Regioselective photocyclization to prepare multifunctional blocks for ladder-conjugated materials

Article abstract of DOI:10.1021/jo400619u

Multifunctional building blocks 8 and 9 were efficiently synthesized by fusing a perylene-3,4,9,10-tetracarboxylic acid bisimide (PBI) core with o-phenylenediamine, and they were condensed with a pyrenedione and a pyrenetetraone, respectively, to construct new ladder-type conjugated oligomers 12 and 13. In the key photocyclization step, an unusual regioselectivity at the position ortho to the nitro group was discovered in the coupling of the o-nitroaniline functional units at the bay sites of PBI. Bulk-heterojunction solar cells based on 12 and 13 as the acceptors exhibited reasonable performance.

Full text of DOI:10.1021/jo400619u

Article
pubs.acs.org/joc
Regioselective Photocyclization To Prepare Multifunctional Blocks
for Ladder-Conjugated Materials
Zhenbo Zhao, Youdi Zhang, and Yi Xiao*
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian 116024, China
S
* Supporting Information
ABSTRACT: Multifunctional building blocks 8 and 9 were efficiently synthesized by fusing a perylene-3,4,9,10-tetracarboxylic
acid bisimide (PBI) core with o-phenylenediamine, and they were condensed with a pyrenedione and a pyrenetetraone,
respectively, to construct new ladder-type conjugated oligomers 12 and 13. In the key photocyclization step, an unusual
regioselectivity at the position ortho to the nitro group was discovered in the coupling of the o-nitroaniline functional units at the
bay sites of PBI. Bulk-heterojunction solar cells based on 12 and 13 as the acceptors exhibited reasonable performance.
Chart 1. Structures of the Ladder-Conjugated Polymers BBL
and PQL, the Known Multifunctional Monomers TBA and
TABEF, and the New Building Block 8 Designed in This
Work
INTRODUCTION
■
Ladder-conjugated oligomers or polymers, because of their
potential applications in electronics and optoelectronics, such
as organic light-emitting diodes (OLEDs), organic thin-film
transistors (OTFTs), organic photovoltaic cells, and organic
solid lasers, have attracted much interest. For example, with a
mobility that rivals that of amorphous Si1 and reasonable air
stability,2 pentacene and its derivatives are a common choice
for the transport layer in TFTs;3 BBL with a planar ladder-
conjugated system (Chart 1) shows high performance in air-
stable organic field-effect transistors and solar cells;4 and LPPP
and its derivatives with ladder-conjugated systems have been
utilized in efficient solution-processable blue LEDs.5 Their rigid
and planar frameworks not only facilitate electron delocaliza-
tion and enhance the conductivity but also exhibit high
resistance to mechanical, thermal, and chemical degradation.6
Among all the basic factors, multifunctional building blocks
are essential for designing and synthesizing ladder-conjugated
oligomers or polymers. For example 1,2,4,5-tetraaminobenzene
(TBA) (Chart 1), as the key building block of BBL-like
heteroaromatic ladder polymers, contributes to such out-
standing electronic and optical properties. However, TBA
lacks solubility-improving substituents, which makes BBL and
its analogue polymer PQL (Chart 1) insoluble in a variety of
organic solvents and causes processing difficulties in device
fabrication. Poor solubility not only inhibits some character-
izations and material processing but also causes some structure
defects such as deterioration in the thermal, physical, and
electrochemical properties.7 2,3,6,7-Tetraamino-9,9-bis(2-
ethylhexyl)fluorene (TABEF) (Chart 1), as an alternative to
TBA, readily undergoes a condensation reaction with
dicarboxylic acid substrates to give corresponding ladder-type
model compounds with good solubility.8 However, the small,
planar, electron-rich fluorenyl moiety is not the most ideal unit
for building n-type ladder-conjugated oligomers or polymers.
