P4VP domains allows acidic species only to be selectively
assembled on the P4VP domain. For example, when the sol–
gel reaction of tetraethoxysilane is carried out on this surface
[
6]
silica grows to form a string structure on the P4VP domain.
Herein, we report a supramolecular approach using rod–coil
diblock copolymers prepared from random-coil PS-b-P4VPs
as hosts and [60]fullerene carboxylic acid as a guest that leads
to the formation of spherical [60]fullerene nanoclusters with
controlled size and morphology, which are changeable
[
7]
depending on the composition of the PS-b-P4VPs. The
examples described herein would offer one of the most
convenient practical methodologies (just by mixing) for the
control and fabrication of [60]fullerene nanoparticles.
[*] Dr. N. Fujita, T. Yamashita, M. Asai, Prof. Dr. S. Shinkai
Department of Chemistry & Biochemistry
Graduate School of Engineering, Kyushu University
6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan)
Fax: (+81)92-642-3611
E-mail: seijitcm@mbox.nc.kyushu-u.ac.jp
[
**] Support was provided by the 21st Century COE Project, Functional
Innovation of Molecular Informatics. We would like to thank H.
Matsukizono and M. Fujita of Kyushu University for the DLS
analysis and AFM measurements, respectively.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Angew. Chem. Int. Ed. 2005, 44, 1257 –1261
DOI: 10.1002/anie.200461174
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Polymer A (1.0 mg) and [60]fullerene carboxylic acid (1,
.0 mg) were dissolved in 3-pentanone (1.0 mL), and soni-
cated for one minute at room temperature. The solution
1
Figure 2. Schematic representation of the formation of supramolecular
rod–coil polymers leading to the generation of micelles.
homopolymer with 1, a mixture of PS and P4VP with 1, and
polymer A with unmodified [60]fullerene or with the methyl
ester analogue of 1 (2, see the Supporting Information). None
of these samples shows any spherical or periodic surface
structure in the TEM images. Thus, the block composition in
the macromolecule and the pyridine–carboxylic acid inter-
action are indispensable to the formation of such a unique
spherical structure.
Spectral analysis of P4VP in the A·1 composite gives an
insight into the type of host–guest interactions occurring in
this system. The 3-pentanone solvent was removed from the
polymer A·1 composite by evaporation, and the resultant
brown solid was dried in vacuo and subjected to attenuated
total reflectance (ATR) FTIR spectroscopic measurements.
The ATR-FTIR spectra of the samples show the formation of
the hydrogen bond between the pyridyl group in PS-b-P4VP
and the carboxylic acid group in 1 very clearly. The A·1
composites were prepared in different molar ratios of 1 (from
became homogeneous and brown in color, thus indicating that
had interacted with polymer A (since 1 was only partially
1
soluble in 3-pentanone without A). A carbon-coated copper
grid was immersed in this solution for a few seconds and then
dried under ambient conditions for 6 hours. After the sample
had been dried in vacuo for 12 hours, it was analyzed by
transmission electron microscopy (TEM) without staining.
TEM analysis revealed that the size and morphology of
the generated spherical [60]fullerene clusters are quite uni-
form. Black spheres with a small distribution range of
diameters (20–30 nm) are clearly recognized (Figure 1). The
0
.20 to 1.0 molar equivalents, where the molar equivalent is
defined as the molar ratio of the carboxylic acid function in 1
with respect to the pyridyl function in polymer A). In the IR
spectra (see the Supporting Information),
a band at
À1
1
597 cm , which is assigned to the ring-stretching vibration,
À1
is gradually shifted to 1609 cm , which is assigned to the
[
8]
hydrogen-bonded pyridyl group. This shift induced by the
interaction with the carboxylic acid group becomes larger as
the molar ratio of added 1 increases. Samples containing more
than 0.6 molar equivalents of 1 result in turbid solutions,
which implies that all the pyridyl groups in polymer A cannot
interact with 1: at most, 0.6 molar equivalents of 1 can form a
hydrogen bond with the pyridyl group in polymer A, probably
as a result of steric crowding. Analysis of the C=O band in the
Figure 1. TEM image of polymer A·1 composite.
same IR spectra clearly shows that hydrogen bonding
samples observed by TEM were not stained, and therefore the
black contrast is a result of electron absorption by the
between the pyridyl group in the block copolymer and 1
[
7a]
plays a key role in the formation of nanoparticles
(for
[
60]fullerenes. Thus, one can propose that a carboxylic acid
details see the Supporting Information). The five samples
prepared for the IR experiments were directly subjected to
TEM analysis, and all the samples showed a spherical
structure similar to that of the TEM image shown in Figure 1.
