Functionalized coronenes: Synthesis, solid structure, and properties

Article abstract of DOI:10.1021/jo302093t

The construction of coronenes using simple building blocks is a challenging task. In this work, triphenylene was used as a building block to construct functionalized coronenes, and their solid structures and optoelectronic properties were investigated. Th

Full text of DOI:10.1021/jo302093t

Note
pubs.acs.org/joc
Functionalized Coronenes: Synthesis, Solid Structure, and Properties
Di Wu,† Hua Zhang,† Jinhua Liang,† Haojie Ge,† Chunyan Chi,‡ Jishan Wu,‡ Sheng Hua Liu,*,†
and Jun Yin*,†
†Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University,
Wuhan 430079, PR China
‡Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
S
* Supporting Information
ABSTRACT: The construction of coronenes using simple
building blocks is a challenging task. In this work, triphenylene
was used as a building block to construct functionalized
coronenes, and their solid structures and optoelectronic
properties were investigated. The single crystal structures
showed that coronenes have different packing motifs. Their
good solubility and photostability make them potential
solution-processable candidates for organic devices.
raphene (I) has been widely applied in optoelectronic
materials since it was first isolated from graphite by Geim
As shown in Scheme 1, triphenylene (IV) is one of the
segments that can be used to construct coronene. In view of the
convenience of its preparation from substituted benzene (V),18
the use of triphenylene as a building block to construct
coronenes offers a convenient and promising approach to
advance the functionalization of coronenes. Some reports have
indicated that biphenyl acetylenes or phenanthrene-based
acetylenes can be cyclized to form aromatic rings in the
presence of catalysts such as gold, ruthenium, platinum, and ICl
(Scheme 2A).19 Herein, we used triphenylene as a building
block to construct functionalized coronenes with good yields
and investigated their solid structures and optoelectronic
properties.
The synthesis of 1a−c is outlined in Scheme 2B. The
intermolecular oxidative cyclodehydrogenation reaction of 2
can facilely generate 3, which was bromated using bromine to
give 4.20 Subsequently, the palladium-catalyzed Sonogashira
coupling reaction was performed to give 5a−c in ∼50−54%
yields, and 5a−c was subjected to a PtCl2-promoted cyclization
to afford 1a−c with 52−57% yields. The chemical structures of
all new compounds were clearly supported by standard
spectroscopic characterizations such as NMR and mass
spectrometry (see Supporting Information).
G
and Novoselov et al. in 2004.1 Polycyclic aromatic hydro-
carbons (PAHs), which make up graphene segments, have large
π-conjugated systems and hence are often regarded as
promising building blocks for the construction of organic
semiconducting materials.2 Hexa-peri-hexabenzocoronene
(HBC, II) is a typical graphene fragment3 with a D6h-
symmetrical structure and displays outstanding performance
in liquid crystal materials due to its strong intermolecular π−π
interactions and highly ordered columnar packing.4 Although
HBC consists of 13 fused benzene rings, there are more than
five strategies to efficiently synthesize functionalized HBCs.5
Coronene (III) can be regarded as a smaller graphene fragment
compared to HBC; it has a unique electronic structure due to
the perfect delocalization of the aromaticity among the six outer
rings (Scheme 1).6 In comparison to HBC, coronene as the
smallest homologue of benzene with 6-fold symmetry is useful
and essential for the film formation and crystallization of
molecules.7 Recently, chemists realized the advantages of
smaller π-conjugated coronene and have developed several
coronene-based optoelectronic materials.7,8 Some methods that
are based on different building blocks have been developed for
the synthesis of coronenes. For example, early synthetic
protocols were reported by Newman in 1940,9 Baker in
1951,10 Clar in 1957,11 Craig in 1975,12 and Reiss in 1977,13
but they typically suffered from lengthy procedures, low yields,
and poor functionalization. In recent years, tremendous efforts
have been made to develop new synthetic strategies, including
the cyclization of perylene-based dianions,14 ruthenium-
catalyzed benzannulation,15 Diels−Alder reactions based on
perylene-3,4:9,10-bis(dicarboximide)s (PDI) with dienophi-
les,8d,g,16 and the cyclization of 1,7-bis(alkynyl)-substituted
PDI.8a,c,e,17 However, the construction of coronenes using
simple starting materials or novel building blocks remains
challenging.