Thus, the design and synthesis of novel multifunctional
Received: March 29, 2013
© XXXX American Chemical Society
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Scheme 1. Synthetic Route to Ladder-Conjugated Oligomer 12
Scheme 2. Synthetic Route to Ladder-Conjugated Oligomer 13
building blocks by introducting functional units, such as
tetraamino and diamino groups, is a significant and ongoing
challenge for building ladder-conjugated oligomers or polymers.
way to obtain ring-expanded multifunctional building blocks. In
our recent work, we found that sunlight-driven photocyclization
at the bay sites of perylene using phenyl substituents can lead
two regioisomers,14 while employing monosubstituted func-
tional units such as thienyl, carbazolyl, thieno[3,2-b]thiophenyl,
monosubstituted phenyl, and Schiff base, affords only one
regioisomer.14,15 The regioselectivity of photocyclization
reactions, especially for photocyclization with disubstituted
functional units, have rarely been mentioned in previous work.
That will be a big obstacle in the further utilization of this
approach for building multifunctional blocks and constructing
ladder-conjugated oligomers and polymers. Thus, it is
instructive to study the photocyclization regioselectivity at the
bay sites of perylene to obtain planar ladder-conjugated
oligomers.
However, in our key photocyclization step, an unusual
regioselectivity was discovered. As shown in Figure 1, for two
substitutents X and Y (corresponding to the NO2 and NH2
substituents, respectively, in compound 4 in Scheme 1 and
compound 5 in Scheme 2), photocyclization at the bay sites of
perylene theoretically could occur at either the ortho position
RESULTS AND DISCUSSION
■
Regioselectivity of Photocyclization and Synthesis. In
our strategy, we designed and synthesized the two multifun-
tional building blocks tetraamine 8 (Scheme 1) and diamine 9
(Scheme 2) for use in constructing novel ladder-conjugated
oligomers 12 and 13, respectively. A perylene-3,4,9,10-
tetracarboxylic acid bisimide (PBI) unit, as a promising
building block, was introduced. First, the electronegativity of
PBI can enhance the stability of oligomers, and second, it also
has a significant impact on the electron distribution and the
capability of self-assembly into ordered supramolecular
structures.9−13 In addition, swallowtail chains and tert-butyl
groups were attached onto the peripheries to ensure good
solubility and suppress molecular aggregation.
In our syntheses, photocyclization of different functional
units at the bay sites of the perylene unit is the key and efficient
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Figure 1. Illustrations of regioselective photocyclization and structures of disubstituted phenyl regioisomeric oligomers.
1
Figure 2. Expanded aromatic regions of the H NMR and gCOSY spectra of compound 12 in 1,2-dichlorobenzene-d4.
or the para position relative to substituent X, generating two
regioisomers. In view of the steric effect, photocyclization
should be more likely to occur at the position para to X.
However, as shown in Scheme 1, we found that photo-
cyclization happened only at the position ortho to the nitro
group. This phenomenon has not been discovered previously.
Suzuki coupling reactions were adopted to link perylene
units 1 and 2 with 2-nitroaniline boronic ester 3 by single
bonds, giving 4 (70%; Scheme 1) and 5 (85%; Scheme 2),
respectively. Next, photocyclization was carried out to
accomplish the fusion to form the corresponding ladder-
conjugated intermediates 6 (90%) and 7 (95%). Hydro-
genations using H2 over Pd/C afforded the tetraamine and
diamine intermediates 8 and 9, respectively. Following typical
condensation−coupling reactions between 1,2-diamines and
1,2-diketones,16 twofold condensations of 8 with 10 and 9 with
11 were carried out, during which excess diketone 10 and
diamine 9 were necessary to ensure completion of the multiple
condensation reactions.
The chemical structures of the targeted oligomers 12 and 13
were unambiguously characterized by NMR spectroscopy and
MALDI-TOF mass spectrometry. In our synthetic strategy to
obtain oligomers 12 and 13, the ring expansion is one key.
Theoretically, photocyclization of compound 4 should generate
two regioisomers, 6 and 6a, but only one dominant product, 6
(yield over 90%), was found. Although this photocylization
product has very good solubility in chloroform and dichloro-
methane, poor signals were still observed in the aromatic region
of the NMR spectra, especially in the 13C NMR spectra. Such a
phenomenon can be attributed to the strong aggregation effect
of the rigid core molecules in solution. Fortunately, the
subsequent two steps (hydrogenation and condensation) also
gave single products in high yields, and the final product
1
showed good resolution in the H NMR and gCOSY spectra
1
(Figure 2). In the H NMR spectrum, two singlet signals were
observed at the lowest field. The chemical shifts of the two
singlet signals at low field were 12.94 and 11.03 ppm. We assign
these singlet resonances to protons H1 and H12, respectively.
