Synthesis and characterization of symmetrical sulfur-fused polycyclic aromatic hydrocarbons with controlled shapes

Article abstract of DOI:10.1016/j.tet.2017.08.020

Here we report and establish a facile synthetic method for these unprecedented sulfur-fused polycyclic aromatic hydrocarbons (S-PAHs) with symmetrical structures (C₂-rectangle and D_6h-hexagonal shape). Characterization by laser desor

Full text of DOI:10.1016/j.tet.2017.08.020

Accepted Manuscript
Synthesis and characterization of symmetrical sulfur-fused polycyclic aromatic
hydrocarbons with controlled shapes
Jianghui Yin, Yumiao Hu, Dengqing Zhang, Xianying Li, Wusong Jin
PII:
S0040-4020(17)30851-7
10.1016/j.tet.2017.08.020
TET 28914
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 19 June 2017
Revised Date: 4 August 2017
Accepted Date: 14 August 2017
Please cite this article as: Yin J, Hu Y, Zhang D, Li X, Jin W, Synthesis and characterization of
symmetrical sulfur-fused polycyclic aromatic hydrocarbons with controlled shapes, Tetrahedron (2017),
doi: 10.1016/j.tet.2017.08.020.
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Synthesis
and
characterization
of
symmetrical sulfur-fused polycyclic aromatic
hydrocarbons with controlled shapes
Jianghui Yina, Yumiao Hua, Dengqing Zhanga, Xianying Lib, Wusong Jina,*
aCollege of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Remin
Road, Songjiang, Shanghai 201620, P. R. China.
bCollege of Environmental Science and Engineering, Donghua University, 2999 North Remin Road, Songjiang,
Shanghai 201620, P. R. China.

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Synthesis and characterization of symmetrical sulfur-fused polycyclic aromatic
hydrocarbons with controlled shapes
Jianghui Yina, Yumiao Hua, Dengqing Zhanga, Xianying Lib, Wusong Jina,
aCollege of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Remin Road, Songjiang, Shanghai 201620, P. R. China.
bCollege of Environmental Science and Engineering, Donghua University, 2999 North Remin Road, Songjiang, Shanghai 201620, P. R. China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Here we report and establish a facile synthetic method for these unprecedented sulfur-fused
polycyclic aromatic hydrocarbons (S-PAHs) with symmetrical structures (C2-rectangle and D6h-
hexagonal shape). Characterization by laser desorption/ionization time-of-flight mass
spectrometry unambiguously validate the successful formation of these novel S-PAHs. The C2-
rectangle and D6h-hexagonal-shaped S-PAHs (1 and 2) are obtained by Scholl-type
cyclodehydrogenation of the corresponding precursor using FeCl3 as an oxidant, and their
spectral characteristics, thermal and electrical properties are investigated.
Available online
Keywords:
Symmetrical
Sulfur-fused
Controlled
Shapes
Corresponding author. Tel.: +86 21 67792391; fax: +86 21 67792387; e-mail: wsjin@dhu.edu.cn (W. Jin).

2
Tetrahedron
ACCEPTED MANUSCRIPT
1. Introduction
Compound 9 was subjected to Diels-Alder reaction with bis(4-
dodecylphenyl)acetylene (10)11, giving 11 in high yield (71%).
Then, the Suzuki-coupling reaction between 11 and thiophene-α-
boronic esters 5 afforded the precursor 12 in 36% yield. Finally,
the Oxidative cyclization of 12 by FeCl3/CH3NO2 in CH2Cl2
resulted in the formation of the fully cyclodehydrogenated 1 in
68% yield.
Enormous interest exists in the development of π-electron
materials because they exhibit electronic, optoelectronic, and
magnetic properties that are suitable for their potential
application in molecular electronics.1,2 Compared to π-conjugated
polymers, polycyclic aromatic hydrocarbons (PAHs) possessing
unique physicochemical characteristics that have served as active
components of organic electronic devices such as field-effect
transistors, light-emitting diodes, solar cells and supramolecular
materials field.3 Compared with full carbon analogues, partially
introduced the heteroatom, such as nitrogen,4 sulfur,5 as well as
oxygen,6 into the aromatic skeleton of PAHs, will unexpectedly
lead to dramatic changes in their physicochemical and/or
electronic properties by changing such as polarity, electron
density, dipole and band-gap of the molecule.7 Sulfur has a
similar electronegativity (2.58) to that of carbon (2.55) in the
graphitic layers,8 which is effective in modifying the electronic
arrangement. Consequently, special emphasis is given to sulfur
heteroatom PAHs (Scheme 1), and their unique electronic,
optical, and redox properties and self-assembling properties are
interesting.9 Herein, we are particularly interested in S-PAHs and
reported the synthesis, characterization of symmetrical S-PAHs
(1 and 2) with controlled shapes (Scheme 2). The C2-rectangle
and D6h-hexagonal-shaped S-PAHs (1 and 2) in which four or six
double bonds in the periphery are thieno-fused, respectively. The
structures of the S-PAHs (1 and 2) were characterized by
MALDI-TOF MS, and their spectral characteristics, thermal and
electrical properties were investigated.
Scheme 3. Synthetic route of 1.
