Supramolecular fullerene polymers and networks directed by molecular recognition between calix[5] arene and C60

Article abstract of DOI:10.1002/chem.201404328

A biscalix[5]arene-C₆₀ supramolecular structure was utilized for the development of supramolecular fullerene polymers. Di- and tritopic hosts were developed to generate the linear and network supramolecular polymers through the complexation of

Full text of DOI:10.1002/chem.201404328

DOI: 10.1002/chem.201404328
Full Paper
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Supramolecular Chemistry
Supramolecular Fullerene Polymers and Networks Directed by
Molecular Recognition between Calix[5]arene and C60
Takehiro Hirao,[a] Masatoshi Tosaka,[b] Shigeru Yamago,[b] and Takeharu Haino*[a]
Dedicated to Professor Dr. Julius Rebek, Jr. on the occasion of his 70th birthday
Abstract: A biscalix[5]arene–C60 supramolecular structure
was utilized for the development of supramolecular fullerene
polymers. Di- and tritopic hosts were developed to generate
the linear and network supramolecular polymers through
the complexation of a dumbbell-shaped fullerene. The mo-
lecular association between the hosts and the fullerene were
carefully studied by using 1H NMR, UV/Vis absorption, and
fluorescence spectroscopy. The formation of the supramolec-
ular fullerene polymers and networks was confirmed by dif-
fusion-ordered 1H NMR spectroscopy (DOSY) and solution
viscometry. Upon concentrating the mixtures of di- or tritop-
ic hosts and dumbbell-shaped fullerene in the range of 1.0–
10 mmolLꢀ1, the diffusion coefficients of the complexes de-
creased, and the solution viscosities increased, suggesting
that large polymeric assemblies were formed in solution.
Scanning electron microscopy (SEM) was used to image the
supramolecular fullerene polymers and networks. Atomic
force microscopy (AFM) provided insight into the morpholo-
gy of the supramolecular polymers. A mixture of the homo-
ditopic host and the fullerene resulted in fibers with
a height of (1.4ꢁ0.1) nm and a width of (5.0ꢁ0.8) nm. Inter-
digitation of the alkyl side chains provided secondary inter-
chain interactions that facilitated supramolecular organiza-
tion. The homotritopic host generated the supramolecular
networks with the dumbbell-shaped fullerene. Honeycomb
sheet-like structures with many voids were found. The
growth of the supramolecular polymers is evidently gov-
erned by the shape, dimension, and directionality of the
monomers.
Introduction
tions with very high affinities to obtain an appreciable degree
of polymerization. This requirement restricts the number of
possible variations of host–guest interactions that can be ex-
ploited for supramolecular polymerization. Crown ethers,[7] cy-
clodextrins,[8] cucurbit[n]urils,[9] calix[n]arenes,[10] and molecular
clefts[11] are well recognized as host molecules with very high
affinities for guest molecules and provide useful supramolec-
ular structures for polymerization. Among calixarene families,
calix[5]arenes are less employed as host molecules for supra-
molecular polymerization.[12] We have been developing calix[5]-
arene-based host molecules,[13] and during the course of our
studies, we discovered that they encapsulate fullerenes.[14] In
one study, biscalix[5]arene structures were observed to be
great host molecules for C60 as well as higher fullerenes.[15]
Thus, we envisioned the development of supramolecular fuller-
ene polymers and networks utilizing the host–guest interaction
between a biscalix[5]arene and C60.
Supramolecular polymers consist of repeating units that are
held together by reversible noncovalent interactions.[1] The
sizes and dimensions of these supramolecular polymers
depend on the directionalities and stabilities of intermolecular
interaction connecting the repeating units. Recent efforts have
devoted to the construction of advanced supramolecular poly-
mer materials, providing innovative features such as stimuli-re-
sponsiveness,[2] self-healing,[3] and easy fabrication.[4] A great
majority of the supramolecular polymers developed to date in-
volve hydrogen-bonding motifs[5] or metal coordination.[6]
Supramolecular polymerization reactions driven by host–guest
interactions have been employed to a lesser extent, although
a vast number of host–guest complexes are known to exist.
