A Three-Dimensional Capsule-like Carbon Nanocage as a Segment Model of Capped Zigzag [12,0] Carbon Nanotubes: Synthesis, Characterization, and Complexation with C70

Article abstract of DOI:10.1002/anie.201804031

Herein we report the synthesis and photophysical and supramolecular properties of a novel three-dimensional capsule-like hexa-peri-hexabenzocoronene (HBC)-containing carbon nanocage, tripodal-[2]HBC, which is the first synthetic model of capped zigzag [12,0] carbon nanotubes (CNTs). Tripodal-[2]HBC was synthesized by the palladium-catalyzed coupling of triboryl hexabenzocoronene and L-shaped cyclohexane units, followed by nickel-mediated C?Br/C?Br coupling and subsequent aromatization of the cyclohexane moieties. The physical properties of tripodal-[2]HBC and its supramolecular host–guest interaction with C₇₀ were further studied by UV/Vis and fluorescence spectroscopy. Theoretical calculations revealed that the strain energy of tripodal-[2]HBC was as high as 55.2 kcal mol^?1.

Full text of DOI:10.1002/anie.201804031

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Accepted Article
Title: A Three-Dimensional Capsule-Like Carbon Nanocage as a Novel
Segment Model of Capped Zigzag [12,0] Carbon Nanotubes:
Synthesis, Characterization, and Complexation with C70
Authors: Pingwu Du
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A Three-Dimensional Capsule-Like Carbon Nanocage as a Novel
Segment Model of Capped Zigzag [12,0] Carbon Nanotubes:
Synthesis, Characterization, and Complexation with C70
Shengsheng Cui,+a Guilin Zhuang,+b Dapeng Lu,a Qiang Huang,a Hongxing Jia,a Ya Wang,a Shangfeng
Yang,a Pingwu Du* a
unit, hexa-peri-hexabenzocoronene (HBC), as the large π-
extended sidewalls into [18]CPP and [12]CPP backbones.[9]
Besides these armchair CNT models, several chiral carbon
nanorings[10] and branched CNT segments[11] have also been
reported. Despite these intense studies, however, the study of
(n,0)-zigzag CNT segments as another important model
compound continues to be limited and no large π-extended
polyaromatic hydrocarbons (PAHs, for example, HBC unit) have
been used as the capping unit to build the segment of a capped
carbon nanotube. The chemical synthesis of finite models of
zigzag single-walled CNTs, for example, cyclacenes, still remains
a great challenge due to its highly reactive open-shell nature.[12]
Abstract: Herein we report the synthesis, photophysical, and
supramolecular properties of a novel three-dimensional capsule-
like hexa-peri-hexabenzocoronene (HBC)-containing carbon
nanocage, tripodal-[2]HBC, which represents the first synthetic
model of the capped zigzag [12,0] carbon nanotubes (CNTs).
Tripodal-[2]HBC was achieved by rationally designed
palladium-catalyzed coupling of triborylhexabenzocoronene and
L-shaped cyclohexane units, followed by nickel-mediated C-
Br/C-Br coupling and the subsequent aromatization of the
cyclohexane moieties. The physical properties of tripodal-
[2]HBC and its supramolecular host-guest interaction with C70
were further studied by UV-vis and fluorescence spectroscopy.
Theoretical calculations reveal that the strain energy of tripodal-
[2]HBC is as high as 55.2 kcal
mol-1.