The D6h-hexagonal-shaped S-PAH (2) possesses six
hydrophilic TEG chains in the periphery. To achieve the D6h-
symmetric functionalization of the core, a strategy with
introduction of hydrophilic segments to 22 followed by oxidative
cyclization was adopted (Scheme 4). 2,2'-(1,2-ethynediyldi-3,1-
phenylene)bis[5-(trimethylsilyl)-thiophene] (20) was synthesized
using thiophene and 3-bromoiodobenzene as starting materials.
The reaction of thiophene with trimethylchlorosilane and further
reaction with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxa-
borolane afforded 4,4,5,5-tetramethyl-2-[5-(trimethylsilyl)-2-
thienyl]-1,3,2-dioxaborolane (14).12 Next, the Suzuki-coupling
reaction between 14 and bis(3-bromophenyl) acetylene (19)13 in
THF using Pd(PPh3)4/K2CO3 afforded 20 in 80% yield. Then the
cobalt-catalyzed cyclotrimerization of 20, giving 2,2'-[2',3',5',6'-
tetrakis[3-[5-(trimethylsilyl)-2-thienyl]phenyl][1,1':4',1''-terphen-
yl]-3,3''-diyl]-bis[5-(trimethylsilyl)-thiophene] (21) in 80% yield,
and further substitution with iodine monochloride afforded 22 in
62% yield. Next, the Suzuki-coupling reaction between 22 and
[4-[2-[2-(2-Methoxyethoxy)-ethoxy]ethoxy]phenyl]boronic acid
(17)14 was carried out in toluene using Pd(PPh3)4/K2CO3,
affording the precursor 23 in 58% yield. Finally, the Oxidative
cyclization of 23 by FeCl3/CH3NO2 in CH2Cl2 resulted in the
formation of 2 in 60% yield. However, the Suzuki-coupling
reaction between 22 and 17 generated a small amount of five
sites substitution impurity, which has brought difficulty to the
purification (Fig. S1). Therefore, we decided to give up this
synthetic route and explore the better one.
Scheme 1. Molecular structures of S-PAHs with specific shapes.
Scheme 2. Molecular structures of 1 and 2.
2. Results and discussion
2.1. Synthesis of S-PAHs (1 and 2)
The C2-rectangle-shaped S-PAH (1) possesses four
hydrophilic TEG chains on the around. To achieve the C2-
symmetric functionalization of the core, a strategy with
introduction of hydrophilic segments to compound 11 followed
by oxidative cyclization was adopted (Scheme 3). 1,3-dibromo-5-
(bromomethyl)-benzene was allowed to react with p-
toluenesulfonylacetonitrile (6) in DMSO-Et2O in the presence of
37% HCl/NaOH, yielding 7 in 65% yield.10 Subsequently, the
reaction of 1,3-bis(3,5-dibromophenyl)-2-propanone (7) with 1,2-
bis(4-dodecylphenyl)-1,2-ethanedione (8)11 in dioxane using
Bu4NOH afforded cyclopentadienone derivative 9 in 41% yield.

3
O
O
theoretical value of molecular weight. The results
unambiguously validated the successful formation of 1 and 2.
ACCEPTED MANUSCRIPT
i-Pr
B
O
n-BuLi
S
S
n-BuLi, TMSCl
THF, -78°C
S
TMS
TMS
B
O
THF, -78°C
3
13
14
HO
HO
1. NaH, THF, reflux;
1. n-BuLi, THF, -78°C;
2. B(OMe)3; 3. HCl
Br
O(CH2CH2O)3CH3
B
O(CH2CH2O)3CH3
Br
OH
2. tris-ethoxy(methoxy)-
p-toluensulfonate
17
16
15
TMS
S
PdCl2(PPh3
)
2, CuI
14, Pd(PPh3
)4, K2CO3
Co2(CO)8
dioxane
I
THF, reflux
DBU, Benzene, TMSA
Br
Br
Br
20
18
19
S
2150 2160 2170 2180
2420 2430 2440 2450
TMS
I
TMS
I
TMS
S
S
S
S
2200
2400
2600
2800
2000 2100 2200 2300 2400 2500
S
S
17, Pd(PPh3
)
4, K2CO3
ICl
I
TMS
I
TMS
Toluene, reflux
THF, 0°C
S
S
Fig. 1. HRMS (MALDI-TOF) spectrum of target S-PAH 1 (a)
and 2 (b), respectively.
S
S
S
S
I
TMS
I
22
TMS
21
2.2. UV-vis spectra of S-PAHs (1 and 2) in toluene
R
R
S
R
R
S
S
The spectral characteristics of S-PAHs (1 and 2) were
characterized by UV-vis spectra. The UV-vis spectra of C2-
rectangle-shaped 1 showed three well-resolved absorption bands
(416, 530, and 577 nm) characteristic for large PAHs. In addition,
the UV-vis spectra of D6h-hexagonal-shaped 2 displayed only one
well-resolved absorption band at 418 nm, which was attributed to
π-π* excitations (Fig. 2). Obvious changes were observed in the
UV-vis spectra probably due to the different shapes of
symmetrical S-PAHs.
S
S
S
FeCl3,CH3NO2
CH2Cl2
R
R
R
R
S
S
S
S
S
R=
)
O(CH2CH2O)3CH3
S
R
23
R
2
R
R
Scheme 4. Synthetic route of 2.