Supramolecular polymerization requires host–guest interac-
The spherical shapes and unusual electronic properties ex-
hibited by molecules of the fullerene family have attracted
great interest for the construction of carbon-based materials
that exhibit magnetic,[16] superconducting,[17] electrochemi-
cal,[18] and photophysical functions,[19] particularly n-type-direct-
ed fullerenes[20] for the development of organic solar cells.
Nanofabrication of fullerene is a prerequisite for efficient pho-
toelectronic conversion in fullerene-based organic solar cells.[21]
Thus, recent endeavors have been dedicated to controlling the
[a] T. Hirao, Prof. Dr. T. Haino
Department of Chemistry
Graduate School of Science, Hiroshima University
1-3-1 Kagamiyama, Higashi-Hiroshima, 739-8526 (Japan)
E-mail: haino@hiroshima-u.ac.jp
[b] Prof. Dr. M. Tosaka, Prof. Dr. S. Yamago
Institute for Chemical Research, Kyoto University
Gokasho Uji 611-0011 (Japan)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201404328.
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organization of fullerene nanoarrays at the molecular level, re-
fining the performance of such devices. Supramolecular fuller-
ene polymers can offer an effective way to organize fullerene
nanoarrays. Hence, intensive research concerning the develop-
ment of fullerene polymers in a noncovalent fashion is current-
ly being conducted. Hummelen et al. reported the pioneering
example of a hydrogen-bonded supramolecular polymer fea-
turing a fullerene array.[22] Liu et al. demonstrated a metallo-
bridged supramolecular fullerene assembly driven by a 1:2
complexation of C60 and b-cyclodextrin.[23] Recently, Martꢁn
et al. reported that exTTF–C60 complexation (exTTF=9,10-
di(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene) is very useful
for constructing supramolecular fullerene polymers and den-
drimers.[24] However, placing fullerene molecules on polymer
main chains is still challenging, because a limited number of
fullerene host molecules have been used for supramolecular
polymerization.
into dumbbell-fullerenes. Herein, we describe the synthesis
and the properties of a new class of linear and network fuller-
ene polymers both in solution and in the solid state. Dumb-
bell-shaped fullerenes were newly designed to be sufficiently
soluble in common organic solvents to study the formation of
supramolecular fullerene polymers in solution (Figure 1). The
supramolecular complexation between the calixarene hosts
(H1 and H2) and the guest fullerenes (G3a,b) should give rise
to linear supramolecular fullerene polymers and extended full-
erene networks (Scheme 1), respectively.
Results and Discussion
The syntheses of tetrakis- and hexakiscalix[5]arene hosts H1
and H2 are outlined in Scheme 2. The reaction of the 4-carbox-
ybenzenediazonium chloride (4)[26] with calix[5]arene 5,[14c] fol-
lowed by the reduction of the azobenzene moiety produced
aminocalix[5]arene 6. 4-Ethynyldimetyl chelidamate (7) was
used in the synthesis of aromatic linker 8.[25] Sonogashira reac-
tion of 7 with 1,4-bis(dodecyloxy)-2,5-diiodobenzene[27] and
the subsequent hydrolysis of ester moieties yielded the corre-
sponding diacid, which was converted to diacid chloride 8.
The acylation reaction of 6 with 8 smoothly proceeded in THF
to afford biscalix[5]arene 9 in good yield. To avoid the tedious
Preliminary results regarding supramolecular fullerene poly-
merization through molecular recognition between a calix[5]ar-
ene and C60 have been reported.[25] However, the macroscopic
properties of the previous linear fullerene polymers in solution
were not studied in detail due to the low solubility in common
organic solvents. To improve the solubility of supramolecular
fullerene polymers, long alkyl chains have been introduced
Figure 1. Molecular structures of calix[5]arene-based hosts H1 and H2 and dumbbell-shaped fullerene G3a,b.
Scheme 1. Schematic illustration of the formation of supramolecular fullerene polymers.
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Figure 2. 1H NMR spectra of a) H1, b) H2, c) a 1:1 mixture of H1 and G3a,
and d) a 2:3 mixture of H2 and G3a at 293 K in [D1]-chloroform.
to the rapid ring flipping. When C60 is encapsulated within
a calix[5]arene cavity, it increases the ring-flipping activation
energy. As a result, the bridge methylenes appear as an AB-like
resonance.[14c] Thus, the proton resonance is a probe for the
detection of the intermolecular association between a calix[5]-
arene and a C60 molecule.