It is expected that the length of the homopolymer
segments in PS-b-P4VPs would affect the size and morphol-
ogy of the [60]fullerene clusters in the core of the micelle-like
PS-b-P4VP·1 composites. We thus tried to construct [60]full-
erene superstructures with PS-b-P4VPs having block seg-
ments of different lengths. The [60]fullerene clusters were
prepared according to the same conditions as above, where
the molar ratio of 1 versus the pyridyl function in the P4VP
segment is fixed to 0.6 molar equivalents. Table 1 summarizes
group in 1 interacts with a pyridine moiety in the P4VP block
in polymer A, which adopts a rodlike rigid conformation
because of the structural bulkiness of bound 1 (Figure 2).
Thus, the random-coil structure of the P4VP block is trans-
formed into a rodlike rigid structure and accompanied by a
decrease in the solubility. The poor solubility of the [60]full-
erene-complexed P4VP block and the high solubility of the
PS block in 3-pentanone should result in the formation of the
micelle-like superstructures seen in Figure 1. To further
support this rationale we carried out TEM analysis of five
reference samples prepared under similar conditions to those
described above: 1 only, PS homopolymer with 1, P4VP
1
258
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Table 1: Compositions of PS-b-P4VPs used and structural parameters of their composites with 1.
the PS segment is so short that the
superstructure requiring coverage
by the solvophilic PS segment is no
longer created. It is clear, there-
fore, that the structural morpholo-
gies of the composites are sharply
correlated with the balance of the
solubility of the [60]fullerene clus-
ters and the length of the PS seg-
ments.
PS-b-P4VP
M of PS and P4VP
M /M of
PS-b-P4VP
m(P4VP)/n(PS)
Morphology and size
observed by TEM
n
w
n
À1
[
gmol
]
polymer A
polymer B
polymer C
polymer D
21400/20700
31900/13200
35500/3680
19900/29400
1.13
1.08
1.06
1.15
0.96
0.41
0.10
1.5
sphere, d=20–30 nm
sphere, d=20–25 nm
sphere, d=15–20 nm
sphere and cylinder,
d=40 nm, l=200–300 nm
–
polymer E
polymer F
3300/18700
109000/27000
1.14
1.15
5.6
0.25
sphere, d=50–60 nm
Dynamic light scattering (DLS)
analysis provides information on
the structures of the PS-b-P4VPs used and the resultant size
and morphology of the PS-b-P4VP·1 composites observed by
TEM. It is seen from Table 1 and Figure 3 that polymers A–C,
which have a shorter P4VP segment length with respect to the
PS segment length, tend to form spherical aggregates in which
the diameter decreases from 20–30 to 20–25 to 15–20 nm,
respectively, as length of the P4VP segment decreases from a
P4VP/PS ratio of 0.96:1 to 0.41:1 to 0.10:1, respectively. The
superstructure formed when the P4VP/PS ratio in the PS-b-
P4VPs becomes larger changes to a mixture of sphere and
cylinder, as seen in the case of polymer D (P4VP/PS = 1.5:1).
Furthermore, polymer E with a P4VP/PS ratio of 5.6:1 does
not form any superstructure, as observed by TEM (not
shown). Polymer F with a P4VP/PS molar ratio of 0.25:1 also
shows spherical morphology when it interacts with 1.
the diameter of the nanoparticles in solution. Figure 4 shows
the size distribution of PS-b-P4VP·1 composites in 3-penta-
none solution, and indicates that the diameters of the
composites are very narrowly distributed. The diameters of
the spherical PS-b-P4VP·1 composites prepared from poly-
The specific difference in the superstructure formed can
be explained as follows. The [60]fullerenes tend to aggregate
into a spherical structure that seems to be a priori the most
stable (polymers A–C, and F) when the PS segment has
sufficient length to induce solubility to the spherical [60]full-
erene clusters. However, the PS domain cannot impart
sufficient solubility to the spherical [60]fullerene clusters
when the length of the PS segment is relatively short (polymer
D), and the structure is transformed into a cylindrical
morphology. This change results in a decrease in the surface
area covered with the PS segment. In the case of polymer E,
Figure 4. DLS profiles of a) polymer A·1, b) polymer B·1, c) polymer
C·1, and d) polymer F·1 composites.