The 1H NMR spectra of 5a−c revealed three different
resonance signals at 9.14−9.48 ppm, indicating that three
protons were unsymmetrical. The structures were further
identified using X-ray crystallographic analysis. A single crystal
of 5a suitable for crystallographic analysis was grown using the
diffusion of MeOH to a CH2Cl2 solution of 5a. As depicted in
Figure 1A (left), three acetylenyl benzene units were attached
on two benzene rings of the triphenylene core. Despite the
well-known fact that triphenylene has a completely planar
Received: September 24, 2012
Published: November 27, 2012
© 2012 American Chemical Society
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The Journal of Organic Chemistry
Note
Scheme 1. Constructing Fragments of Grapheme
Scheme 2. (A) Cyclization of Acetylenes; (B) Synthesis of Compounds 1a−c
configuration,21 the molecule will be twisty when the
1,4,5,8,9,12-positions of triphenylene are substituted, even by
small groups such as a methyl group.22 The single-crystal
structure of 5a displayed a contorted structure in the side view
(middle) shown in Figure 1A; this was attributed to the large
steric hindrance caused by the substituted groups on the
triphenylene. Additionally, the molecules involved in the π−π
interactions and C−H···π, C−H···O hydrogen bonds (see
Figure S1 in Supporting Information) led to the ordered
packing shown in Figure 1A (right).
1
In the H NMR spectra for 1a−c, the resonance of the
coronene core displayed 0.15−0.46 ppm upfield shifts
compared with the triphenylene core of 5a−c, and only two
peaks could be observed because of the overlapping of the
proton signals. Single crystals of 1a and 1c suitable for
crystallographic analysis were obtained using a method similar
to that used for 5a. As shown in Figure 1B and C, the coronene
cores presented an absolutely flat structure. Again, distinct
dihedral angles were found between the phenyl moieties and
the coronene plane, as a result of the steric effects of the
functionalized groups. Both molecules were packed in a one-
dimensional columnar structure, and the average distances
between the coronene discs were 4.41−4.79 Å.23 This showed
that there were no obvious π−π interactions involved in the
Figure 1. Single crystal structures and packing views of 5a (A), 1a (B),
and 1c (C). Top, side, and packing view from left to right. Hydrogen
atoms have been omitted in packing views.
molecular packing, in contrast with Mullen’s report.7 In that
̈
case, weak π−π interactions were observed, due to the smaller
substituted groups (-OCH3) on the coronene core. Alter-
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The Journal of Organic Chemistry
Note
natively, the C−H···π interaction and C−H···O hydrogen bond
promoted ordered packing (Figures S2 and S3 in Supporting
Information). Interestingly, two distinct intercolumn packing
modes were observed for 1a and 1c (Figure 1B and C (right)).
1a displayed lamellar packing, whereas 1c formed a
herringbone-like packing motif. The slight structural change
produced by the introduction of three methoxyl units into 1c
resulted in an obvious change in the packing form. It is well-
known that molecular stacking is very important for the
properties of a material.24 Hence, this result afforded an
alternative approach to explore organic optoelectronic materials
via the simple decoration of their structure. In addition, we
used density functional theory (DFT) to optimize their
structures at the B3LYP/6-31G* level in a suite of Gaussian
09 programs. It is worth noting that the results showed good
agreement with the crystal structures of 1a and 1c (Figures S4
and S6 in Supporting Information). Despite the fact that a
single crystal of 1b was not obtained, it can be easily predicted
that 1b possessed a similar geometry (Figure S5 in Supporting
Information). The crystal data and structural refinements of
these molecules are summarized, and the bond lengths and
angles are listed in the Supporting Information (Tables S1−
S6).
with a long-wavelength absorption maximum at 375 nm (p
band, εmax = 1.06 × 105 M−1 cm−1) in CH2Cl2, which suggested
that the introduction of the three phenyl moieties led to an
extended π-conjugation and a red shift of the absorption
spectrum.
Similar phenomena were also observed for the absorption
spectra of 1a and 1c from 300 to 500 nm (Figure S7 in
Supporting Information). These results were in agreement with
a previous report.7 Their UV−vis absorption spectra were also
measured in the thin-film state. As can be seen in Figure 2 and
Table 1, these compounds revealed similar absorption spectra.