Eventually, we established a facile and rapid synthetic method
for S-PAH 2 (Scheme 5). Bis(3-bromophenyl) acetylene was
allowed to react with bispinacolatebiboron in DMF in the
presence of PdCl2(dppf)/AcOK, yielding 25 in 70%. And then the
Suzuki-coupling reaction between 25 and 28 in toluene using
Pd(PPh3)4/K2CO3 gave 29 in 65% yield. The cobalt-catalyzed
cyclotrimerization of 29, giving the precursor 23 in 78% yield,
which was transformed into the target compound 2 by
cyclodehydrogenation in 60% yield.
0.6
1
2
0.5
0.4
0.3
0.2
0.1
0.0
400
600
800
O
O
B
O
O
O
O
Pd(dppf)Cl2, K(OAc)2
DMF
+
B
24
B
Fig. 2. Normalized UV-vis spectra of 1 (solid) and 2 (dashed)
(1.0×10-5 M in toluene), using a 1 cm quartz cell.
Br
Br
B
19
25
O
O
OH
16, Pd(PPh3
)
4, K2CO3
NBS, CHCl3
DMF
S
2.3. Thermal gravity analysis profile of S-PAHs (1 and 2)
B
O(CH2CH2O)3CH3
THF, reflux
OH
S
R
26
27
The bulk thermotropic properties of S-PAHs (1 and 2) were
investigated by thermogravimetric analysis (TGA). The
decomposition temperatures of 1 and 2 were detected as 370 and
348 °C, respectively (Fig. 3). The results showed that the C2-
rectangle and D6h-hexagonal-shaped S-PAHs (1 and 2) both have
good thermal stability, which has potential applications in
nanodevices with high thermal stability requirements.
S
25, Pd(PPh3
)4, K2CO3
Co2(CO)8
dioxane
O(CH2CH2O)3CH3
Toluene, reflux
S
Br
28
29
S
R
R
R
R
R
S
S
S
S
S
S
FeCl3, CH3NO2
CH2Cl2
R
R
R
R
S
S
100
1
2
80
S
S
S
S
R
23
2
60
40
20
R
)
R
R
R=
O(CH2CH2O)3CH3
Scheme 5. Synthetic route of 2.
0
The recording of NMR spectroscopy did not succeed for S-
PAHs (1 and 2) due to the aggregation propensity of the
molecules in solution,15 so they were characterized by MALDI-
TOF mass spectrometry. MALDI-TOF mass spectra showed the
molecular ion-peak at 2164.3990 for 1 (Fig. 1a) and 2433.5918
for 2 (Fig. 1b) respectively, which coincided with their
200 400 600 800
Fig. 3. TGA profile of 1 (solid) and 2 (dashed).

4
Tetrahedron
ACCEPTED MANUSCRIPT
2.4. Cyclic voltammetry and energy levels of S-PAHs (1 and
spectra were recorded on
a
Persee model TU-1901
2)
spectrophotometer (Beijing Purkinje General Instrument Co.,
Ltd.), using a quartz cell of 1 cm path length. Thermal gravity
analysis (TGA) was measured using TG-2091F1 (NETZSCH
Scientific Instruments Trading (Shanghai) Ltd.). The tests were
performed at an increasing rate of 10 °C/min under nitrogen
atmosphere.
To elucidate the influence of the peripheral thiophenes on the
molecular energy levels of the molecular core, the HOMO
energies of the S-PAHs with symmetrical structures were
obtained via cyclic voltammetry. As shown (Fig. 4), both 1 and 2
in CH2Cl2 exhibited one well-resolved irreversible oxidation
wave, with the onset of the oxidation indicating a HOMO energy
of -4.92 and -4.95 eV, respectively, which were comparable to
the values reported for trithiopheno[a,g,m]coronene (TTC) (-5.51
eV)16a and contorted dibenzotetrathienocoronene (c-DBTTC) (-
5.10 eV).16b The energy levels from electrochemistry were
summarized in SI Table S1 for comparison. Thus, the S-PAHs (1
and 2) are stronger donors than TTC and c-DBTTC and might
serve as efficient active layers in photovoltaic devices.16c
4.2. Synthesis
4.2.1. Synthesis of compound 4. Copper iodide (1.16 g, 6.1
mmol) and sodium hydride (1.12 g, 46 mmol) were added to a
solution of triethylene glycol monomethyl ether (24.63 g, 0.15
mol) in 10 mL of dry pyridine and allowed to stir at 25 °C for 30
min. 2-bromothiophene (4.97 g, 30.5 mmol) was then added and
the mixture was heated at 100 °C for 7 d. The mixture was slowly
cooled down to room temperature and then poured into a water-
CH2Cl2 mixture. Then the organic solution was extracted three
times with 10% HCl to remove pyridine. The CH2Cl2 organic
phase was dried over anhydrous magnesium sulfate. The solution
was concentrated to dryness, and the residue was purified by
flash column chromatography (SiO2, PE/EA=4/1) to yield yellow
liquid 4 (3.15 g, 42%). 1H NMR (400 MHz, CDCl3) δ 7.17 (dd, J
= 5.2, 3.1 Hz, 1H), 6.79 (dd, J = 5.2, 1.5 Hz, 1H), 6.27 (dd, J =
3.1, 1.5 Hz, 1H), 4.15 – 4.11 (m, 2H), 3.88 – 3.82 (m, 2H), 3.77 –
3.63 (m, 6H), 3.56 (dd, J = 5.6, 3.6 Hz, 2H), 3.39 (s, 3H). 13C
NMR (101 MHz, CDCl3) δ 157.58, 124.62, 119.57, 97.54, 71.92,
70.77, 70.63, 70.54, 69.68, 69.58, 59.00.
