Functional Sulfur-Doped Buckybowls and Their Concave–Convex Supramolecular Assembly with Fullerenes

Article abstract of DOI:10.1002/anie.201606383

Buckybowls are fascinating components of supramolecular assemblies owing to their unique bowl-shaped π-surfaces. Herein we present a protocol for the functionalization of a sulfur-doped buckybowl, trithiasumanene, via a brominated intermediate, from which thiolated trithiasumanenes were derived. The curved surface and electron-donating properties of thiolated trithiasumanenes promote their ready assembly with fullerenes to form concave–convex complexes. The supramolecular assembly behavior in solution was investigated by NMR analysis. The structures of supramolecular complexes were unambiguously characterized by crystallography. The crystals of the concave–convex complexes showed high thermal stability and photoconductivity.

Full text of DOI:10.1002/anie.201606383

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International Edition: DOI: 10.1002/anie.201606383
German Edition: DOI: 10.1002/ange.201606383
Supramolecular Assembly
Functional Sulfur-Doped Buckybowls and Their Concave–Convex
Supramolecular Assembly with Fullerenes
Yu-Min Liu+, Dan Xia+, Bo-Wei Li, Qian-Yan Zhang, Tsuneaki Sakurai, Yuan-Zhi Tan,*
Shu Seki, Su-Yuan Xie,* and Lan-Sun Zheng
Abstract: Buckybowls are fascinating components of supra-
molecular assemblies owing to their unique bowl-shaped p-
surfaces. Herein we present a protocol for the functionalization
of a sulfur-doped buckybowl, trithiasumanene, via a bromi-
nated intermediate, from which thiolated trithiasumanenes
were derived. The curved surface and electron-donating
properties of thiolated trithiasumanenes promote their ready
assembly with fullerenes to form concave–convex complexes.
The supramolecular assembly behavior in solution was inves-
tigated by NMR analysis. The structures of supramolecular
complexes were unambiguously characterized by crystallog-
raphy. The crystals of the concave–convex complexes showed
high thermal stability and photoconductivity.
modulate and reinforce the supramolecular assembly of
buckybowls. The substituents can not only tune the electronic
nature of buckybowls,[5a,12] but can also introduce additional
supramolecular interactions,[5b–d] such as hydrogen bonding.
In general, multiply substituted buckybowls are needed to
efficiently amplify the electronic effects and promote the
supramolecular assembly.[5a–d,12,13] For example, by employing
a pentathiolated corannulene, Scott and co-workers realized
the first supramolecular assembly of buckybowls with C60 in
solution.[5a] As another example, Aida and co-workers con-
structed electric-field-responsive liquid crystals[5b] and chiral
supramolecular polymers[5c] by using deca- or pentathiolated
corannulenes bearing multiple hydrogen-bonding sites on the
peripheral thiol groups. The combination of heteroatom
doping and multisubstitution can lead to more effective
building blocks for the construction of supramolecular
architectures. However, studies on the functionalization and
application of heteroatom-doped buckybowls in supramolec-
ular assembly have been rare.
Herein we report a protocol for the functionalization of
a sulfur-doped buckybowl, trithiasumanene (1), by perbromi-
nation and nucleophilic substitution. The hexathiolated
trithiasumanenes 3–5 were readily synthesized by this strat-
egy. The curved and electron-rich nature of hexathiolated
trithiasumanenes makes them good hosts for supramolecular
assembly with fullerenes. The supramolecular assembly in
solution was confirmed and characterized by NMR spectros-
copy and fluorescence quenching. The crystal structures of the
complexes clearly revealed close concave–convex p–p inter-
actions between the hexathiolated trithiasumanenes and
fullerenes, as well as the packing structure of the supramolec-
ular complexes in the crystalline state. The crystal of the
3ꢀC60 complex showed remarkably high thermal stability and
intrinsic charge-carrier transporting that was not achieved by
the drop-cast 3/C60 1:1 mixture.