C
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Figure 3. (a) UV−vis absorption spectra of 12 and 13 in chloroform solution at 1× 10−5 M. (b) Normalized UV−vis absorption spectra of 12 and
13 in thin films. (c) Fluorescence spectra of 12 and 13 in chloroform. (d) Electrochemical characterization of 12 and 13 in DCM containinig 0.1 M
TBAPF6. The scan speed was 100 mV/s, and ferrocene/ferrocenium (Fc/Fc+) was used as an external reference.
Table 1. Optical and Electrochemical Data for 12 and 13
a
b
(nm) [ε (M−1 cm−1)]
λ
(nm)
abs
Eogpt (eV)
Er°ed1 (V vs Fc/Fc+)
ELUMO (eV)
EHOMO (eV)
soln
abs
film
oligomer
λ
12
13
458 [69 200]
440 [130 400]
464
445
2.19
2.27
−1.37
−1.29
−3.71
−3.79
−5.90
−6.06
Optical band gap energies determined from thin films.18 Based on the assumption that the energy of Fc/Fc+ is 5.08 eV relative to vacuum.18
a
b
We also found four doublet signals in the aromatic regions of
oligomer 12, and all of the J values were 8 Hz. The gCOSY
spectrum suggested that these are two-group coupling signals
that should be assigned to protons H5 and H6 and protons H10
and H11. This evidence clearly indicates that the final product
was compound 12 and not its regioisomer 12a. Thus, we can
infer that the photocyclization reaction occurred at the position
ortho to the nitro group and that the product of photo-
cyclization was 6 and not its regioisomer 6a.
cm−1, respectively). Oligomer 12 containing only one PBI
segment also displays strong absorption over a broad range
from 300 to 550 nm, but its maximum extinction coefficient
(εmax = 69 200 M−1 cm−1) is considerably smaller than that of
13. The emission peak of 12 located at 535 nm is red-shifted by
10 nm relative to the corresponding peak for 13 (Figure 3c).
The quantum yields of 12 and 13 in chloroform are 0.17 and
0.15 respectively (with Rhodamine 6G as reference).17 In thin
films (Figure 3b), the absorption spectra of 12 and 13 become
slightly broader and show red shifts compared with those in
solution. Broad absorption and high extinction coefficients
make 12 and 13 potential materials for solar cells and
photodetectors.
The electrochemical properties of 12 and 13 were studied by
cyclic voltammetry (CV) and differential pulse voltammetry
(DPV) (see the Supporting Information) in DCM solution.
Their reduction potentials and the calculated LUMO energies
are shown in Table 1. As shown in Figure 3d, electrochemically
reversible reduction waves are observed for 12 and 13. The
half-wave potentials (Er°ed1) of oligomers 12 and 13 are −1.37
and −1.29 V vs Fc/Fc+, respectively. Oligomer 12 shows three
reduction peaks and 13 shows four reduction peaks, implying
their ability to accept at least three and four electrons,
respectively. No obvious redox waves were observed upon
oxidation up to 1.5 V. The LUMO energies (electron affinity)
derived from the half-wave potentials are −3.71 and −3.79 eV
respectively. The optical band gap energies (Eogpt) derived from
the low-energy absorption edges in thin films are 2.19 and 2.27
eV, respectively, from which the HOMO energies were
estimated as EHOMO = ELUMO − Eogpt. These data indicate that
oligomers 12 and 13 are potential n-type materials.