Scheme 2. Synthesis of host molecules. DMF=dimethylformamide, THF=te-
trahydrofuran, TMS=trimethylsilyl.
protection-deprotection procedures of the hydroxyl groups, an
ethynyl group was directly introduced into 9. Although oxida-
tive coupling of 9 under Eglinton conditions was unsuccessful,
modified Sonogashira conditions worked nicely to furnish di-
topic host H1 via compounds 10 and 11. Sonogashira reaction
of 9 with 1,3,5-triethynylbenzene proceeded smoothly to
afford host H2.
Calix[5]arene hosts H1 and H2 displayed broad resonances
of the bridge methylene protons at approximately 3.8 ppm, in-
dicating that the ring-inversion process occurred rapidly even
though the calix[5]arene moieties were close to their neigh-
bors. Upon the addition of dumbbell-shaped fullerene G3a in
solutions of hosts H1 and H2, the broad methylene resonances
split roughly into two broad resonances, suggesting that the
ring inversion of the calix[5]arene moieties became slower due
to the complexation of the C60 moieties within the calix[5]ar-
ene cavity.
The synthesis of dumbbell-shaped fullerenes G3a,b is out-
lined in Scheme 3. Condensation reaction of 12[28] and 13[29]
H1 and H2 displayed absorption bands at 419 and 397 nm,
attributable to the p–p* transition of the di(pyridylethynylphe-
nyl)butadieyne and tri(pyridylethynylphynylethynyl)benzene
moieties. Upon the addition of dumbbell-shaped fullerenes
G3b to the solutions of H1 and H2, new bands emerged at ap-
proximately 420 and 400 nm, which are characteristic of the
formation of a C60·calix[5]arene complex (Figure S1 in the Sup-
porting Information).[14c] When cooling the solution from 343
to 303 K, the absorption bands gradually increased in intensity.
This finding implied that the host–guest complexations of H1
and H2 with G3b were enhanced, resulting in the supramolec-
ular aggregates. However, the overlap of the absorption bands
of H1, H2, G3b, and their complexes restricted the precise ana-
lytical treatments required to determine the intermolecular as-
sociation. The highly conjugated aromatic linker moieties of
H1 and H2 generated intense fluorescence at 451 and 464 nm,
most likely corresponding to p–p* transitions (Figure 3a,b).
Fullerene is known to be a good energy acceptor;[15b] thus,
these emissions can be quenched when a C60 moiety is encap-
sulated within the cavities of the hosts. The addition of G3b
quenched the emissions of H1. The emission of H2 was more
efficiently quenched than that of H1 in the presence of G3b;
H1 possesses two fullerene-binding cavities, each of which is
composed of two calix[5]arenes, whereas three fullerene-bind-
ing cavies are implemented in H2. Accordingly, the concentra-
tion of the fullerene moieties closer to the fluorophores result-
ed in the effective quenching of H2.
Scheme 3. Synthesis of guest molecules. HOBt=1-hydroxybenzotriazole,
DMAP=N,N-dimethyl-4-aminopyridine, DCC=N,N’-dicyclohexylcarbodiimide.
yielded G3a. The synthesis of G3b began with compound
14.[30] Sonogashira reaction of 14 with 4-etynylbenzaldehyde
followed by the reduction of the aldehyde groups and then
a condensation reaction with 13 afforded G3b.
Intermolecular associations between the homotopic hosts
and dumbbell-shaped fullerenes in solution were studied using
1H NMR, fluorescence, and UV/Vis absorption spectroscopy.
1
Figure 2 shows the H NMR spectra of H1 and H2 before and
after the addition of G3a in [D1]-chloroform. A calix[5]arene
adopts a cone conformation due to the cyclic hydrogen bonds
of the five phenolic hydroxyl groups. When the ring flipping of
a calix[5]arene is very slow on the NMR timescale, the bridge
methylene protons are magnetically non-equivalent, resulting
in an AB-type resonance. The bridge methylene protons com-
monly appear as a broad resonance at room temperature due
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shows the Stern–Volmer plots obtained from fluorescent inten-
sity measurements upon the addition of G3b in toluene. The
plots of the relative fluorescence intensities I0/I of H1 and H2
versus the concentrations of G3b gave rise to a steeply
upward curvature above a concentration of 4.0ꢂ10ꢀ5 molLꢀ1.