B
uckybowls, viewed structurally as a substructure of ful-
lerenes[1] or the cap of carbon nanotubes,[2] have attracted
much attention.[3] Their bowl-shaped conjugated structure
leads to asymmetrical polarized concave–convex p-faces,[3,4]
which are particularly attractive for supramolecular assem-
bly.[5] The concave p-face of buckybowls has a higher electron
density than the opposite convex p-face.[5a,6] Buckybowls tend
to stack into a columnar supramolecular structure in a con-
cave–convex fashion,[7] although packing devoid of a columnar
structure was also observed.[8] Meanwhile, the electron-rich
concave p-face of buckybowls can serve as an electronically
and geometrically suitable electron-donating host for full-
erenes.[6a,9] Doping of the buckybowls with heteroatoms,[10]
such as sulfur and nitrogen, can enhance their electron-
donating and polarizing ability,[10e,11] thus leading to stronger
supramolecular interactions between buckybowls and elec-
tronic-deficient acceptors.[10e]
Besides heteroatom doping, functionalization with adapt-
able substituents is one of the most promising strategies to
[*] Y. M. Liu,[+] D. Xia,[+] B. W. Li, Dr. Q. Y. Zhang, Prof. Dr. Y. Z. Tan,
Prof. Dr. S. Y. Xie, Prof. Dr. L. S. Zheng
Halogenated buckybowls are key intermediates for the
synthesis of functionalized, especially multisubstituted,
buckybowls.[14] Trithiasumanene (1) was perbrominated with
bromine in the presence of a catalytic amount of iron powder
at 808C to afford perbromotrithiasumanene (2) in 95% yield
(Figure 1a; see also Figure S1 in the Supporting Information).
Compound 2 is the first reported perbrominated buckybowl,
and its chemical identity was characterized by matrix-assisted
laser desorption/ionization time-of-flight mass spectrometry
(see Figure S2). Only one dominant peak in the mass
spectrum was observed, with an isotopic distribution pattern
identical to that calculated for compound 2 (see Figure S2).
However, the poor solubility of 2 in common organic solvents
hindered its further structural elucidation.
Collaborative Innovation Center of Chemistry for Energy Materials,
State Key Laboratory for Physical Chemistry of Solid Surfaces and
Department of Chemistry, College of Chemistry and Chemical
Engineering, Xiamen University
Xiamen 361005 (China)
E-mail: yuanzhi_tan@xmu.edu.cn
syxie@xmu.edu.cn
Dr. T. Sakurai, Prof. Dr. S. Seki
Department of Molecular Engineering
Graduate School of Engineering, Kyoto University
Nishikyo-ku, Kyoto 615-8510 (Japan)
[+] These authors contributed equally.
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.201606383.
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The optical properties of 3–5 were elucidated
by UV/Vis and fluorescence spectroscopy. Com-
pounds 3–5 have nearly identical absorption
profiles (Figure 2a), with the highest absorption
peak at 365 nm (loge = 4.64) and a shoulder peak
at 385 nm (loge = 4.35), which can be assigned as
the b and p absorption bands. The weak absorp-
tion peak (loge = 3.38) located at 445 nm was
assigned as the a absorption band, which corre-
sponds to a HOMO–LUMO gap of 2.30 eV.
Similarly, the fluorescence spectra of 3–5 were
nearly identical, with emission at 464 nm (Fig-
ure 2a). The optical absorption and fluorescence
of 3–5 are redshifted by 0.047 and 0.064 eV as
compared to pristine trithiasumanene and by
0.052 and 0.088 eV as compared to hexabutoxyl-
trithiasumanene.[10a,b] These data revealed the
strong perturbation effect of peripheral thiol
groups on the electronic nature of trithiasuma-
nene. The sulfur doping in the skeleton and
peripheral thiol substituents was expected to
greatly enhance the electron-donating ability of
the buckybowl. From electrochemical measure-
ments, compounds 3–5 showed a much lower
Figure 1. a) Synthetic route towards hexathiolated trithiasumanenes 3–5 (DMI=1,3-
dimethyl-2-imidazolidinone). b) Top view and c) side view of 3. d) Concave–convex
dimer of 3 (phenyl groups are not shown). In (b–d), all hydrogen atoms have been
omitted for clarity, and thermal ellipsoids are set at the 50% probability level.