By cyclizing the 2-nitroanilinyl substituents at the bay sites of
the PBI core, we found an unusual regioselectivity of the
photocyclization compared with that in previous work. The
strong electron-withdrawing effect of the nitro group activates
the ortho H more than the para H and thus favors the
dehydrogenation ring closure at the ortho site. To our
knowledge, most of the functional blocks that have been
introduced by photocyclization at the bay sites of a perylene
have been monosubstituted and electron-rich functional units,
and the regioisomeric selectivity of this photocyclization has
been rarely discovered and discussed. For example, functional
blocks such as disubstituted phenyl, carbazolyl, thieno[3,2-
b]thiophenyl, truxenyl, and Schiff base have been introduced by
our group,14,15 and monosubstituted phenyl units were
introduced by Li, Zhu, and co-workers.15e,f Thienyl groups
were introduced by Ko and co-workers15g and Duan and
Zhan,15h and a 1,8-dicarboxymethylnaphthalene unit was
introduced by Bock and co-workers.15i However, in order to
obtain multifunctional blocks, it is important to understand the
regioselectivity of the photocyclization resulting from the
introduction of functional units containing electron-deficient or
electron-rich groups. Thus, this finding is of guiding significance
for future regioselective photocyclization and the introduction
of multifunctional units at the bay sites of the PBI core.
Physical Characterization. The absorption and photo-
luminescence (PL) spectra of oligomers 12 and 13 in
chloroform solution (1 × 10−5 mol/L) and in thin films are
shown in Figure 3, and the data are listed in Table 1. In
solution (Figure 3a), oligomer 13 possessing two PBI segments
shows a strong absorption bands across a broad range from 300
to 550 nm. There are three well-defined absorption peaks at
336, 440, and 508 nm (ε = 69 400, 130 400, and 76 300 M−1
The decomposition temperatures (Td, corresponding to 5%
weight loss) of 12 and 13 under nitrogen are 232.7 and 389.5
°C, respectively (see the Supporting Information). The Td
values for 12 and 13 indicate the upper temperature limits of
thermal annealing during processing. The difference in the Td
values for 12 and 13 may be attributed to the fact that 13 has
more PBI units, which can increase the thermal stability.
Solar Cell J−V Characterization. Bulk heterojunction
(BHJ) solar cells using poly(3-hexylthiophene) (P3HT) as the
donor and oligomers 12 and 13 and their parent compound
D
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1
([M]−), 1306.8385; found, 1306.8409. H NMR (400 MHz, CDCl3):
δ 0.84 (t, 12H), 1.20 (m, 72H), 1.83 (b, 4H), 2.23 (b, 4H), 5.15 (b,
2H), 6.41 (s, 4H), 6.94 (b, 2H), 7.45 (b, 2H), 7.98 (m, 2H), 8.20 (d,
1H, J = 8 Hz), 8.24 (d, 1H, J = 8 Hz), 8.6 (m, 4H). 13C NMR (125
MHz, CDCl3): δ 14.3, 27.1, 29.5, 29.8, 32.0, 32.5, 54.9, 120.9, 122.1,
122.6, 122.9, 123.3, 126.8, 128.12, 129.8, 129.9, 130.2, 130.8, 131.2,
132.4, 133.0, 134.7, 135.0, 135.7, 136.8, 138.8, 139.8, 144.9, 163.6,
164.7.
N,N′-bis(12-undecyldodecyl)perylene-3,4,9,10-bis-
(dicarboximide) (PBI-C23) as the acceptors were investigated
in a preliminary study. The current density−voltage (J−V)
characteristics of the BHJ solar cells are shown in Figure S3 in
the Supporting Information, and the corresponding solar cell
data are summarized in Table S1 in the Supporting
Information. The power conversion efficiencies (PCEs) of
solar cells constructed from oligomers 12 and 13 were 0.13%
and 0.06%, respectively, under AM 1.5G simulated solar
illumination. The moderate PCEs may result from the nonideal
surface morphology of BHJ solar cell films (Figure S4 in the
Supporting Information). Even so, the results for 12 and 13 are
better than that for their parent compound PBI-C23 under the
same conditions.
Compound 5. A mixture of 2 (334 mg, 0.3 mmol), 3 (88 mg, 0.33
mmol), K2CO3 (223 mg, 1.65 mmol), Pd(PPh3)4 (38 mg, 0.033
mmol), toluene (20 mL), H2O (0.9 mL), and EtOH (0.9 mL) was
stirred at 90 °C for 8 h. Next, the crude product was purified through
silica gel column chromatography with 2:3 DCM/hexane as the eluent.