Static as well as dynamic quenching clearly participated in the
overall quenching process. At low concentrations at which dy-
namic quenching was dominant, the distinct temperature de-
pendence of the fluorescence quenching provided additional
support for the static quenching mechanism that was involved
in the host–guest complexation between fluorescent hosts H1,
H2, and G3b (Figure S4 in the Supporting Information). To
gain stoichiometric insight into the intermolecular associations
of hosts H1, H2, and G3b, Job plots confirmed that H1 bound
G3b in a ratio of 1:1, whereas the complexation of H2 and
G3b resulted in host–guest complex in a ratio of 2:3 (Fig-
ure 3e,f).
The sizes and dimensions of supramolecular polymers in so-
1
lution can be determined by diffusion-ordered H NMR spec-
troscopy (DOSY). According to the Stokes–Einstein relation,
D=kBT/6phR, the diffusion coefficient (D) of a molecular spe-
cies is inversely proportional to the hydrodynamic radius (R).
Therefore, the degree of polymerization (DP) can be estimated
by the weighted diffusion coefficients of existing molecular
species. Figure 4a demonstrates that diffusion coefficients of
H1, H2, and G3b were concentration-independent. No aggre-
gate was formed in solution. By contrast, the diffusion coeffi-
Figure 3. Fluorescence changes in a) 1 (2.0ꢂ10ꢀ5 molLꢀ1, lex =420 nm) and
b) H2 (2.0ꢂ10ꢀ5 molLꢀ1, lex =400 nm) in the presence of G3b (a–k: 0.0, 0.1,
0.3, 0.6, 0.9, 1.0, 1.2, 1.5, 1.8, 2.0, 3.0ꢂ10ꢀ5 molLꢀ1) at 298 K in toluene.
Stern–Volmer plots for c) H1 (2.0ꢂ10ꢀ5 molLꢀ1, lex =420 nm) and d) H2 with
G3b. Job plots for e) H1 with G3b ([H1]+[G3b]=2.0ꢂ10ꢀ5 molLꢀ1) and f)
H2 with G3b ([H2]+[G3b]=2.0ꢂ10ꢀ5 molLꢀ1). X1 and X2 indicate the molar
fractions of H1 and H2, respectively. DI’ indicates jIꢀI0Xj.
Fluorescence quenching can occur by dynamic quenching
(molecular collision), static quenching (complex formation), or
by both dynamic and static quenching mechanisms simultane-
ously. In dynamic quenching, a quencher diffuses to a fluoro-
phore during the lifetime of the excited state, and the fluoro-
phore returns to the ground state without emission of
a photon. In this case, the Stern–Volmer equation is expressed
as I0/I=1+Kd[Q], in which Kd and [Q] are the Stern–Volmer
constant for dynamic process and the concentrations of
quencher, respectively. In common host–guest complexation,
strong molecular association participates in the quenching pro-
cess; thus, in combined dynamic quenching for partitioning
molecules and static quenching for binding molecules, the
Stern–Volmer equation is expressed as I0/I=(1+Kd[Q])-
(1+Ka[Q]), in which Ka is the associate constant between
quencher and fluorophore. In this case, the plot of I0/I versus
[Q] based on the equation should bend upward.[31] Figure 3c,d
Figure 4. a) Diffusion coefficients (D) and b) viscosities (h) of H1 (open
circle), H2 (open square), G3b (open triangle), H1 with one equivalent of
G3b (filled circle), and H2 with 1.5 equivalents of G3b (filled square) at
297 K in chloroform. Relative viscosities (hꢀh0) of c) H1 in the presence of
one equivalent of G3b at 297 (filled circle), 287 (open rhombus), and 277 K
(filled rhombus), and d) H2 in the presence of 1.5 equivalents of G3b at 297
(filled square), 287 (open rhombus), and 277 K (filled rhombus) in chloro-
form. C denotes the weighted-average concentrations of H1 or H2 when
G3b is present.