However, the spectra for the thin films were broader than those
measured in solution, indicating that the chromophores had a
strong tendency to aggregate in the solid state. We also
measured their photoluminescence spectra, which exhibited a
0.95 eV Stokes shift and similar emission (excited at 345 nm,
Figure 2). The lower fluorescence quantum yields for 1a−c
(0.098, 0.094, 0.089) could have been due to the symmetric
cyclic conjugated structure. It is surprising that 1a−c possessed
very similar optical properties not only in the solution state but
also in the thin film state; this indicated that the different
substituents (H, Me, and OMe) on the benzene rings had only
small effects on their optical properties. The optical energy gaps
(Eg) of ∼3.02−3.07 eV were calculated from the low-energy
absorption onset in the absorption spectra, as shown in Table 1.
The electrochemical properties of these coronenes were
investigated using cyclic voltammetry (CV). The measurements
were carried out in dry dichloromethane at room temperature.
As shown in Figure 3, two quasi-reversible oxidation waves
Because of the presence of alkoxyl chains, these molecules
showed very good solubility in common solvents. This good
solubility allowed them to be processed in solution and allowed
the formation of thin films. The optical properties were
investigated using UV−vis absorption and fluorescence
spectrometry. Figure 2 shows the UV−vis absorption and
Figure 2. Normalized UV−vis absorption and photoluminescence
spectra of 1b in CHCl3 (1.0 × 10−5 M) and in thin film.
Figure 3. Cyclic voltammogram (CV) of coronenes 1a−c in dry DCM
with 0.1 M Bu4NPF6 as supporting electrolyte.
fluorescence spectra for 1b. Compared with the p band at 342
nm (ε = 7.08 × 104 M−1 cm−1) for nonsubstituted coronene,25
1b showed well-resolved absorption bands at 323 and 345 nm,
were observed for 1a−c in the range from 0.50 to 1.00 V.
Again, the changes in the substituted groups on the benzene
Table 1. Optical and Electrochemical Data of Coronenes 1a−c
b
εmax
a
a
c
d
e
f
compd
λAbs [nm]
λmax (PL) [nm]
[M−1cm−1
]
Eox1 [V] Eoxonset [V] HOMO [eV] LUMO [eV] Eg [eV] Eg [eV]
321, 345, 375 (solution)
320, 347, 375 (film)
470, 498, 534 (solution)
467, 496, 526 (film)
1a
101900
0.84
0.88
0.78
0.68
0.65
0.63
−5.48
−5.45
−5.43
−2.44
−2.38
−2.41
3.07
3.07
3.02
3.65
3.64
3.61
323, 345, 375 (solution)
324, 347, 375 (film)
472, 498, 536 (solution)
472, 494, 528 (film)
1b
1c
105700
112400
327, 347, 377 (solution)
325, 349, 377 (film)
474, 501, 540 (solution)
464, 492, 526 (film)
a
b
c
Wavelength of absorption and photoluminescence in CHCl3 (1.0 × 10−5 M). Molar extinction coefficient. HOMO energy levels were calculated
d
e
from the onset of the first oxidation according to the equation HOMO = −(4.8 + Eoxonset) eV. LUMO = HOMO + Eg. Eg was calculated from the
low-energy absorption onset in the absorption spectra according to the equation Eg = 1240/λonset
26
f
.
Obtained from theoretical caculation by DFT.
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rings had little effect on the redox behavior of the coronenes
1a−c (also see data in Table 1). For example, compound 1c
showed two quasi-reversible oxidation waves at 0.78 and 1.21 V
(vs Fc/Fc+). However, no obvious reduction waves were
observed upon a cathodic scan down to −2.0 V. HOMO energy
levels of −5.48, −5.45, and 5.43 eV were estimated for 1a−c,
respectively, based on the onset potential (Eox1) of the first
oxidation waves. The LUMO energy levels of 1a−c were
calculated on the basis of the equation described in Table 1.26
From these calculated LUMO levels, we determined that the
compounds 1a−c had similar HOMO and LUMO energy
levels because of the small contribution of the substituted
groups to the frontier orbitals. To gain a better insight into the
molecular orbitals of 1a−c, the structures and frontier
molecular orbital profiles of these coronene molecules were
optimized by DFT calculations at the B3LYP/6-31G* level in a
suite of Gaussian 09 programs (Figure S4−S6 in Supporting
Information). Figure 4 presents the frontier molecular orbital
worthy of note that successful multiple cyclization can be used
to build novel organic conjugated molecules.
EXPERIMENTAL SECTION
■
General Methods. All manipulations were carried out under an
argon atmosphere by using standard Schlenk techniques, unless
otherwise stated. All commercials were used as received without
further purification. 1H and 13C NMR spectra were collected on a 400
or 600 MHz spectrometer. UV−vis and fluorescence spectra were
obtained on a UV or fluorescent spectrophotometer, respectively.