Compound 5 was obtained as a dark-red honeylike substance (298 mg,
85%). HRMS (MALDI-TOF MS) m/z: calcd for C76H106N4O6
1
([M]−), 1170.8112; found, 1170.8149. H NMR (400 MHz, CDCl3)
In addition, adopting more suitable hole-transporting
materials to fabricate the BHJ solar cells would be a good
choice.19 For example, using a lower HOMO energy
polythiophene derivative with conjugated side chains (PT1)
as the donor to fabricate BHJ solar cells with PBI-based
polymers led to better film morphology and higher efficiencies
than obtained using P3HT, as shown by the Hashimoto
group.20 Thus, oligomers 12 and 13 can be used as a promising
n-type materials in organic solar cells.
δ 0.84 (t, 12H), 1.20 (m, 72H), 1.83 (b, 4H), 2.23 (b, 4H), 5.19 (m,
2H), 6.37 (s, 2H, NH2), 6.93 (d, 1H, J = 8 Hz), 7.37 (d, 1H, J = 8 Hz),
8.05 (d, 1H, J = 8 Hz), 8.22 (m, 1H), 8.45 (s, 1H), 8.65 (m, 5H). 13C
NMR (125 MHz, CDCl3): δ 14.2, 22.8, 27.0, 29.4, 29.7, 32.0, 32.5,
54.9, 120.9, 122.6, 122.9, 123.2, 123.8, 126.4, 127.7, 128.3, 128.7,
129.4, 129.6, 131.3, 132.5, 133.1, 134.5, 134.8, 135.8, 136.4, 139.2,
144.8, 163.5, 164.7.
Compound 6. A mixture of 4 (261 mg, 0.2 mmol), toluene (20
mL), and I2 (4 mg) was illuminated with sunlight at reflux for 6 h.
After distillation, the crude product was purified through silica gel
column chromatography with 3:2 DCM/hexane as the eluent.
Compound 6 was obtained as a red solid (234 mg, 90%). Mp: >300
°C. HRMS (MALDI-TOF MS) m/z: calcd for C82H106N6O8 ([M]−),
1302.8072; found, 1302.8138. 1H NMR (400 MHz, CDCl3): δ 0.78 (t,
12H), 1.14 (m, 54H), 1.42 (m, 18H), 2.11 (m, 4H), 2.45 (m, 4H),
5.41 (m, 2H), 6.05 (s, 4H), 7.57 (d, 2H, J = 8 Hz), 9.18 (s, 2H), 9.70
(d, 2H, J = 8 Hz), 10.15 (s, 2H). 13C NMR (125 MHz, CDCl3): δ
14.2, 22.8, 27.5, 29.5, 29.8, 32.0, 32.8, 55.7, 120.9, 122.0, 122.7, 122.1,
123.9, 124.4, 124.9, 125.4, 127.1, 129.5, 131.4, 143.3.
CONCLUSION
■
In summary, two multifunctional building blocks, tetraamine 8
and diamine 9, were efficiently synthesized and used to
construct novel, soluble ladder-conjugated oligomers. In the
key step of photocylization at the bay sites of PBI, nitro-group-
induced regioisomeric selectivity has been discovered. Tetra-
amine 8 and diamine 9 readily underwent condensation
reactions with a pyrene-4,5-dione and a pyrene-4,5,9,10-
tetraone, respectively, to give the corresponding ladder-
conjugated oligomers 12 and 13. These oligomers were
preliminarily applied as electron acceptors and blended with
P3HT as the donor to fabricate BHJ solar cells, which exhibited
reasonable performance.
Compound 7. A mixture of 5 (234 mg, 0.2 mmol), toluene (20
mL), and I2 (4 mg) was illuminated with sunlight at reflux for 6 h.
After distillation, the crude product was purified through silica gel
column chromatography with 1:1 DCM/hexane as the eluent.