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cients of H1 with G3b and H2 with G3b depended on concen-
trations. In the low-concentration range, the diffusion coeffi-
cients for H1 and H2 in the presence of G3b were similar to
those for H1 and H2. As the concentrations of the mixtures
were increased, the diffusion coefficients of H1 and H2 de-
creased nonlinearly by approximately 80%. These findings indi-
cate that large polymeric aggregates are formed through the
host–guest complexation between the biscalix[5]arene and the
C60 moieties. Assuming the aggregates were hydrospherical,[32]
the DPs for a 1:1 mixture of H1 and G3b and a 2:3 mixture of
H2 and G3b were roughly estimated to be 83-mer and 151-
mer, respectively, in the high-concentration range.
mensionally grown polymer network structures are formed, ex-
plaining the temperature-dependent viscosity of the solution.
Scanning electron microscopy (SEM) provided insight into
the morphology of the supramolecular polymers in the solid
state. Dumbbell-shaped fullerenes G3a,b gave rise to particle-
like morphologies due to their cohesive nature (Figure S6 in
the Supporting Information). A 1:1 mixture of H1 and G3a
gave rise to fibrillar morphologies with a diameter of (180ꢁ
50) nm (Figure 5a), whereas a 2:3 mixture of H2 and G3a pro-
Viscometry provides useful information for determining the
dimensions of supramolecular polymers and networks in solu-
tion. The viscosities of solutions of H1 and G3b and of H2 and
G3b in chloroform were directly determined using a viscome-
ter. Figure 4b displays the concentration-dependent behavior
of the solution viscosities. The solution viscosities were not af-
fected when H1, H2, and G3b were individually dissolved. The
solutions of H1 and H2 became viscous when G3b was added.
The meaningful changes in the viscosities as a function of the
concentration are indicative of the semidilute concentration
regime in which overlap between chains contributes to viscous
drag. The concentration dependence of the viscosity for the
solution of H2 is more distinct than that for H1, implying that
the structures of the supramolecular aggregates formed from
H2 and G3b are dimensionally extended, resulting in the
supramolecular polymeric networks.
In general, a host–guest interaction is enhanced by cooling
the host–guest solution. As a result, supramolecular polymers
grow and shrink in response to temperature. Cooling the mix-
ture solutions should facilitate the growth of the polymers.
The solution viscosities of the mixtures were measured at
three temperatures: 24, 14, and 48C. Although the intermolec-
ular association between H1 and G3b must be promoted by
cooling the solutions, the viscosities were not significantly af-
fected (Figure 4c), whereas the solution of H2 and G3b
became more viscous upon cooling (Figure 4d). These highly
contrasting viscometric behaviors provided insight into the
nature of the polymeric aggregates formed in solution.
Compounds H1, H2, and G3b are rigid. Therefore, the linear
polymers formed by the complexation of H1 and G3b can be
rigid “rod-like” macromolecules that cannot entangle. Molecu-
lar collisions affect solution viscosity because the rods cannot
pass through each other. In the dilute regime, the rods can be
randomly oriented and rotate freely without being constrained
by neighboring rods. In the semidilute regime, the solution vis-
cosity are slightly affected, because molecular rotations are
fairly impeded.[33] However, upon cooling, the newly grown ter-
mini can be randomly placed at the polymer ends with a negli-
gible probability of the termini increasing the contact between
other rods. The rod-like structures are characterized by a low-
temperature sensitivity of the polymer solutions. In contrast,
the supramolecular association between H2 and G3b can pro-
mote extended polymeric networks in solution upon cooling.
The networks can be cross-linked, and each of the binding
sites might participate in a cooperative fashion. As a result, di-
Figure 5. SEM images of cast films of a) a 1:1 mixture of H1 and G3a, b)
a 2:3 mixture of H2 and G3a, c) a 1:1 mixture of H1 and G3b, d) a 2:3 mix-
ture of H2 and G3b, e) a 1:2 mixture of H1 and G3b, f) a 2:5 mixture of H2
and G3b, g) a 2:1 mixture of H1 and G3b, and h) a 2:1 mixture of H2 and
G3b prepared from their solutions in toluene on a glass plate.
duced thin-film morphologies (Figure 5b). The large morpho-
logical differences between H1 and H2 with G3a most likely
arise from the dimensions of the host molecules; the polymer
formed from H1 and G3a grows in a linear fashion, whereas
that formed from H2 and G3a results in widespread sheet-like
growth. Although the supramolecular polymers were success-
fully obtained, the polymeric structures were thin, most likely
due to the limited attractive interchain interactions of the alkyl
side chains. More alkyl chains must be incorporated to gener-
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ate the attractive interpolymer interactions required to facili-
tate the further growth of the supramolecular polymers. In
fact, when G3b, which possesses six long alkyl chains, was em-
ployed, H1 produced thicker and entwined fibrillar networks
with diameters of (250ꢁ30) nm (Figure 5c). Figure 5d shows
the thicker widespread film produced by the molecular associ-
ation of H2 and G3b.