Carbon nanotubes (CNTs) have attracted much attention over
the last few decade due to their interesting physical and electronic
properties,[1] which greatly depend on their size, edge structure,
and chirality.[2] So far, It is still a great challenge to achieve
controlled synthesis of CNTs.[3] To mimic the segment models of
CNTs, organic molecules with hoop-shaped π-conjugated
systems have gained a great deal of attention due to their
interesting curved structures and physical properties.[4]
Cycloparaphenylenes (CPPs), the simplest structural unit of
armchair carbon nanotubes, are envisioned as precursors for the
bottom-up synthesis of armchair CNTs with a fixed chirality and
diameter.[4a,5] In 2003, using a top-down strategy by detraction of
the conjugated system of [60]fullerene, the successful synthesis
of a cyclic benzenoid [10]cyclophenacene as a segment model of
(5,5)-armchair SWNTs was reported.[6] Since 2008, a variety of
[n]CPP nanorings (n=5-18) have been reported by using different
bottom-up approaches.[7] Subsequently, the congeneric armchair
variants began quickly to flourish.[8] The Müllen group reported a
pre-construction strategy to insert large π-extended sidewalls into
CPPs.[8a] Owing to the difficulty of directly functionalizing CPPs to
create a fully π-extended CNT sidewall segment, our group
developed a post-construction method to insert a nanographene
Figure 1. The design of tripodal-[2]HBC carbon nanocage as a
novel finite model of capped [12,0] carbon nanotube.
Herein we report the synthesis of a novel three-dimensional
capsule-like large π-conjugated molecule, tripodal-[2]HBC which
represents the zigzag [12,0] CNT model with two large polycyclic
aromatic hydrocarbon end caps (Figure 1). Unlike the previously
reported sidewall type segments in the infinite CNT structures,
this molecule is the first example of a closed CNT model with a
fixed length by connecting two end caps with three olig(para-
phenylene) rims symmetrically. Our synthesis involves the
construction of one key building precursor, namely tripodal HBC
units, and the subsequent cyclic assembly through transition
metal mediated multi-fold coupling reactions. The resulting
molecule was characterized by mass spectrometry (MALDI-TOF-
MS) combined with nuclear magnetic resonance (NMR)
spectroscopy. In addition, its photophysical and electronic
properties were investigated by steady-state spectroscopy and
theoretical calculations.
[a]
S. Cui,[+] D. Lu, Q. Huang, H. Jia, Y.Wang, Prof. S. Yang, Prof. P.
Du
Hefei National Laboratory for Physical Sciences at Microscale, CAS
Key Laboratory of Materials for Energy Conversion, Department of
Materials Science and Engineering, iChEM (Collaborative
Innovation Center of Chemistry for Energy Materials), University of
Science and Technology of China (USTC)
Hefei, Anhui Province 230026 (China)
The HBC unit with mesityl groups is a good building block
because of its high solubility in most common organic solvents,
which was firstly reported by Shinokubo and co-workers.[13]
Mesityl groups can be introduced at the HBC periphery by the
E-mail: dupingwu@ustc.edu.cn
[b]
Prof. G. Zhuang[+]
coupling of 1,3,5-tri(3′-chlorobiphen-2-yl)benzene
3 with 2-
College of Chemical Engineering, Zhejiang University of
Technology, 18, Chaowang Road, Hangzhou, Zhejiang Province
310032 (China)
mesitylmagnesium bromide, followed by cyclodehydrogenation
with dry FeCl3 (see details in supporting information). It is worth to
mention that the cyclic product of HBC cannot be realized when
the cyclodehydrogenation reaction is conducted after cyclization,
[+]
contributed equally to this work
studies.[8a,8c,14]
The
Supporting information for this article is given via a link at:
http://onlinelibrary.wiley.com.
as
was
shown
in
previous
cyclodehydrogenation step might be quite difficult due to high ring
strain resulting from macrocyclization and the resulting
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complicated mixtures will make the subsequent separation and
purification problematic. Therefore, it is better to conduct
cyclodehydrogenation reaction prior to the macrocyclization
reaction. Then the trimesityl-substituted HBC 5 was subsequently
converted into the 2,8,14-triborylated trimesityl HBC 6 (Figure 2)
by treatment with an excess amount of bis(pinacolato)diboron
(6.0 equiv.) under iridium-catalyzed borylation conditions.[13] This
convenient protocol for the introduction of boryl groups into π-rich
hydrocarbons through direct C-H borylation provides a reliable
method for the preparation of large quantities of meta-borylated
trimesityl HBC, which is a key precursor for the synthesis of
tripodal HBC units.
the HBC fragment in the backbone of the building precursor
probably have a deleterious effect on the conformation for
cyclization, since the yield for this step is relatively low.