Compound 7 was obtained as a red solid (222 mg, 95%). Mp:
151.9−153.4 °C. HRMS (MALDI-TOF MS) m/z: calcd for
1
C76H104N4O6 ([M]−), 1168.7956; found, 1168.7979. H NMR (400
MHz, CDCl3): δ 0.87 (t, 12H), 1.17 (m, 56H), 1.39 (m, 16H), 2.01
(m, 4H), 2.33 (m, 4H), 5.26 (m, 2H), 6.20 (s, 2H), 7.54 (d, 1H, J = 8
Hz), 8.90 (m, 5H), 9.23 (d, 1H, J = 8 Hz), 9.59 (s, 1H). 13C NMR
(125 MHz, CDCl3): δ 14.3, 22.8, 27.4, 29.5, 29.8, 32.1, 32.6, 55.3,
121.1, 122.9, 123.0, 123.2, 123.8, 123.9, 124.2, 125.3, 125.9, 126.6,
126.9, 127.1, 127.9, 129.3, 129.6, 130.3, 131.0, 131.8, 132.8, 133.3,
143.6, 163.9, 164.9.
Compound 8. A mixture of 6 (261 mg, 0.2 mmol), THF (20 mL),
and 10% Pd/C (30 mg) was shaken under hydrogen (5 psi) at 90 °C
for 6 h, after which the reaction mixture was filtered under reduced
pressure and the organics were concentrated by evaporation. In view of
the unstability of the tetraamine, the resulting brown oil (218 mg, 88%
yield) was used without further purification.
Compound 9. A mixture of 7 (234 mg, 0.2 mmol), THF (20 mL),
and 10% Pd/C (26 mg) was shaken under hydrogen (5 psi) at 90 °C
for 6 h, after which the reaction mixture was filtered under reduced
pressure and the organics were concentrated by evaporation. In view of
the unstability of the diamine, the resulting dark-red oil (205 mg, 90%
yield) was used in the next step without further purification.
Oligomer 12. An oxygen-free mixture of CHCl3 (4 mL) and acetic
acid (16 mL) was added to a flask containing tetraamino compound 8
(124 mg, 0.1 mmol) and compound 10 (103 mg, 0.3 mmol) under the
protection of Ar, and then the system was stirred at 135 °C overnight.
After the mixture was cooled to ambient temperature, the solvent was
removed under reduced pressure to give a residue. Flash silica gel
column chromatography (DCM/hexane eluent) was performed to
obtain the pure product 12 (112 mg, 60% yield). Mp: >300 °C (dec).
HRMS (MALDI-TOF MS) m/z: calcd for C130H150N6O4 ([M]−),
EXPERIMENTAL SECTION
■
Materials and Characterization. 1,7-Dibromoperylene bisimide
1,15a 1-bromoperylene bisimide 2,15a 2-nitro-4-(4,4,5,5-tetramethyl-
1,3,2-dioxaborolan-2-yl)aniline (3),21 pyrene-4,5-dione 10,22 and
pyrene-4,5,9,10-tetraone 1122 were synthesized according to literature
methods. The other reactants were purchased from commercial
sources. NMR spectra were measured using TMS as an internal
standard for 1H and 13C NMR spectroscopy. CV was performed with a
standard commercial electrochemical analyzer in a three-electrode
single-component cell under argon at a scan rate of 100 mV/s with a
glassy carbon working electrode, a Ag/AgNO3 reference electrode, a Pt
disk auxiliary electrode, Bu4NPF6 as the supporting electrolyte, and
ferrocene (Fc) as an internal standard. Thermogravimetric analysis
(TGA) was performed using dynamic scans under nitrogen. Tapping-
mode atomic force microscopy (TM-AFM) was performed on an
atomic force microscope. Photovoltaic devices were fabricated on
indium tin oxide (ITO)-coated glass substrates with a layered structure
of ITO/PEDOT:PSS/P3HT:12 or 13 blend/LiF/Al. Photovoltaic
performance was characterized through J−V curves recorded with a
source meter under AM 1.5G illumination.
Compound 4. A mixture of 1 (597 mg, 0.5 mmol), 3 (291 mg, 1.1
mmol), K2CO3 (744 mg, 5.5 mmol), Pd(PPh3)4 (127 mg, 0.11 mmol),
toluene (30 mL), H2O (2.3 mL), and EtOH (2.3 mL) was stirred at 90
°C for 12 h. Next, the crude product was purified through silica gel
column chromatography with 1:1 DCM/hexane as the eluent.