The introduction of thiol groups at the periphery would
enhance the electron-donating ability of trithiasumanene and
thus promote its donor–acceptor supramolecular assembly
with fullerenes.[5a,12a] Hence, we carried out the thiolation of 2
with different aryl thiolates to produce hexakis(phenylthio)-
trithiasumanene (3), hexakis(p-tolylthio)trithiasumanene (4),
and hexakis(4-methoxyphenylthio)trithiasumanene (5) in 35–
40% yield (see the Supporting Information). The mass
spectra of 3–5 displayed one dominant peak, which matched
the formulae of 3–5 perfectly (see Figure S3). Unlike 2, 3–5
showed sufficient solubility in organic solvents, such as
dichloromethane, toluene, and chloroform, to allow for their
characterization by 1H and 13C NMR spectroscopy (see
Figures S3–S6), which confirmed their proposed chemical
structures as well as their high purity.
The detailed structure of the hexathiolated trithiasuma-
nene 3 was determined by crystallography (see the Supporting
Information).[15] Single crystals of 3 were obtained by slowly
diffusing n-hexane into a solution of 3 in chloroform. The
trithiasumanene core was decorated with six phenylthio
groups (Figure 1a). The hub six-membered ring of the bowl
in 3 showed slight bond alternation (1.393(8)–1.414(8) ꢀ),
whereas the outside rim of the flanking six-membered rings
showed clearly elongated bond lengths (1.434(7) ꢀ; see
Figure S7). Compound 3 exhibited a shallower bowl depth
(0.76 ꢀ) and smaller Haddon p-orbital axis vector angle (6.28)
as compared to sumanene (1.11 ꢀ and 8.88;[16] Figure 1b),
thus indicating less strain in trithiasumanene owing to the
larger atomic radius of the doping sulfur atoms. In the crystal,
3 forms a concave–convex dimer by p–p interactions with
a shortest bowl-to-bowl distance of 3.30 ꢀ (Figure 1c), which
Figure 2. Optical and electrochemical properties of 3–5. a) Absorption
(solid lines) and fluorescence spectra (dashed lines) of 3–5 in CH2Cl2.
b) Cyclic voltammograms of 3–5 in anhydrous CH2Cl2 containing
0.1 molmLÀ1 tetra-n-butylammonium hexafluorophosphate as the sup-
is significantly shorter than that of pristine trithiasumanene
(3.48 ꢀ),[10a] hexabutoxytriselenasumanene (3.56 ꢀ),[10b] and
sumanene (3.86 ꢀ),[16] thus implying the existence of strong
p–p interactions between the bowls.
porting electrolyte at a scan rate of 100 mVsÀ1
.
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oxidation potential (0.74 V for 3, 0.72 V for
4, and 0.69 V for 5 versus FeCp2+/0; Fig-
ure 2b) in comparison with that of coran-
nulene (1.57 V).[12b]
The curved p-surface in combination
with their electron-rich nature renders 3–5
suitable supramolecular hosts for electron-
deficient fullerene. The supramolecular
assembly of 3–5 with fullerenes in solution
was confirmed by NMR spectroscopy.
Upon the addition of an equimolar
amount of C60 to solutions of 3–5, the
proton signals of the peripheral thiol group
of 3–5 were shifted downfield by 0.037–
0.030 ppm and 0.015–0.011 ppm (Figure 3)
as a result of the deshielding effect of C60,
thus manifesting the formation of supra-
molecular complexes. Furthermore, hydro-
gen atoms Hc closer to the buckybowl
exhibited a downfield shift that was twice
as large as that of the meta and para
hydrogen atoms Hb and Ha (Figure 3), thus
suggesting that C60 locates at the concave
Figure 3. 1H NMR spectra before (blue) and after (red) the addition of C60 (1 equiv) to
a solution of 3–5 (1.9ꢀ10À3 mÀ1) in CS2/CCl2D2 (3:1).
center of trithiasumanene in the supramolecular complexes
(see below). In contrast, the addition of C60 to a solution of
pristine trithiasumanene did not result in any shifting of the
1H signal of the bowl, thus implying that multithiolation is
critical for the formation of a supramolecular complex in
solution.
neously within 2 days. In 3ꢀC60, C60 is located in the center of
the bowl without any disorder in a concave–convex relation-
ship with 3. Notably, all the peripheral aryl thiol groups of 3 in
the supramolecular complex point away from C60 (Figure 4a).