Figure 3. TEM images of PS-b-P4VP·1 composites. a) Polymer A·1, b) polymer B·1, c) polymer C·1, d) polymer D·1, and e) polymer F·1. The scale
bars correspond to 100 nm.
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mers B, C, and F are larger than those determined by TEM.
However, the diameter of the spherical PS-b-P4VP·1 compo-
sites prepared from polymer A is almost the same as that
determined by TEM. These discrepancies are rationalized as
follows. In the PS-b-P4VP·1 composites obtained from
polymers B, C, and F, the molecular weights of the PS
segments are sufficiently higher than those of the P4VP
segments that the PS corona surrounding the [60]fullerene
cluster can be extended into the bulk solution. This situation
results in the diameters determined by DLS studies being
larger than those determined by TEM. In the case of polymer
A, however, the molecular weight of the PS segment is
comparable to that of the P4VP segment and the PS corona is
mainly distributed near the surface of the [60]fullerene
cluster. As a result, the diameter of the A·1 composite
determined by DLS studies is nearly the same as that
determined by TEM.
The size and morphology of the composites can be directly
confirmed by scanning electron microscopy (SEM, Fig-
ure 5a), which supports the narrow size distribution of the
polymer A·1 composite. The diameter of the spherical
nanoparticles seen in Figure 5a is comparable with that
observed by DLS measurements. Furthermore, the AFM
image of the A·1 composite in Figure 5b also shows the
spherical morphology with a diameter of about 20 nm. These
results consistently support the view that the [60]fullerene
clusters created from the PS-b-P4VP·1 composites are stable
both in solution and on the surface, even under ultrahigh
vacuum conditions.
Figure 6. a) TEM image of the sample prepared from a mixture of 1
and polymers A and F in 3-pentanone. b) Schematic representation of
“homo” aggregation processes.
Mixing two different PS-b-P4VP copolymers with 1
provided a very interesting result. Firstly, it was confirmed
from TEM analysis that when polymer A or F, which have
long PS block segments, is mixed with 1 in 3-pentanone, the
resultant composites show small or large black dots with
diameters of 20–30 or 50–60 nm, respectively. Next, polymer
A (1.0 mg), polymer F (1.0 mg), and 1 (2.4 mg) were dissolved
together in 3-pentanone (2.0 mL). Interestingly, the TEM
image of the sample prepared from this solution shows two
different small and large black dots, with the smaller dots
excluded from the peripheral area of the larger dots; thus, this
finding clearly shows the presence of the PS corona region
which have different block compositions, to form a mixed
aggregate in the 3-pentanone solution, because their rod–coil
shapes are mismatched (Figure 6b). As a result, the formation
of two “homo” aggregates is more stable than that of one
“mixed” aggregate.
In summary, we have demonstrated the construction of
novel supramolecular aggregates by utilizing the formation of
hydrogen bonds between host block copolymers and a guest
[60]fullerene carboxylic acid. Treatment of these supramolec-
ular rod–coil diblock copolymers under appropriate condi-
tions led to the creation of [60]fullerene nanoparticles with
narrow distributions in size and morphology. This method-
ology is also applicable to the controlled construction of other
organic nanoparticles. It is well-known that control of the size
and morphology of nanoparticles plays an important role in
nanomaterials chemistry; therefore, the methodology de-
(
Figure 6a). These observations imply that the two copoly-
mers tend to aggregate with 1 separately, thus inducing an
intriguing phase-separation phenomenon in the same so-
lution. It is energetically unfavorable for polymers A and F,
Figure 5. a) SEM and b) AFM images of polymer A·1 composite. The scale bar in the SEM image corresponds to 200 nm and the side of the AFM
image is 2 mm long.
1
260
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scribed here should provide a novel approach to nanomate-
rials chemistry and functions. The organic nanoparticles
obtained from these experiments should show interesting
redox, electrochemical, and photochemical properties.