Molecular arrangements in different dimensions were further
investigated as indicated below.
Atomic force microscopy (AFM) imaging provided detailed
insights into the nanoscale molecular array of the polymers
formed. Cast films of the supramolecular polymer and network
were prepared on a mica surface. The linear polymers of H1
and G3a were aligned on a mica sheet (Figure 6a), exhibiting
Binary supramolecular polymers are maintained by noncova-
lent intermolecular interactions, and the dimensions of the
supramolecular polymers can be reorganized by stoichiometric
regulation and the addition of a competitive guest molecule.
An excess amount of guest G3b filled most of the guest bind-
ing pockets, which completely collapsed the supramolecular
polymeric fibers and sheets, giving rise to agglomerated mor-
phologies due to the random aggregation of the uncomplexed
C60 moieties (Figure 5e,f). An excess of the hosts also affected
the morphologies of the supramolecular polymers. End-cap-
ping of the polymeric fibers with H1 terminated polymer
growth, resulting in thinner fibers with dangling bonds (Fig-
ure 5g). Surprisingly, in the presence of an excess amount of
H2, the film transformed into fibers (Figure 5h). This remark-
able morphological transition can be rationalized by consider-
ing that two of the C60 moieties of G3b were fully encapsulat-
ed by two of the binding sites of H2, the rest of which did not
participate in supramolecular polymerization; as a result,
supramolecular polymers developed linearly. The addition of
C60 interfered with the growth of the supramolecular polymers
and networks, which completely collapsed the fibers and films
(Figure S6 in the Supporting Information). Accordingly, the for-
mation of fibers, films, networks and agglomerates was driven
by the intermolecular calix[5]arene–C60 interaction.
Figure 6. AFM images of cast films of a) a 1:1 mixture of H1 and G3a
(5.0 mmꢂ5.0 mm, topography), b) a 2:3 mixture of H2 and G3a
(10 mmꢂ10 mm, topography), c) a 1:1 mixture of H1 and G3b
(0.22 mmꢂ0.22 mm, phase), and d) a 2:3 mixture of H2 and G3b
(0.18 mmꢂ0.18 mm, phase) prepared from their solutions in toluene on mica.
Information about the microstructure of the supramolecular
polymers was obtained by solid-phase wide-angle X-ray diffrac-
tion (WAXD). As shown in Figure S7 in the Supporting Informa-
tion, monomers H1 and H2 presented strong scattering in the
small-angle region, indicating large-scale density fluctuation.
The broad scattering peak of H1 at q’15 nmꢀ1 indicates the
amorphous nature of the sample, whereas the small sharp
peaks of H2 at q’3, 11 and 16 nmꢀ1 suggest crystallinity. This
difference in crystallinity is thought to derive from the different
dimensional features between H1 and H2; relative to H1, H2
has a more planar (two-dimensional) structure that is advanta-
geous for the formation of crystal nuclei by stacking upon
evaporation of the solvent. Fullerene G3b has two peaks at
q’2 and 14 nmꢀ1, which were not as sharp as the crystalline
peaks but not as broad as the amorphous halo. The intermedi-
ately ordered structure related to this type of WAXD spectrum
is attributed to a so-called mesophase. The WAXD spectra of
a 1:1 mixture of H1 and G3b and a 2:3 mixture of H2 and
G3b showed features similar to those of G3b, but with differ-
ent peak q values. Furthermore, the WAXD spectra of the mix-
tures were not explained by a mathematical summation of
those of the individual monomers H1, H2, and G3b. These re-
sults indicate that different mesomorphic structures were gen-
erated in the mixtures as a result of host–guest complexation.