As a result, there is no direct interaction between the phenyl
groups and C60 (see Figure S15), and the concave–convex p–p
interactions between the bowl and C60 are dominant (Fig-
ure 4a; see also Figure S16). In contrast, the substituent
groups wrapped around C60 in the previously reported
To understand the assembly behavior between 3–5 and C60
further, we carried out NMR titrations and determined the
binding constants of the supramolecular complexes (Ka =
(193 Æ 26)mÀ1 for 3ꢀC60, (247 Æ
32)mÀ1 for 4ꢀC60, (395 Æ 32)mÀ1 for
5ꢀC60; see Figures S8–S13 and details
in the Supporting Information). The
binding constants of the complexes
between 3–5 and C60 are comparable
with that of pentathiolated corannu-
lene/C60 complexes.[12a] Job plot anal-
ysis revealed the formation of 1:1
complexes between 3–5 and C60 in
solution, which was exemplified by
the crystal structure of complex
3ꢀC60. The formation of supramolec-
ular complexes in solution was also
supported by fluorescence quenching
when C60 was titrated into solutions of
3–5 (see Figure S14); this behavior
indicates intermolecular charge–
transfer interactions between 3–5
and C60.
The detailed structure of the con-
cave–convex complexes was validated
Figure 4. Concave–convex supramolecular complexes of 3 and fullerenes. a) Concave–convex
complex 3ꢀC60; b) one-dimensional supramolecular chain of 3ꢀC60 along the b axis; c) concave–
convex complex 3ꢀC70; d) dimer of 3ꢀC70. The centroids of fullerenes and the hub six-membered
ring of 3 are represented as red and blue dots, respectively. The p–p interactions are represented
by cyan dotted lines. All hydrogen atoms have been omitted for clarity, and thermal ellipsoids are
set at the 30% probability level.
by single-crystal X-ray diffraction
(Supporting Information).[15] Upon
the addition of n-hexane to a solution
of 3 and C60 (1:1) in carbon disulfide,
single crystals of 3ꢀC60 grew sponta-
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complexes of thiolated corannulenes and C60.[5a,17] The UV/
Vis/NIR spectrum of 3ꢀC60 crystals showed a charge-transfer
band at 930 nm, which can be attributed to donor–acceptor
charge transfer from the bowl of 3 to C60 (see Figure S17).
However, we could not find the charge-transfer band in
solution when C60 was titrated into the solution of 3 (see
Figure S18). The shortest distance from the concave surface
of 3 to C60 is 3.22 ꢀ, and the distance from the centroid of hub
six-membered ring of 3 to the centroid of C60 is 6.65 ꢀ
(Figure 4). These distances are shorter than those observed in
an azabuckybowl/C60 complex (3.29 and 6.82 ꢀ, respective-
ly).[10e] The complex 3ꢀC60 can serve as a supramolecular
building block and pack into a one-dimensional chain through
p–p interactions between C60 cages (Figure 4b). In the one-
dimensional supramolecular chain, the shortest distance
between the surfaces and the centroids of the cages is 3.18
and 9.95 ꢀ, respectively.
Figure 5. Typical conductivity transients observed for a single crystal of
3ꢀC60 (black) and a drop-cast solid composed of a mixture of 3 and
C60 (gray). Photoexcitation was carried out by using 355 nm laser
pulses with a photon density of 1.4ꢀ1016 photonscmÀ2 pulseÀ1
.
C70 can also assemble with 3, as demonstrated by
obtaining single crystals of 3ꢀC70 (see the Supporting
Information).[15] As shown in Figure 4c, C70 sits in the concave
surface of 3 to form a concave–convex complex. The shortest
distance from the concave surface of 3 to the convex surface
of C70 is 3.15 ꢀ, and the intercentroid distance is 6.80 ꢀ, thus
demonstrating strong p–p interactions between the two
structures (Figure 4c). The peripheral thiol groups adopted
a conformation similar to that in 3ꢀC60. In contrast to 3ꢀC60,
which packs into a one-dimensional chain, 3ꢀC70 only forms
a dimer through p–p interactions (3.13 ꢀ) between C70 cages
(Figure 4c). Surprisingly, although the bowl framework was
thought to be rigid, the bowl core of 3 was slightly deeper in
both complexes as compared with that of its free form, as
evidenced by X-ray crystallography (depth of 0.76 ꢀ for 3
versus 0.83 ꢀ for 3ꢀC60 and 3ꢀC70) and the Haddon p-orbital
axis vector angle (6.28 for 3 versus and 6.68 for 3ꢀC60 and
3ꢀC70), probably to maximize the host–guest interactions.