Experimental Section
The block copolymers and [60]fullerene carboxylic acid (1) were
dissolved in 3-pentanone in a capped test tube and the mixture was
sonicated (IUCHI, VS-150) in a water bath at room temperature at a
power level of 150 W (50 kHz). The solution became homogeneous
after 1 min. This sonication procedure did not affect the polymers or
1, as confirmed by gel-permeation chromatography and mass
spectrometry. A carbon-coated copper grid was immersed in the
solution and dried under ambient conditions for 6 h. After drying the
sample in vacuo for 12 h at room temperature, it was subjected to
TEM observation.
Received: July 3, 2004
Revised: November 12, 2004
Published online: January 20, 2005
Keywords: block copolymers · fullerenes · host–guest systems ·
.
nanostructures · supramolecular chemistry
[
1] For recent reviews, see: a) S. Fꢀrster, T. Plantenberg, Angew.
Chem. 2002, 114, 712 – 739; Angew. Chem. Int. Ed. 2002, 41, 688 –
714; b) S. Fꢀrster, M. Antonietti, Adv. Mater. 1998, 10, 195 – 217.
[
2] For recent work, see: D. M. Vriezema, J. Hoogboom, K. Velonia,
K. Takazawa, P. C. M. Cristianen, J. C. Maan, A. E. Rowan,
R. J. M. Nolte, Angew. Chem. 2003, 115, 796 – 800; Angew. Chem.
Int. Ed. 2003, 42, 772 – 776, and references therein; for recent
reviews, see: I. W. Hamley, Angew. Chem. 2003, 115, 1730 – 1752;
Angew. Chem. Int. Ed. 2003, 42, 1692 – 1712.
[
3] For selected papers, see: a) Y. N. C. Chan, R. R. Schrock, R. E.
Cohen, Chem. Mater. 1992, 4, 24 – 27; b) J. P. Spatz, S. Mꢀßmer, M.
Mꢀller, Chem. Eur. J. 1996, 2, 1552 – 1555; c) M. Antonietti, S.
Fꢀrster, J. Hartmann, S. Oestreich, Macromolecules 1996, 29,
3
800 – 3806; d) S. Klingelhꢀfer, W. Heitz, A. Greiner, S. Oes-
treich, S. Fꢀrster, M. Antonietti, J. Am. Chem. Soc. 1997, 119,
0116 – 10120; e) M. Moffitt, L. McMahon, V. Pessel, A. Eisen-
1
berg, Chem. Mater. 1995, 7, 1185 – 1192; f) M. Mꢀller, J. P. Spatz,
Curr. Opin. Colloid Interface Sci. 1997, 2, 177 – 187; g) V.
Sankaran, J. Yue, R. E. Cohen, R. R. Schrock, J. Am. Chem.
Soc. 1993, 115, 4409 – 4410; h) O. A. Platonova, L. M. Bronstein,
S. P. Solodovnikov, I. M. Yanovskaya, E. S. Obolonkova, P. M.
Valetsky, E. Wenz, M. Antonietti, Colloid Polym. Sci. 1997, 275,
426 – 431; i) A. V. Kabanov, S. V. Vinogradov, Y. G. Suzdaltseva,
V. Y. Alakhov, Bioconjugate Chem. 1995, 6, 639 – 643.
[
4] R. Schlꢀgl, S. Bee, A. Hamid, Angew. Chem. 2004, 116, 1656 –
1667; Angew. Chem. Int. Ed. 2004, 43, 1628 – 1637, and references
therein.
[
5] H. Kasai, S. Okazaki, T. Hanada, S. Okada, H. Oikawa, T.
Adschiri, K. Arai, K. Yase, H. Nakanishi, Chem. Lett. 2000, 1392 –
1
393, and references therein.
6] N. Fujita, H. Otsuka, A. Takahara, S. Shinkai, Chem. Lett. 2003,
2, 352 – 353.
[
[
3
7] For representative examples of self-assemblies of polymeric
supramolecules, see: a) T. Kato, J. M. J. Frꢁchet, Macromolecules
1989, 22, 3818 – 3819; b) O. Ikkala, G. ten Brinke, Science 2002,
295, 2407 – 2409, and references therein.
[
8] a) A. Sidorenko, I. Tokarev, S. Minko, M. Stamm, J. Am. Chem.
Soc. 2003, 125, 12211 – 12216; b) H. Peng, D. Chen, M. Jian,
Langmuir 2003, 19, 10989 – 10992.
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