Subsequently, the crude product
9
obtained via the
macrocyclization step was directly subjected to aromatization
without thorough purification. The cyclohexane-1,4-diyl moieties
were facilely converted to the corresponding benzene rings with
NaHSO4H2O in mixed DMSO and m-xylene at 150 °C for 2 days
in air. After extensive purification initially by flash column
chromatography and then by preparative thin layer
chromatography, the target molecule 10 was obtained in ~8 %
yield over two steps as a yellow solid.
1
This target compound 10 was characterized by H NMR, and
MALDI-TOF mass spectrometry, and elemental analysis. Its
isotopic mass peak pattern obtained in the high resolution MALDI-
TOF mass spectrometry was in good agreement with the
simulated values (Figure 3a, observed at m/z 3117.2997,
calculated for C246H162 [M]+: 3117.2944). Further characterization
by 1 H NMR spectroscopy confirmed the successful synthesis of
10 (see SI).
Figure 3. (a) MALDI-TOF MS and (b) Expanded 2D 1H-1H COSY
NMR spectrum (400 MHz, CD2Cl2) of tripodal-[2]HBC.
Figure 2. Synthesis procedures of meta-triborylated trimesityl
HBC 6 precursor and tripodal-[2]HBC 10.
The characteristic singlets at δ = 9.58 ppm and 9.29 ppm should
be assigned to protons in the HBC units (a and b type protons in
Figure 3b), on the basis of anisotropy effect of the HBC
structure.[13,15] Another six doublets from δ = 8.23 to δ = 7.49 are
rooted in the benzene rings which connect two HBC units after
the acid-mediated aromatization of compound 9. In addition, the
singlet at δ = 7.19 and the singlets at δ = 2.48 ppm and δ = 2.31
ppm should be assigned to the mesitylene unit and methyl groups,
respectively, verifying the highly symmetric character of the
nanocage structure. To fully assign the aromatic protons in
The synthesis procedure of the tripodal-[2]HBC 10 is also
illustrated in Figure 2. The L-shaped building block 7 was
prepared by addition of 4-bromophenyllithium into cyclohexane-
1,4-dione solution, followed by protection of the hydroxyls using
the methoxymethyl (MOM) groups.[7c] The next step was
performed to construct the tripodal HBC-containing building block
8. The yellow solid 8 can be prepared in a high yield of 68% by
the Suzuki-Miyaura cross-coupling reaction of triboryltrimesityl
HBC 6 (1 equiv.) with an excess amount of 7 (12 equiv.) in the
presence of Pd(dppf)Cl2 catalyst (8.75 mol%), K2CO3 (12 equiv.),
and anhydrous DMF at 90 °C for 48 h under nitrogen atmosphere.
Next, the Ni(cod)2-mediated Yamamoto coupling reaction was
applied for the synthesis of 9 in the presence of 8 (1 equiv.),
Ni(cod)2 (6.0 equiv.), 1,5-cyclooctadiene (0.1 mL), and 4,4′-di-tert-
butyl-2,2′-bipyridyl (6.0 equiv.) in dry DMF at 90 °C for 72 h under
nitrogen atmosphere.[13,15] The good planarity and high rigidity of
1
tripodal-[2]HBC 10. 2D H-1H COSY NMR spectrum was further
measured and the results are shown in Figure 3b. The singlet at
δ = 9.29 exhibits a correlation relationship with proton signal at δ
= 8.23, suggesting that proton at δ = 9.29 can be assigned to b
site and the doublet δ = 8.23 belongs to c site. Moreover, this
proton signal at δ = 8.23 is strongly correlated with the proton at
δ = 7.95, confirming the latter is ascribed to d site. Based on the
same analysis, all other aromatic peaks (d, e, f, g, and h protons)
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can be well assigned. As a result, 1H NMR, 2D 1H-1H COSY NMR
spectra, and the mass spectrometry confirmed the successful
synthesis of tripodal-[2]HBC.