It is noted that the above-mentioned results were obtained for
the bulk solid (three-dimensional aggregates) of the samples.
a height of (1.4ꢁ0.1) nm and a width of (40ꢁ10) nm (Fig-
ure S8k in the Supporting Information). Judging from the cal-
culated structure of the oligomers (Figure 7a), the height
matched the diameter of the C60–biscalix[5]arene complex, and
the alkyl side chains measured approximately 3.6 nm in length,
which is larger than the observed height. These findings sug-
gest that the alkyl chains were arranged parallel to the mica
surface, and the polymer chains formed a bundle of approxi-
mately ten polymer chains created by the intertwining of alkyl
side chains via van der Waals interactions. Figure 6b shows
that widespread sheet-like morphologies were obtained for
the cast films of H2 and G3a. The uniform height of (1.2ꢁ
0.1) nm (Figure S8l in the Supporting Information) is consistent
with the height of the diameter of the C60-biscalix[5]arene
complex, clearly indicating that two-dimensionally-grown,
single-layered spread sheets were formed on a mica surface
(Figure 6b).
To investigate the interchain interactions of the supramolec-
ular polymers, G3b was employed instead of G3a for polymer-
ization. AFM images of the cast films of H1 and H2 with G3b
provided more detailed information regarding the organization
of the polymeric arrays. In Figure 6c, highly oriented supra-
molecular polymeric chains of H1 and G3b with a rather uni-
form interchain distance of (5.0ꢁ0.8) nm (Figure S9a in the
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oshima University, for helpful discussions about solution rheol-
ogy. This work was supported by JSPS Grants-in-Aid for Scien-
tific Research (B) (No. 24350060) and Challenging Exploratory
Research (No. 23655105), as well as MEXT Grants-in-Aid for Sci-
entific Research on Innovative Areas, “Stimuli-responsive
Chemical Species for Creation of Functional Molecules” and
“New Polymeric Materials Based on Element-Blocks” (Nos.
25109529, 25102532), and Platform for Dynamic Approaches
to Living System.
Keywords: calixarenes
·
fullerenes
·
supramolecular
chemistry · supramolecular polymers
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Figure 7. Calculated structures of the oligomeric assemblies of a) H1 and
G3a, b) H1 and G3b, and c) H2 and G3a (one of the biscalix[5]arene moiet-
ies and the alkyl chains are omitted for clarity).
Supporting Information) can be observed, most likely due to
the microphase separation between the C60-containing poly-
mer chains and the long flexible alkyl side chains; in fact, the
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Conclusion
We described a facile process for fabricating fullerene polymers
driven by host–guest interactions between calix[5]arene and
C60. The formation and structures of the supramolecular poly-
mers and networks were carefully examined using a variety of
spectroscopic techniques. During the experiments, the dimen-
sions of the supramolecular polymers were controlled by the
rational design of the monomer components. Although each
of the monomers was connected via noncovalent interactions,
supramolecular polymers belong to the class of polymers in
terms of macroscopic properties. The designability of supra-
molecular polymers could open up new possibilities for molec-
ular organization in nanospace.
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Received: July 10, 2014
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Published online on && &&, 0000
Chem. Eur. J. 2014, 20, 1 – 10
www.chemeurj.org
9
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
FULL PAPER
Let’s do some networking! A bisca-
lix[5]arene-C60 supramolecular structure
was utilized for the development of
supramolecular fullerene polymers. Di-
and tritopic hosts were developed to
generate the linear and network supra-
molecular polymers (see figure) through
the complexation of a dumbbell-shaped
fullerene. The growth of the supra-
molecular polymers is governed by the
shape, dimension, and directionality of
the monomers.
&
Supramolecular Chemistry
T. Hirao, M. Tosaka, S. Yamago, T. Haino*
&& – &&
Supramolecular Fullerene Polymers
and Networks Directed by Molecular
Recognition between Calix[5]arene
and C60
New linear and networked……fullerene polymeric
organizations were synthesized through self-assembly
directed by molecular recognition of a biscalix[5]arene
and C60. The cover represents the schematic representa-
tion of the supramolecular organization processes for
the formation of the linear and network fullerene poly-
mers. For more details see the Full Paper by T. Haino et
al. on page && ff.
&
&
Chem. Eur. J. 2014, 20, 1 – 10
www.chemeurj.org
10
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!