1
2
4
2
0
0.0 0.2 0.4 0.6 0.8
1.0
Fig. 4. Cyclic voltammetric profile of 1 (solid) and 2 (dashed) in
CH2Cl2 (0.5 mM) containing 0.1 M (C4H9)4NBF4. Potentials are
reported versus the Fc/Fc+ redox couple as an internal standard,
scan rate = 100 mV/s.
4.2.2. Synthesis of compound 5. Compound 4 (2 g, 8.12 mmol)
was dissolved in THF (35 mL) and cooled to -78 °C. To this
solution, 5.6 mL of n-butyllithium solution (1.6 mol/L PE
solution) was added dropwise, and stirred for
1
h.
3. Conclusions
Isopropoxyboronic acid pinacol ester (1.2 g, 12.18 mmol) was
added dropwise to the solution, and was stirred at room
temperature for 12 h. 10 mL of water and 50 mL of CH2Cl2 were
added to the resulting solution to separate the organic layer. The
organic layer was washed with 150 mL of water and dried over
anhydrous magnesium sulfate. The solution was concentrated to
dryness, and the residue was purified by flash column
chromatography (SiO2, PE/EA=3/1) to yield yellow liquid 5
In summary, we have reported and established a facile
synthetic method for these unprecedented S-PAHs with
symmetrical structures (C2-rectangle and D6h-hexagonal shape).
The TG results indicated that they have potential applications in
nanodevices with high thermal stability. Furthermore, the cyclic
voltammetry results suggested that they are strong donors and
might serve as efficient active layers in photovoltaic devices.
1
(1.45 g, 48%). H NMR (400 MHz, CDCl3) δ 7.26 (d, J = 3.8
4. Experimental Section
4.1. General
Hz,1H), 6.27 (d, J = 3.8 Hz, 1H), 4.18 – 4.14 (m,2H), 3.81 – 3.77
(m, 2H), 3.68 – 3.57 (m, 6H), 3.49 (dd, J = 5.6, 3.6 Hz, 2H), 3.32
(s, 3H), 1.26 (s, 12H). 13C NMR (101 MHz, CDCl3) δ 171.45,
136.36, 107.11, 83.71, 72.97, 71.86, 70.78, 70.56, 70.51, 69.26,
58.94, 24.73, 24.69.
Unless otherwise noted, all commercial reagents were used as
received without further purification. Tetrahydrofuran (THF) was
refluxed over a mixture of Na and benzophenone ketyl under
argon and distilled just before use. DMF was dried over CaH2
under argon and freshly distilled prior to use. CH2Cl2 was dried
over CaH2 under argon and freshly distilled prior to use. CHCl3
was dried over molecular sieve and freshly distilled under argon
4.2.3. Synthesis of compound 9. A MeOH solution of Bu4NOH
(1.0 mol/L, 0.27 mL, 0.27 mmol) was added all at once to a 1,4-
dioxane (3 mL) solution of a mixture of 7 (140 mg, 0.27 mmol)
and 8 (146 mg, 0.27 mmol) at 125 °C. After stirred at 125 °C for
10 min, the reaction mixture was poured into water and extracted
with CH2Cl2.The combined extract was evaporated to dryness,
and the residue was purified by flash column chromatography
(SiO2, CH2Cl2/PE=1/4) to yield purple solid 9 (113 mg, 41%). 1H
NMR (400 MHz, CDCl3) δ 7.51 (t, J = 1.7 Hz, 1H), 7.29 (d, J =
1.8 Hz, 2H), 7.26 (s, 1H), 7.26 (s, 1H), 7.03 (d, J = 8.2 Hz, 2H),
6.80 (d, J = 8.2 Hz, 2H), 2.59 (t, J = 7.5 Hz, 2H), 1.62 – 1.52 (m,
3H), 1.25 (s, 17H), 0.88 (t, J = 6.8 Hz, 3H). 13C NMR (101 MHz,
CDCl3) δ 197.96, 156.75, 144.77, 134.13, 132.89, 131.55,
129.05, 128.90, 128.42, 122.57, 122.40, 35.73, 31.94, 31.04,
29.71, 29.67, 29.65, 29.53, 29.38, 29.02, 22.71, 14.13. MALDI-
TOF Mass: calcd. for C53H64Br4O [M]+: m/z = 1032.1691; found:
[M+Na]+: 1053.6042.
1
before use. H and 13C NMR spectra were recorded on a Bruker
model Bruker AV-400 spectrometer, operating at 400 MHz.
Matrix-assisted laser desorption ionization time-of-flight mass
spectrometry (MALDI-TOF mass) was performed on an AB
Sciex model AB Sciex 4800 Plus MALDI TOF/TOF Analyzer,
using dithranol as a matrix. CV measurements were carried out
on a comW3Wputer-controlled CHI600E/700E in a three-
electrode cell in a dichloromethane solution of (C4H9)4NBF4 (0.1
M) with a scan rate of 100 mV/s at room temperature. The Pt
wire, Ag/Ag+ electrode, and glassy carbon electrode were used as
the assisting electrode, the reference electrode, and the working
electrode, respectively. Gel permeation chromatography (GPC)
analyses were performed on JAI model LC-9201 recycling
preparative HPLC, using CHCl3 as eluent. Electronic absorption

5
4.2.4. Synthesis of compound 11. Compound 9 (480 mg, 0.47
mmol) and 10 (264 mg, 0.51 mmol) were placed into a 50 mL
schlenk tube. After addition of diphenyl ether (2 mL), the
mixture was refluxed for 24 h and allowed to cool to room
temperature, The filtrate was evaporated to dryness, and the
residue was purified by flash column chromatography (SiO2, PE)
degassed by three “freeze-pump-thaw” cycles and then stirred
ACCEPTED MANUSCRIPT
at 120 °C for 12 h under argon. The reaction mixture was
allowed to cool to room temperature and evaporated to dryness.