at the PBE/DNP theoretical level using DMol3 software.[17] The
geometrical optimization result shows that the cage structure of
tripodal-[2]HBC 10 has the cavity of c.a. 10.5 Å (Figure S2).
Specifically, six trimethyl-benzol groups generate torsion angles
averaging 64.4o with top or bottom aromatic moieties, while a
torsion angle averaging 32.3o appears on the three para-linked
aromatic chains. As shown in Figure 5, the frontier molecular
orbital results indicate that HOMO mainly involves π-type bonding
orbitals on the top and bottom HBC moieties, while LUMO mainly
concentrates on π-type anti-bonding orbitals on one longitudinal
aromatic chain and two caps. Furthermore, following two reported
methods[7c,18] (Figure S3), the strain energy is estimated to be
55.20 kcalmol-1, compatible with the accepted value for
cycloparaphenylenes.[18]
Furthermore,
the
single-point
calculations under the level of B3LYP/6-31G* reveal that the
HOMO-LUMO gap of 3.19 eV (389 nm) is close to the
experimentally observed longest-band of 402 nm.
Figure 4. (a) UV-vis absorption (solid lines) and fluorescence
spectra (dash lines) of tripodal-[2]HBC (blue) and trimesityl-
triphenyl HBC (red) in CH2Cl2. (b) The photograph of the
fluorescence of tripodal-[2]HBC in CH2Cl2 under a UV lamp (365
nm).
UV-vis absorption spectroscopy and steady-state fluorescence
spectroscopy were used to investigate the photophysical
properties of tripodal-[2]HBC 10 (Figure 4a, blue plot). For
comparison, we synthsized trimesityl-triphenyl HBC as the
reference compound (see details in supporting information), the
spectra of trimesityl-triphenyl HBC was also depicted in Figure 4a
(red plot). The absorption bands of 10 in dichloromethane are
observed at 300-430 nm and the absorption maximum peak (λmax
)
is observed at 374 nm with the molecular absorption coefficient
(ε) of ~1 × 105 cm-1 M-1. Two moderate absorption peaks were
also observed with maxima at λmax = 358 nm and 402 nm. It is
noteworthy that the λmax of the absorption bands have obvious
redshift in comparison with the reference compound (trimesityl-
triphenyl HBC) and those of other three-dimensional π-
conjugated molecule.[11,16] This can be ascribed to a much larger
π conjugation in the graphenic HBC units of the molecular
structure. The fluorescence emission spectrum of 10 was studied
at room temperature under an excitation of 350 nm. Multiple
emission peaks were observed at 480 nm, 503 nm, and 536 nm,
respectively, which also have redshift compared to the reference
compound. The fluorescence quantum yield was determined to
be ФF = 17.1% using anthracene in ethanol as the reference (ФF
= 30%). This value is higher than that of trimesityl-triphenyl HBC
(ФF = 14.3%), which might be due to the effect of the larger π
conjugation after aromatization. Compound 10 shows intense
green photoluminescence in CH2Cl2 solution under UV irradiation
(Figure 4b).
Figure 5. HOMO (a-b) and LUMO (c-d) of tripodal-[2]HBC with
top view and side view.
Considering the concave cavity of tripodal-[2]HBC 10, it could
act as a supramolecular host for π-conjugated molecules with a
convex surface, such as fullerenes. We next investigated the
supramolecular host-guest interaction behavior between tripodal-
[2]HBC and fullerene C60 and C70. Note that no appreciable
change was observed when mixing C60 with tripodal-[2]HBC 10.