Mass spectra were measured in the MALDI-TOF mode. The crystal
structure was recorded by X-ray diffraction spectrometer. Cyclic
voltammetry (CV) was performed on a potentiostat. Elemental
analyses were performed by investigation of C, H, N. A three-electrode
one-compartment cell was used to contain the solution of complexes
and supporting electrolyte in dry CH2Cl2. Deaeration of the solution
was achieved by bubbling argon through the solution for about 10 min
before measurement. The ligand and electrolyte (n-Bu4NPF6)
concentrations were typically 0.001 and 0.1 M, respectively. A 500
μm diameter platinum disk working electrode, a platinum wire counter
electrode, and an Ag/Ag+ reference electrode were used. The Ag/Ag+
reference electrode contained an internal solution of 0.01 M AgNO3 in
acetonitrile and was incorporated into the cell with a salt bridge
containing 0.1 M n-Bu4NPF6 in CH2Cl2. All electrochemical
experiments were carried out under ambient conditions. The
theoretical calculation in the present studies were performed at the
B3LYP/6-31G* level by using the Gaussian 03 program.
General Synthetic Procedure for 5a−c. A suspension of 1,4,8-
tribromo-2,3,6,7,10,11-hexabutoxytriphenylene (2.0 mmol), Pd-
(PPh3)4 (0.1 mmol), and CuI (0.08 mmol) in a mixture of THF
and Et3N (50 mL each) was degassed with nitrogen for 15 min at
room temperature. Phenylacetylene (6.0 mmol) in THF(50 mL) that
was degassed with nitrogen was added to the mixture dropwise with
stirring. The mixture was stirred at reflux for 12 h, and then the
versatile solvents were removed under reduced pressure. The residue
was purified by column chromatography packed with silica gel using
dichloromethane/petroleum ether (1:3, v/v) as eluent to afford pure
product as a yellow solid.
Figure 4. Frontier molecular orbital profiles of molecules based on
DFT (B3LYP/6-31G*) calculations.
Compound 5a. Yellow solid. Yield: 0.98 g, 51%. Mp = 82−83 °C.
1H NMR (600 MHz, CDCl3): δ 9.44 (s, 1H); 9.21 (s, 1H); 9.15 (s,
1H); 7.56−7.59 (b, 6H, coverlay); 7.35−7.37 (b, 9H, coverlay); 4.23−
4.27 (m, 6H); 3.99−4.03 (m, 6H); 1.89−1.91 (m, 6H); 1.64−1.67 (m,
6H); 1.57−1.62 (m, 6H); 1.24−1.27 (m, 6H); 0.96−0.98 (m, 9H);
0.78−0.80 (m, 9H). 13C NMR (100 MHz, CDCl3): δ 153.4, 153.1
151.6, 149.6, 147.6, 147.3, 132.8, 131.2, 130.0, 128.5, 128.2, 128.0,
127.6, 127.4, 126.2, 125.7, 124.3, 124.0, 123.8, 123.3, 113.7, 113.2,
112.9, 111.7, 110.1, 99.6, 99.0, 98.0, 87.8, 87.6, 73.8, 73.2, 68.5, 68.4,
32.4, 31.0, 26.3, 19.3, 18.8, 13.8, 13.5. MS (MALDI-TOF) m/z: calcd
for C66H72O6 960.5329, found 960.5371. Anal. Calcd for C66H72O6: C,
82.46; H, 7.55. Found: C, 82.39; H, 7.61.
Compound 5b. Yellow solid. Yield: 1.06 g, 53%. Mp = 82−83 °C.
1H NMR (600 MHz, CDCl3): δ 9.44 (s, 1H); 9.23 (s, 1H); 9.16 (s,
1H); 7.44−7.49 (m, 6H); 7.15−7.18 (m, 6H); 4.22−4.26 (m, 6H);
3.99−4.04 (m, 6H); 2.38 (s, 9H); 1.87−1.91 (m, 6H); 1.65−1.71 (m,
6H); 1.59−1.61 (m, 6H); 1.24−1.25 (m, 6H); 0.97−0.98 (m, 9H);
0.80−0.83 (m, 9H). 13C NMR (100 MHz, CDCl3): δ 153.4, 153.2,
149.7, 147.8, 147.4, 138.5, 138.4, 138.1, 131.4, 131.3, 130.0, 129.1,
129.1, 129.0, 128.6, 126.3, 124.5, 124.2, 121.0, 120.6, 113.4, 99.8, 99.3,
98.3, 87.2, 87.2, 87.1, 76.6, 73.9, 73.3, 68.8, 32.5, 31.3, 31.2, 21.4, 19.4,
19.0, 18.9, 13.8, 13.7, 13.6. MS (MALDI-TOF) m/z: calcd for
C69H78O6 1002.5798, found 1002.5812. Anal. Calcd for C69H78O6: C,
82.60; H, 7.84. Found: C, 82.66; H, 7.79.