A CH2Cl2 solution of the residue was washed with water, dried
over anhydrous MgSO4, and evaporated to dryness. The residue
was purified by flash column chromatography (SiO2,
1
1
PE/CH2Cl2=1/5) to yield yellow solid 21 (360 mg, 80%). H
to yield yellow solid 11 (500 mg, 71%). H NMR (400 MHz,
NMR (400 MHz, CDCl3) δ 7.20 – 7.06 (m, 1H), 6.93 – 6.55 (m,
5H), 0.04 (t, J = 18.3 Hz, 9H). MALDI-TOF Mass: calcd. for
C84H91S6Si6 [M+H]+: m/z = 1459.4061; found: 1459.8222.
CDCl3) δ 7.12 (t, J = 1.7 Hz, 1H), 6.86 (d, J = 1.7 Hz, 2H), 6.74
(d, J = 8.1 Hz, 4H), 6.67 (d, J = 8.1 Hz, 4H), 2.40 (t, J = 7.4 Hz,
4H), 1.44 (dd, J = 14.5, 7.2 Hz, 4H), 1.33 – 1.13 (m, 40H), 0.89
(t, J = 6.8 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ 144.28,
140.39, 140.27, 138.41, 136.71, 133.19, 130.96, 130.59, 127.11,
120.86, 35.40, 31.96, 31.23, 29.77, 29.75, 29.70, 29.56, 29.41,
28.89, 22.72, 14.14. MALDI-TOF Mass: calcd. for C90H122Br4
[M]+: m/z = 1523.5820; found: [M+Na]+: 1546.2096, [M+K]+:
1564.4425.
4.2.9. Synthesis of compound 22. To a stirred solution of 21 (150
mg, 0.084 mmol) in THF (50 mL) cooled at 0 °C was added a
solution of iodine monochloride in CH2Cl2 (1.0 mol/L, 3 mL, 3
mmol) dropwise over 20 min. The reaction mixture was stirred
for 24 h at 25 °C. The reaction was quenched with a 10%
aqueous solution of sodium thiosulfate (20 mL) and washed by
methanol to afford yellow solid 22 (95 mg, 62%). MALDI-TOF
Mass: calcd. for C66H36I6S6 [M]+: m/z = 1781.5409; found:
1780.5237.
4.2.5. Synthesis of compound 12. To a solution of 11 (100 mg,
0.066 mmol) and 5 (294 mg, 0.79 mmol) in toluene (30 mL)
were added Pd(PPh3)4 (20 mg, 0.012 mmol) and K2CO3 aqueous
(2 mol/L, 1 mL). The mixture was stirred at 110 °C for 48 h. The
solvent was removed in vacuo and the residue was dissolved in
CH2Cl2. The solution was washed with water and dried over
magnesium sulfate. The solution was concentrated to dryness,
and the residue was purified by flash column chromatography
(SiO2, EA) to yield yellow solid 12 (50 mg, 36%). 1H NMR (400
MHz, CDCl3) δ 7.14 (d, J = 1.2 Hz, 1H), 7.05 (d, J = 1.3 Hz,
1H), 6.88 – 6.67 (m, 24H), 6.53 (d, J = 3.8 Hz, 2H), 6.12 (t, J =
4.1 Hz, 2H), 4.25 – 4.13 (m, 8H), 3.86 (dd, J = 10.5, 6.0 Hz, 8H),
3.77 – 3.65 (m, 24H), 3.61 – 3.55 (m, 8H), 3.40 (s, 12H), 2.35 (t,
J = 7.0 Hz, 8H), 1.35 – 1.03 (m, 80H), 0.90 (t, J = 6.7 Hz, 12H).
13C NMR (101 MHz, CDCl3) δ 145.48, 141.62, 141.19, 140.51,
140.37, 139.77, 133.45, 131.37, 127.98, 126.86, 125.62, 124.70,
122.50, 119.85, 72.55, 71.90, 70.58, 70.48, 70.31, 61.74, 59.03,
31.93, 31.68, 30.23, 29.68, 29.67, 29.65, 29.58, 29.41, 29.36,
29.14, 22.70, 14.13. MALDI-TOF Mass: calcd. for C134H190O16S4
[M]+: m/z = 2183.2937; found: [M+Na]+: 2205.8623, [M+K]+:
2221.9170.
4.2.10. Synthesis of compound 23. To a solution of 22 (120 mg,
0.0673 mmol) and 17 (347 mg, 1.22 mmol) in toluene (40 mL)
were added Pd(PPh3)4 (10 mg, 0.006 mmol) and K2CO3 aqueous
(2 mol/L, 1 mL). The mixture was stirred at 110 °C for 48 h. The
solvent was removed in vacuo and the residue was dissolved in
CH2Cl2. The solution was washed with water and dried over
magnesium sulfate. The solution was concentrated to dryness,
and the residue was purified by flash column chromatography
(SiO2, CH2Cl2/CH3OH=40/1) to yield yellow solid 23 (96 mg,
1
58%). H NMR (400 MHz, CDCl3) δ 7.55 – 7.30 (m, 3H), 7.17
(s, 1H), 7.11 – 6.65 (m, 6H), 4.23 – 3.92 (m, 2H), 3.88 (d, J =
18.9 Hz, 2H), 3.80 – 3.64 (m, 6H), 3.58 (s, 2H), 3.40 (s, 3H).
MALDI-TOF Mass: cacld. for C144H150O24S6 [M]+: m/z =
2454.8841; found: [M]+: 2455.1096, [M+K]+: 2489.0112.