In contrast to the ready efflorescence of 3ꢀC70 crystals,
the single crystals of 3ꢀC60 were highly stable and maintained
their crystallinity even after heating at 1208C under vacuum
for 12 h, as demonstrated by resolving the structure of an
annealed crystal of 3ꢀC60.[15] The resolved structure showed
that C60 was still assembled with 3 in a concave–convex
manner, but that the cocrystallized solvent was partially lost
after heating (see Figure S19). Interestingly, the orientation of
C60 in 3ꢀC60 was changed, whereas the conformation of 3
remained intact after vacuum annealing (see Figure S19). The
high stability of 3ꢀC60 crystals motivated us to investigate
their photoconductivity by flash-photolysis time-resolved
microwave conductivity (FP-TRMC) measurements.[7c,18]
When photoexcited with 355 nm laser pulses, a single crystal
of 3ꢀC60 mounted on a quartz rod showed isotropic transient
conductivity with prompt-rise and slow-decay features
(Figure 5; see also the Supporting Information). Its maximum
transient conductivity (fSm)max was 2.9 ꢁ 10À5 cm2 VÀ1 sÀ1
(Figure 5), which is lower than the conductivity of an
azabuckybowl/C60 complex (2.4 ꢁ 10À4 cm2 VÀ1 sÀ1).[10e] How-
ever, a reference solid, composed of a drop-cast mixture of 3
and C60 in a 1:1 molar ratio, indicated a smaller conductivity
transient: The maximum transient conductivity (fSm)max of
drop-cast mixture was 0.7 ꢁ 10À5 cm2 VÀ1 sÀ1 and thus about
one-quarter of that observed for the single crystal of 3ꢀC60
(Figure 5). This result indicates that the formation of a supra-
molecular complex can enhance charge transfer, which could
be useful in organic field-effect transistors.
In summary, a synthetic protocol for the functionalization
of trithiasumanene was developed that enabled the straight-
forward synthesis of versatile functional trithiasumanenes.
The curved and electron-rich nature of hexathiolated trithia-
sumanenes makes them suitable electron-donating hosts for
fullerene, with the formation of concave–convex supramolec-
ular complexes. The supramolecular assembly in solution was
confirmed and investigated by NMR spectroscopy and
fluorescence quenching. The structures of the supramolecular
complexes were validated unambiguously by crystallography,
which revealed close p–p interactions between trithiasuma-
nenes and fullerenes. The single crystals of 3ꢀC60 showed
remarkable thermal stability and high photoconductivity. Our
synthetic strategy in combination with supramolecular assem-
bly enables the rational design of functional trithiasumanene
structures and the construction of supramolecular architec-
tures based on functional trithiasumanene. We expect our
results to stimulate the investigation of heteroatom-doped
buckybowls in supramolecular materials, organic nanostruc-
tures, and organic electronics.
Acknowledgements
This research was supported financially by the National
Natural Science Foundation of China (21401156, U1205111,
21390390), the “Thousand Youth Talents Plan”, the 973
Project (2014CB845603), and Fundamental Research Funds
for the Central Universities from Xiamen University.
Keywords: buckybowls · fullerenes · p interactions · sulfur ·
supramolecular assemblies
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Received: July 1, 2016
Revised: August 3, 2016
Published online: && &&, &&&&
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Supramolecular Assembly
Like a hand in a glove: When decorated
with electron-donating thiol groups, tri-
thiasumanenes assembled with fuller-
enes both in solution and in the solid
state. The supramolecular complexes
were unambiguously characterized by X-
ray diffraction, which revealed their con-
cave–convex supramolecular recognition
(see picture). The crystals of the supra-
molecular complexes showed remarkable
thermal stability and high photoconduc-
tivity.
Y. M. Liu, D. Xia, B. W. Li, Q. Y. Zhang,
T. Sakurai, Y. Z. Tan,* S. Seki, S. Y. Xie,*
L. S. Zheng
&&&& — &&&&
Functional Sulfur-Doped Buckybowls and
Their Concave–Convex Supramolecular
Assembly with Fullerenes
6
www.angewandte.org
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
These are not the final page numbers!