profiles, which showed that the substituted groups on the
benzene rings of coronenes had only slight effects on the
molecular orbital profiles. In addition, although the calculated
energy gaps (3.65, 3.64, and 3.61 eV) were approximately 0.6
eV higher than the experimental data, the differences between
the values for the molecules were negligible, which was in
agreement with the experimental data.
The photostability of compounds 1a−c was investigated in
toluene under different irradiation conditions (Figure S8 in
Supporting Information). The photoinduced degradation was
quantified by monitoring the decrease of absorption in the
UV−vis region (325−375 nm). No degradation was observed
when compounds 1a−c were subjected to irradiation with
white light (100 W) for 8 h. Furthermore, these compounds
revealed only slight decomposition upon irradiation with UV
light (6 W) for 8 h. Such remarkable photostability can be
ascribed to the high HOMO energy level derived from the
coronene core.
In conclusion, three functionalized coronenes were synthe-
sized from triphenylene blocks, with good yields. All of them
displayed good solubility and photostability, which makes them
potential solution-processable candidates for organic devices. It
should be noted that compounds 1a and 1c had very different
packing motifs in their single crystal structures; this affords an
alternative approach to the exploration of organic optoelec-
tronic materials with good performance in devices, using only
small amounts of structural decoration. Additionally, it is
Compound 5c. Yellow solid. Yield: 1.13 g, 54%. Mp = 82−85 °C.
1H NMR (400 MHz, CDCl3): δ 9.48 (s, 1H); 9.27 (s, 1H); 9.20 (s,
1H); 7.50−7.55 (m, 6H); 6.89−6.92 (m, 6H); 4.23−4.28 (m, 6H);
4.01−4.04 (m, 6H); 3.84 (s, 9H); 1.89−1.91 (m, 6H); 1.71−1.90 (m,
6H); 1.62−1.69 (m, 6H); 1.29−1.31 (m, 6H); 0.96−1.01 (m, 9H);
0.83−0.86 (m, 9H). 13C NMR (100 MHz, CDCl3): δ 159.8, 159.7,
159.5, 153.2, 149.7, 147.6, 147.3, 132.9, 132.8, 132.8, 129.9, 128.6,
11322
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Note
126.4, 124.5, 124.2, 116.3, 115.8, 114.1, 114.0, 113.9, 113.8, 113.4,
99.6, 99.1, 98.0, 86.5, 73.9, 73.3, 68.7, 68.6, 55.3, 32.6, 31.3, 31.2, 19.4,
19.0, 18.9, 13.9, 13.7, 13.7. MS (MALDI-TOF) m/z: calcd for
C69H78O9 1050.5646, found 1050.5709. Anal. Calcd for C69H78O9: C,
78.83; H, 7.48. Found: C, 78.92; H, 7.56.
Meng for measurement and analysis of single crystal structures
and Dr. Yanliang Ren for theoretical calculation. We thank Prof.
Anxin Wu for his sugesstions and dedicate to him on the
occasion of his 50th birthday.
General Synthetic Procedure for 1a−c. 1,4,8-Triphenyl-
2,3,6,7,10,11-hexabutoxytriphenylene (1.0 mmol) was dissloved in 10
mL of dry toluene. After addition of PtCl2 (0.2 mmol), the reaction
vessel was flushed with nitrogen and stirred at 90 °C for 48 h. The
solvent was removed under reduced pressure. The residue was purified
by column chromatography packed with silica gel using dichloro-
methane/petroleum ether (1:4, v/v) as eluent to afford pure product
as an orange solid.