4.2.11. Synthesis of compound 27. To a solution of 2-
thienylboronic acid (724 mg, 5.66 mmol) and 16 (1.2 g, 3.78
mmol) in THF (50 mL) were added Pd(PPh3)4 (436 mg, 0.38
mmol) and K2CO3 aqueous (2 mol/L, 10 mL). The mixture was
stirred at 80 °C for 12 h. The solvent was removed in vacuo and
the residue was dissolved in CH2Cl2. The solution was washed
with water and dried over magnesium sulfate. The solution was
concentrated to dryness, and the residue was purified by flash
column chromatography (SiO2, PE/EA=4/1) to yield yellow
4.2.6. Synthesis of compound 1. A MeNO2 (3 mL) solution of
anhydrous FeCl3 (357 mg, 2.20 mmol) was slowly added to a dry
CH2Cl2 (60 mL) solution of 12 (120 mg, 0.055 mmol) with argon
bubbling through a glass tube. After stirred for 90 min with argon
bubbling, MeOH (100 mL) was added to the reaction mixture to
quench the reaction. the resulted precipitate was collected by
filtration, washed by methanol to afford red solid 1 (81 mg, 68%).
MALDI-TOF Mass: calcd. for C134H171O16S4 [M+H]+: m/z =
2164.1450; found: 2164.3990.
1
liquid 27 (1 g, 85%). HNMR (400 MHz, CDCl3) δ 7.57 – 7.52
(m, 2H), 7.23 (ddd, J = 4.9, 4.3, 1.1 Hz, 2H), 7.07 (dd, J = 5.0,
3.6 Hz, 1H), 6.97 – 6.92 (m, 2H), 4.21 – 4.15 (m, 2H), 3.92 –
3.87 (m, 2H), 3.78 – 3.66 (m, 6H), 3.58 (dd, J = 5.7, 3.7 Hz, 2H),
3.41 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 158.41, 144.31,
127.91, 127.47, 127.17, 123.84, 122.09, 115.00, 71.95, 70.87,
70.68, 70.59, 69.74, 67.55, 59.05.
4.2.7. Synthesis of compound 20. To a solution of 14 (2 g, 7.1
mmol) and 19 (900 mg, 2.70 mmol) in THF (50 mL) were added
Pd(PPh3)4 (460 mg, 0.4 mmol) and K2CO3 aqueous (2 mol/L, 20
mL). The mixture was stirred at 80 °C for 24 h. The solvent was
removed in vacuo and the residue was dissolved in CH2Cl2. The
solution was washed with water and dried over magnesium
sulfate. The solution was concentrated to dryness, and the residue
was purified by flash column chromatography (SiO2,
4.2.12. Synthesis of compound 28. To a stirred solution of 27
(800 mg, 2.48 mmol) in CHCl3 (20 mL) was gradually added
NBS (486 mg, 2.73 mmol) at -10 °C under argon. After being
stirred at -10 °C for 6 h, the mixture was evaporated under
reduced pressure. The residue was purified by flash column
chromatography (SiO2, PE:EA=4/1) to yield yellow liquid 28
1
PE/CH2Cl2=10/1) to yield white solid 20 (1 g, 80%). H NMR
(400 MHz, CDCl3) δ 7.67 (s, 1H), 7.44 (d, J = 7.7 Hz, 1H), 7.29
(d, J = 7.6 Hz, 1H), 7.25 (d, J = 3.4 Hz, 1H), 7.20 (t, J = 7.7 Hz,
1H), 7.07 (d, J = 3.4 Hz, 1H), 0.19 (s, 9H). 13C NMR (101 MHz,
CDCl3) δ 148.63, 140.74, 135.12, 134.73, 130.57, 129.13,
129.01, 126.03, 124.90, 123.75, 89.47, 0.00.
1
(760 mg, 77%). H NMR (400 MHz, CDCl3) δ 7.47 – 7.42 (m,
2H), 7.01 (d, J = 3.8 Hz, 1H), 6.96 – 6.94 (m, 2H), 6.93 (d, J =
1.9 Hz, 1H), 4.20 – 4.14 (m, 2H), 3.92 – 3.86 (m, 2H), 3.80 –
3.64 (m, 6H), 3.58 (dd, J = 5.6, 3.6 Hz, 2H), 3.40 (s, 3H). 13
C
NMR (101 MHz, CDCl3) δ 158.71, 145.80, 130.73, 126.90,
126.68, 122.21, 115.11, 110.18, 71.95, 70.87, 70.68, 70.60,
69.70, 67.56, 59.06.
4.2.8. Synthesis of compound 21. To a dioxane (50 mL) solution
of 20 (460 mg, 1 mmol), Co2(CO)8 (80 mg, 0.23 mmol) was

6
Tetrahedron
ACCEPTED MANUSCRIPT
Y. H.; Jeong, D. H.; Kim, D. Angew. Chem., Int. Ed. 2000, 39,
1458-1462; (d) Tsuda, A.; Osuka, A. Science 2001, 293, 79-82.