Interestingly, the supramolecular interaction between 10 and C70
was clearly observed. The interaction between 10 and C70 was
initially studied by MS spectrometry (Inset, Figure 6a). The peak
observed at m/z 3958.2807 (calculated for C316H162 [C70@10]+:
3958.2777) suggests the formation of a 1:1 complex. The
Fluorescence decay measurements were performed using a
nanosecond pulsed laser system in degassed CH2Cl2 solution at
room temperature. The fluorescence decay of 10 follows first-
order kinetics with a lifetime (τs) = 16.1 ns at 503 nm with single-
exponential decay when excited at ~390 nm (Figure S1a). For
comparison, trimesityl-triphenyl HBC shows a similar single-
exponential decay with τs = 18.0 ns at 495 nm under the same
excitation wavelength (Figure S1b). The fluorescence lifetime of
10 is longer than other three-dimensional π-conjugated molecule
(τs = 1.4 ns for [6.6.6] carbon nanocage[11] and τs = 2.1 ns for ball-
like π-conjugated molecule[16]). Taking the long fluorescence
lifetime of HBC unit into consideration, the inserted HBC could
contribute to the long fluorescence lifetime of 10.9b
interaction
between
tripodal-[2]HBC
and
C70
was
1
further observed by H NMR spectroscopy when C70 was added
to tripodal-[2]HBC in CD2Cl2 (Figure S4). The complexation
between tripodal-[2]HBC and C70 was further examined by the
UV-vis titration experiment and an isosbestic point located at 423
nm was observed (Figure 6a). When C70 was added into a
solution of 10 in dichloromethane, the solution exhibited an
obvious color change from yellow to light brown (Figure 6b). The
resulting Job’s plot of the UV-vis spectra at 374 nm in toluene
showed a maximum absorption change when the ratio of tripodal-
[2]HBC and C70 reached approximately 1:1 (Figure 6c), confirming
their 1:1 complexation. Based on the UV-vis titration experiments
(Figure S5), we determined the binding constant Ka of the tripodal-
[2]HBC with C70 in toluene to be ~1.06 × 105 M-1 (Figure 6d). This
Ka agrees well with the value obtained from the fluoresence
To further understand the physical properties of the present
capsule-like carbon nanocage, we optimized the structure of
tripodal-[2]HBC 10 by density functional theory (DFT) calculations
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×
105 M-1, Figure S6) within
Soc. 1986, 108, 2932-2938. c) S. Kammermeier, P. G. Jones, R.
Herges, Angew. Chem. Int. Ed. 1996, 35, 2669-2671; Angew.
Chem. 1996, 108, 2834-2836; d) T. Kawase, H. R. Darabi, M.
Oda, Angew. Chem. Int. Ed. 1996, 35, 2664-2666;
Angew. Chem. 1996, 108, 2803-2805.
titration experiment (~1.03
experimental error.
[5] E. H. Fort, L. T. Scott, J. Mater. Chem. 2011, 21, 1373-1381.
[6] E. Nakamura, K. Tahara, Y. Matsuo, M. Sawamura, J. Am. Chem.
Soc. 2003, 125, 2834-2835.
[7] Selective references: a) R. Jasti, J. Bhattacharjee, J. B. Neaton,
C. R. Bertozzi, J. Am. Chem. Soc. 2008, 130, 17646-17647; b) E.
R. Darzi, T. J. Sisto, R. Jasti, J. Org. Chem. 2012, 77, 6624-6628;
c) H. Takaba, H. Omachi, Y. Yamamoto, J. Bouffard, K. Itami,
Angew. Chem. Int. Ed. 2009, 48, 6112-6116; Angew. Chem.
2009, 121, 6228-6232; d) S. Yamago, Y. Watanabe, T. Iwamoto,
Angew. Chem. Int. Ed. 2010, 49, 757-759; Angew. Chem. 2010,
122, 769-771; e) T. Iwamoto, Y. Watanabe, Y. Sakamoto, T.