REFERENCES
■
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̈
Compound 1a. Orange solid. Yield: 0.51 g, 51%. Mp = 143−145
1
°C. H NMR (400 MHz, CDCl3): δ 9.01−9.03 (s, 3H, coverlay);
7.78−7.80 (b, 6H, coverlay); 7.49−7.54 (b, 9H, coverlay); 4.55 (b, 6H,
coverlay); 3.79 (b, 6H, coverlay); 2.00−2.05 (m, 6H); 1.69−1.70 (m,
6H); 1.03−1.11 (m, 9H), 0.79−0.85 (m, 9H). 13C NMR (100 MHz,
CDCl3): δ 146.4, 146.0, 145.5, 144.5, 144.4, 137.0, 136.8, 136.5, 129.8,
129.7, 129.7, 129.6, 127.0, 126.9, 126.1, 124.5, 124.4, 124.4, 124.2,
124.0, 123.1, 122.8, 122.6, 121.7, 121.4, 120.1, 119.8, 74.2, 74.1, 73.7,
73.7, 32.8, 32.7, 32.6, 31.1, 31.0, 19.6, 19.5, 19.1, 19.0, 14.0. MS
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Anal. Calcd for C66H72O6: C, 82.46; H, 7.55. Found: C, 82.31; H, 7.39.
Compound 1b. Orange solid. Yield: 0.53 g, 53%. Mp = 120−122
°C. 1H NMR (400 MHz, CDCl3): δ 8.99−9.01 (s, 3H, coverlay); 7.79
(b, 6H, coverlay); 7.34−7.36 (m, 6H); 4.53−4.55 (m, 6H); 3.76−3.78
(m, 6H); 2.55 (s, 9H); 2.01−2.03 (m, 6H); 1.66−1.68 (m, 6H); 1.03−
1.25 (m, 21H); 0.79−0.85 (m, 9H). 13C NMR (100 MHz, CDCl3): δ
147.7, 146.5, 146.4, 146.0, 145.8, 144.4, 144.4, 142.7, 137.0, 136.8,
136.5, 135.5, 129.8, 129.7, 129.6, 129.5, 127.7, 127.6, 124.4, 124.2,
124.0, 124.0, 122.9, 122.9, 121.8, 119.7, 74.2,74.1, 73.7, 73.6, 32.7,
32.6, 31.3, 31.2, 21.3, 19.5, 19.1, 19.0, 14.1, 14.1, 14.1, 14.0. MS
(MALDI-TOF) m/z: calcd for C69H78O6 1002.5798, found 1002.5834.
Anal. Calcd for C69H78O6: C, 82.60; H, 7.84. Found: C, 82.71; H, 7.96.
Compound 1c. Orange solid. Yield: 0.60 g, 57%. Mp = 165−167
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1
°C. H NMR (400 MHz, CDCl3): δ 8.99−9.01 (s, 3H, coverlay);
7.70−7.74 (m, 6H); 7.08−7.11 (m, 6H); 4.54−4.56 (m, 6H); 3.97 (s,
9H); 3.76−3.78 (m, 6H); 2.03−2.05 (m, 6H); 1.69−1.71 (m, 6H);
1.04−1.26 (m, 21H); 0.79−0.88 (m, 9H).; 13C NMR (100 MHz,
CDCl3): δ 158.4, 147.7, 147.6, 146.5, 145.9, 144.4, 144.3, 138.0, 138.0,
136.4, 136.1, 130.8, 130.7, 130.7, 124.5, 124.3, 124.2, 124.0, 123.0,
122.8, 122.6, 122.3, 121.8, 121.5,120.0, 119.8, 119.4, 112.6, 112.4, 74.2,
74.1, 73.8, 55.4, 32.7, 32.6, 31.3, 30.9, 19.5, 19.1, 19.0, 14.1. MS
(MALDI-TOF) m/z: calcd for C69H78O9 1050.5646, found 1050.5680.
Anal. Calcd for C69H78O9: C, 78.83; H, 7.48. Found: C, 78.66; H, 7.33.
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ASSOCIATED CONTENT
* Supporting Information
Details on the synthesis, characterization, NMR, MS spectra of
interminates and coronenes. This material is available free of
charge via the Internet at http://pubs.acs.org.
■
S
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AUTHOR INFORMATION
Corresponding Author
*E-mail: yinj@mail.ccnu.edu.cn; chshliu@mail.ccnu.edu.cn.
Notes
■
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ACKNOWLEDGMENTS
■
This work was financially supported by National Natural
Science Foundation of China (Nos. 20931006, 21072070,
21072071), Program for Changjiang Scholars and Innovative
Research Team in University (No. IRT0953), the Program for
Academic Leader in Wuhan Municipality (No.201271130441),
and self-determined research funds of CCNU from the college's
basic research and operation of MOE. We thank Dr. Xianggao
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