3. (a) Katz, H. E.; Bao, Z.; Gilat, S. L. Acc. Chem. Res. 2001, 34,
359-369; (b) Bendikov, M.; Wudl, F.; Perepichka, D. F. Chem.
Rev. 2004, 104, 4891-4945; (c) Schmidt-Mende, L.;
Fechtenkötter, A.; Müllen, K.; Moons, E.; Friend, R. H.;
MacKenzie, J. D. Science 2001, 293, 1119-1122.
4.2.13. Synthesis of compound 29. To a solution of 28 (500 mg,
1.25 mmol) and 25 (180 mg, 0.42 mmol) in toluene (40 mL)
were added Pd(PPh3)4 (48 mg, 0.042 mmol) and K2CO3 aqueous
(2 mol/L, 2 mL). The mixture was stirred at 110 °C for 12 h. The
solvent was removed in vacuo and the residue was dissolved in
CH2Cl2. The solution was washed with water and dried over
magnesium sulfate. The solution was concentrated to dryness,
and the residue was purified by flash column chromatography
(SiO2, CH2Cl2/THF=20/1) to yield yellow solid 29 (223 mg,
4. (a) Matena, M.; Stöhr, M.; Riehm, T.; Björk, J.; Martens, S.; Dyer,
M. S.; Persson, M.; Lobo-Checa, J.; Müller, K.; Enache, M.;
Wadepohl, H.; Zegenhagen, J.; Jung, T. A.; Gade, L. H. Chem.
Eur. J. 2010, 16, 2079-2091; (b) Draper, S. M.; Gregg, D. J.;
Madathil, R. J. Am. Chem. Soc. 2002, 124, 3486-3487; (c) Takase,
M.; Enkelmann, V.; Sebastiani, D.; Baumgarten, M.; Müllen, K.
Angew. Chem., Int. Ed. 2007, 46, 5524-5527.
5. (a) Chernichenko, K. Y.; Sumerin, V. V.; Shpanchenko, R. V.;
Balenkova, E. S.; Nenajdenko, V. G. Angew. Chem., Int. Ed. 2006,
45, 7367-7370; (b) Sun, Y.; Tan, L.; Jiang, S.; Qian, H.; Wang, Z.;
Yan, D.; Di, C.; Wang, Y.; Wu, W.; Yu, G.; Yan, S.; Wang, C.;
Hu, W.; Liu, Y.; Zhu, D. J. Am. Chem. Soc. 2007, 129, 1882-1883;
(c) Jiang, W.; Zhou, Y.; Geng, H.; Jiang, S.; Yan, S.; Hu, W.;
Wang, Z.; Shuai, Z.; Pei, J. J. Am. Chem. Soc. 2010, 133, 1-3; (d)
Zöphel, L.; Enkelmann, V.; Rieger, R.; Müllen, K. Org. Lett.
2011, 13, 4506-4509.
1
65%). H NMR (400 MHz, CDCl3) δ 7.85 (s, 1H), 7.62 (d, J =
7.8 Hz, 1H), 7.60 – 7.54 (m, 2H), 7.48 (d, J = 7.6 Hz, 1H), 7.40
(t, J = 7.7 Hz, 1H), 7.34 (dd, J = 3.5, 1.9 Hz, 1H), 7.22 (dd, J =
3.5, 1.9 Hz, 1H), 6.97 (d, J = 6.9 Hz, 2H), 4.19 (d, J = 3.5 Hz,
2H), 3.91 (d, J = 3.4 Hz, 2H), 3.78 – 3.67 (m, 6H), 3.59 (d, J =
3.0 Hz, 2H), 3.41 (d, J = 1.9 Hz, 3H). 13C NMR (101 MHz,
CDCl3) δ 158.58, 144.11, 141.49, 134.69, 130.35, 128.98,
128.55, 127.22, 126.92, 125.46, 124.44, 123.77, 123.05, 115.09,
89.47, 71.95, 70.87, 70.68, 70.59, 69.73, 67.57, 59.05. MALDI-
TOF Mass: calcd. for C48H50O8S2 [M]+: m/z = 818.29; found:
817.95.
6. Wu, D.; Pisula, W.; Haberecht, M. C.; Feng, X.; Müllen, K. Org.
Lett. 2009, 11, 5686-5689.
7. Stang, P. J.; Olenyuk. B. Acc. Chem. Res. 1997, 30, 502-518.
8. Jeon, I. -Y.; Zhang, S.; Zhang, L.; Choi, H. -J.; Seo, J. -M.; Xia, Z.;
Dai, L.; Baek, J. -B. Adv. Mater. 2013, 25, 6138-6145.