Suzuki, S. Yamago, J. Am. Chem. Soc. 2011, 133, 8354-8361.
[8] a) F. E. Gölling, M. Quernheim, M. Wagner, T. Nishiuchi, K.
Müllen, Angew. Chem. Int. Ed. 2014, 53, 1525-1528; Angew.
Chem. 2014, 126, 1551-1554; b) T. Iwamoto, E. Kayahara, N.
Yasuda, T. Suzuki, S. Yamago, Angew. Chem. Int. Ed. 2014, 53,
6430-6434;
Angew.
Chem.
2014,
126,
6548-6552; c) M. Quernheim, F. E. Golling, W. Zhang, M.
Wagner, H. J. Rader, T. Nishiuchi, K. Müllen, Angew. Chem. Int.
Ed. 2015, 54, 10341-10346; Angew. Chem. 2015, 127, 10482-
10487; d) T. Matsuno, S. Kamata, S. Hitosugi, H. Isobe, Chem.
Sci. 2013, 4, 3179; e) K. Okada, A. Yagi, Y. Segawa, K. Itami,
Chem. Sci. 2017, 8, 661-667; f) T. J. Sisto, X. Tian, R. Jasti, J.
Org. Chem. 2012, 77, 5857-5860.
Figure 6. (a) UV-vis spectra of tripodal-[2]HBC and C70 at different
ratios in toluene for Job’s plot analysis. Insert: mass spectrometry
data for the C70@tripodal-[2]HBC complex. (b) Schematic drawing
of the C70@tripodal-[2]HBC complex. (c) Job’s plot of tripodal-
[2]HBC and C70. (d) The plot of the absorption changes at 470 nm
versus [C70] in toluene for calculating the Ka. R2 is the standard
deviation.
[9] a) D. P. Lu, H. T. Wu, Y. F. Dai, H. Shi, X. Shao, S. F. Yang, J. L.
Yang, P. W. Du, Chem. Commun. 2016, 52, 7164-7167; b) D. P.
Lu, G. L. Zhuang, H. T. Wu, S. Wang, S. F. Yang, P. W. Du,
Angew. Chem., Int. Ed. 2017, 56, 158-162; Angew. Chem. 2017,
129, 164-168; c) D. P. Lu, S. S. Cui, P. W. Du, Synlett 2017, 28,
1671-1677.
[10] a) H. Omachi, Y. Segawa, K. Itami, Org. Lett. 2011, 13, 2480-
2483; b) S. Hitosugi, W. Nakanishi, T. Yamasaki, H. Isobe, Nat.
Commun. 2011, 2, 492; c) S. Hitosugi, T. Yamasaki, H. Isobe, J.
Am. Chem. Soc. 2012, 134, 12442-12445.
[11] a) K. Matsui, Y. Segawa, T. Namikawa, K. Kamada, K. Itami,
Chem. Sci. 2013, 4, 84-88; b) K. Matsui, Y. Segawa, K. Itami, J.
Am. Chem. Soc. 2014, 136, 16452-16458.
[12] R. Gleiter, B. Esser, S. C. Kornmayer, Acc. Chem.Res. 2009, 42,
1108-1116.
In conclusion, we have successfully synthesized a three-
dimensional, capsule-like carbon nanocage tripodal-[2]HBC 10 as
a segment model compound of capped [12,0] carbon nanotubes.
A straightforward method was developed for the nanocage
construction using three L-shaped diphenylcyclohexane
monomers to connect two HBC units. This synthesis strategy
provides a rational route for the bottom-up construction of three-
dimensional π-conjugated carbon nanocage. Further challenges,
including designing and synthesizing large π-extended carbon
nanocages more similar to capped CNT segments are the focus
of ongoing work in our laboratory.