4.2.14. Synthesis of compound 23. To a dioxane (30 mL) solution
of 29 (300 mg, 0.37 mmol), Co2(CO)8 (13 mg, 0.037 mmol) was
degassed by three “freeze-pump-thaw” cycles and then stirred at
120 °C for 12 h under argon. The reaction mixture was allowed
to cool to room temperature and evaporated to dryness. A CH2Cl2
solution of the residue was washed with water, dried over
anhydrous MgSO4, and evaporated to dryness. The residue was
9. (a) Chen, L.; Puniredd, S. R.; Tan, Y. -Z.; Baumgarten, M.;
Zschieschang, U.; Enkelmann, V.; Pisula, W.; Feng, X.; Klauk,
H.; Müllen, K. J. Am. Chem. Soc. 2012, 134, 17869-17872; (b)
Chen, L.; Mali, K. S.; Puniredd, S. R.; Baumgarten, M.; Parvez,
K.; Pisula, W.; De Feyter, S.; Müllen, K. J. Am. Chem. Soc. 2013,
135, 13531-13537; (c) Kang, S. J.; Kim, J. B.; Chiu, C. -Y.; Ahn,
S.; Schiros, T.; Lee, S. S.; Yager, K. G.; Toney, M. F.; Loo, Y. -L.;
Nuckolls, C. Angew. Chem., Int. Ed. 2012, 51, 8594-8597; (d)
Feng, X.; Wu, J.; Ai, M., Pisula, W., Zhi, L., Rabe, J. P.; Müllen,
K. Angew. Chem., Int. Ed. 2007, 46, 3033-3036.
purified
by
flash
column
chromatography
(SiO2,
CH2Cl2/CH3OH=40/1) to yield yellow solid 23 (236 mg, 78%).
10. Possel, O.; Van Leusen, A. Heterocycles 1977, 7, 77-78.
11. Hill, J. P., Jin, W., Kosaka, A., Fukushima, T., Ichihara, H.,
Shimomura, T., Ito, K., Hashizume, T., Ishii, N., Aida, T. Science
2004, 304, 1481-1483.
12. (a) Borshchev, O. V.; Ponomarenko, S. A.; Kleymyuk, E. A.;
Luponosov, Y. N.; Surin, N. M.; Muzafarov, A. M. Russ. Chem.
Bull. 2010, 59, 797-805; (b) Zhu, E.; Hai, J.; Wang, Z.; Ni, B.;
Jiang, Y.; Bian, L.; Zhang, F.; Tang, W. J. Phys. Chem. C. 2013,
117, 24700-24709.
4.2.15. Synthesis of compound 2. Compound 23 (80 mg, 0.0326
mmol) was dissovled in anhydrous CH2Cl2 (30 mL) and bubbled
with argon for 20 min. Then a solution of FeCl3 (254 mg, 1.56
mmol) in CH3NO2 (2.5 mL) was added dropwise. The reaction
mixture was further stirred at room temperature with argon
bubbling for 90 min. Methanol was added, the resulted
precipitate was collected by filtration, washed by methanol to
afford black solid 2 (48 mg, 60%). MALDI-TOF Mass: calcd. for
C144H127O24S6 [M+H]+: m/z = 2433.9360; found: 2433.5918.
13. Mio, M. J., Kopel, L. C., Braun, J. B., Gadzikwa, T. L., Hull, K.
L., Brisbois, R. G., Markworth, C. J., Grieco, P. A. Org. Lett.
2002, 4, 3199-3202.
14. Warther, D.; Bolze, F.; Leonard, J.; Gug, S.; Specht, A.; Puliti, D.;
Sun, X. -H.; Kessler, P.; Lutz, Y.; Vonesch, J. -L.; Winsor, B.;
Nicoud, J. -F.; Goeldner, M. J. Am. Chem. Soc. 2010, 132, 2585-
2590.
15. (a) Wu, J.; Tomovic, Z.; Enkelmann, V.; Müllen, K. J. Org. Chem.
2004, 69, 5179-5186; (b) Tomovic, Z.; Watson, M. D.; Müllen, K.
Angew. Chem., Int. Ed. 2004, 43, 755-758.
16. (a) Li, Z.; Zhi, L.; Lucas, N. T.; Wang, Z. Tetrahedron 2009, 65,
3417-3424; (b) Chiu, C. -Y.; Kim, B.; Gorodetsky, A. A.; Sattler,
W.; Wei, S.; Sattler, A.; Steigerwald, M.; Nuckolls, C. Chem. Sci.
2011, 2, 1480-1486; (c) Gorodetsky, A. A.; Chiu, C. -Y.; Schiros,
T.; Palma, M.; Cox, M.; Jia, Z.; Sattler, W.; Kymissis, I.;
Steigerwald, M.; Nuckolls, C. Angew. Chem., Int. Ed. 2010, 49,
7909-7912.
Acknowledgments
This work was supported by National Foundation of Natural
Science in China (No. 21172035), Chinese Universities Scientific
Found (No. CUSF-DH-D-201552) and The Science and
Technology Commission of Shanghai Municipality (No.
12JC1400200).
Supplementary date
Supplementary date associated with this article can be found
in the online version.
References and notes
1. (a) Laschat, S.; Baro, A.; Steinke, N.; Giesselmann, F.; Hägele, C.;
Scalia, G.; Judele, R.; Kapatsina, E.; Sauer, S.; Schreivogel, A.;
Tosoni, M. Angew. Chem., Int. Ed. 2007, 46, 4832-4887; (b)
Pisula, W.; Feng, X.; Müllen, K. Chem. Mater. 2011, 23, 554-567;
(c) Sergeyev, S.; Pisula, W.; Geerts, Y. H. Chem. Soc. Rev. 2007,
36, 1902-1929.
2. (a) Jones, L. II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997,
62, 1388-1410; (b) Nakanishi, H.; Sumi, N.; Aso, Y.; Otsubo, T. J.
Org. Chem. 1998, 63, 8632-8633; (c) Aratani, N.; Osuka, A.; Kim,