[13] R. Yamaguchi, S. Hiroto, H. Shinokubo, Org. Lett. 2012, 14,
2472-2475.
[14] T. Nishiuchi, X. L. Feng, V. Enkelmann, M. Wagner, K. Müllen,
Chem. - Eur. J. 2012, 18, 16621-16625.
Acknowledgements
[15] a) M. F. Semmelhack, P. M. Helquist, L. D. Jones, J. Am. Chem.
Soc. 1971, 93, 5908-5910; b) Y. Segawa, S. Miyamoto, H.
Omachi, S. Matsuura, P. Senel, T. Sasamori, N. Tokitoh, K. Itami,
Angew. Chem. Int. Ed. 2011, 50, 3244-3248; Angew. Chem.
2011, 123, 3302-3306; c) A. Yagi, Y. Segawa, K. Itami, J. Am.
Chem. Soc. 2012, 134, 2962-2965.
[16] E. Kayahara, T. Iwamoto, H. Takaya, T. Suzuki, M. Fujitsuka, T.
Majima, N. Yasuda, N. Matsuyama, S. Seki, S. Yamago, Nat.
Commun. 2013, 4. 2694.
This work was financially supported by the National Key Research
and Development Program of China (2017YFA0402800), the
National Natural Science Foundation of China (51772285,
21473170), and the Fundamental Research Funds for the Central
Universities.
Keywords: nanocapsule • polyaromatic hydrocarbons • π-
extended • carbon nanotube segment • three-dimensional
[17] a) B. Delley, J. Chem. Phys. 1990, 92, 508-517; b) B. Delley, J.
Chem. Phys. 1991, 94, 7245-7250; c) B. Delley, J. Chem. Phys.
2000, 113, 7756-7764.
[1] a) M. S. Dresselhaus, G. Dresselhaus, J. C. Charlier, E.
Hernández, Philos. Trans. R. Soc. London, Ser. A 2004, 362,
2065-2098; b) L. Yu, C. Shearer, J. Shapter, Chem. Rev. 2016,
116, 13413-13453.
[18] Y. Segawa, H. Omachi, K. Itami, Org. Lett. 2010, 12, 2262-2265.
[2] S. Louie, in Carbon Nanotubes, Vol. 80, Chapter 6 (Eds.: M.
Dresselhaus, G. Dresselhaus, P. Avouris), Springer Berlin
Heidelberg, 2001, pp. 113-145.
[3] F. Yang, X. Wang, M. Li, X. Liu, X. Zhao, D. Zhang, Y. Zhang, J.
Yang, Y. Li, Acc. Chem. Res. 2016, 49, 606-615.
[4] a) R. Friederich, M. Nieger, F. Vögtle, Chem. Ber. 1993, 126,
1723-1732; b) J. E. Mcmurry, G. J. Haley, J. R. Matz, J. C. Clardy,
G. Vanduyne, R. Gleiter, W. Schafer, D. H. White, J. Am. Chem.
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Entry for the Table of Contents
COMMUNICATION
For the first time, three-
dimensional capsule-like hexa-
peri-hexabenzocoronene
Shengsheng
Cui,†a
Guilin
Zhuang,†b Dapeng Lu,a Qiang
Huang,a Hongxing Jia,a Ya
(HBC)-containing
carbon
Wang,a
Shangfeng
Yang,a
nanocage was successfully
synthesized and isolated, which
represents a novel synthetic
model of the capped zigzag
[12,0] carbon nanotubes. The
photophysical properties and
supramolecular interaction with
C70 of the capsule were
Pingwu Du* a
Page No. – Page No.
A Three-Dimensional Capsule-
Like Carbon Nanocage as a
Novel Segment Model of
Capped Zigzag [12,0] Carbon
Nanotubes:
Characterization,
Synthesis,
and
investigated.
Theoretical
calculations reveal that that its
strain energy is as high as 55.2
kcalmol-1.
Complexation with C70
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