Compound 4 was obtained as a dark-red honeylike substance (457
mg, 70%). HRMS (MALDI-TOF MS) m/z: calcd for C82H110N6O8
E
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1859.1719; found, 1859.1830. 1H NMR (400 MHz, CDCl3): δ 0.97 (t,
12H), 1.36 (m, 20H), 1.51 (m, 20H), 1.56 (m, 8H), 1.69 (m, 8H),
1.84 (s, 18H), 1.88 (m, 8H), 2.08 (m, 8H), 2.22 (s, 18H), 2.75 (m,
4H), 3.11 (m, 4H), 6.12 (m, 2H), 8.13 (d, 2H, J = 8 Hz), 8.29 (d, 2H,
J = 8 Hz), 8.34 (s, 2H), 8.73 (s, 2H), 9.04 (d, 2H, J = 8 Hz), 9.91 (d,
2H, J = 8 Hz), 10.04 (s, 2H), 10.26 (s, 2H), 11.03 (s, 2H), 12.94 (s,
2H). 13C NMR (125 MHz, CDCl3): δ 14.2, 22.8, 28.1, 29.5, 29.9, 30.3,
31.8, 32.0, 32.3, 33.3, 35.4, 36.1, 55.6, 56.2, 120.8, 121.4, 122.2, 122.4,
122.8, 123.4, 123.9, 124.3, 125.4, 126.2, 126.8, 127.3, 128.0, 128.6,
130.0, 130.6, 131.4, 140.6, 141.4, 142.2, 149.3, 150.2, 164.6, 165.0,
165.6.
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(b) Weitz, R. T.; Amsharov, K.; Zschieschang, U.; Villas, E. B.;
Goswami, D. K.; Burghard, M.; Dosch, H.; Jansen, M.; Kern, K.; Klauk,
H. J. Am. Chem. Soc. 2008, 130, 4637. (c) Schmidt, R.; Ling, M. M.;
Oligomer 13. An oxygen-free mixture of CHCl3 (4 mL) and acetic
acid (16 mL) was added to a flask containing diamino compound 9
(114 mg, 0.1 mmol) and compound 11 (11 mg, 0.03 mmol) under the
protection of Ar, and then the system was stirred at 135 °C overnight.
After the mixture was cooled to ambient temperature, the solvent was
removed under reduced pressure to give a residue. Flash silica gel
column chromatography (DCM/hexane eluent) was performed to
obtain the pure product 13 (43 mg, 55% yield). Mp: >300 °C. HRMS
(MALDI-TOF MS) m/z: calcd for C176H226N8O8 ([M]−), 2579.7524;
Oh, J. H.; Winkler, M.; Konemann, M.; Bao, Z.; Wurthner, F. Adv.
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Mater. 2007, 19, 3692.
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Faraday Trans. 1998, 94, 2919.
(12) (a) Quante, H.; Mullen, K. Angew. Chem., Int. Ed. Engl. 1995, 34,
̈
1
found, 2579.7427. H NMR (400 MHz, CDCl3): δ 0.71 (m, 18H),
1323. (b) Pschirer, N. G.; Kohl, C.; Nolde, F.; Qu, J.; Mullen, K.
̈
0.82 (m, 24H) 1.19 (m, 160H), 1.80 (m, 8H), 2.00 (m, 8H), 5.43 (m,
4H), 8.91 (m, 4H), 9.19−9.78 (m, 10H), 10.02 (s, 2H), 10.22 (s, 2H),
12.12 (s, 2H). 13C NMR (125 MHz, CDCl3): δ 14.1, 22.7, 27.3, 29.4,
29.7, 32.0, 32.6, 54.9, 122.8, 123.2, 124.2, 125.2, 125.9, 126.2, 126.7,
127.1, 127.2, 127.6, 129.1, 129.3, 130.1, 130.4, 131.1, 133.6, 141.4,
164.4, 165.2.
Angew. Chem., Int. Ed. 2006, 45, 1401. (c) Holtrup, F. O.; Muller, G. R.
̈
J.; Quante, H.; De Feyter, S.; De Schryver, F. C.; Mullen, K. Chem.
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Eur. J. 1997, 3, 219.
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44, 1788. (b) Yang, Y.; Wang, Y.; Xie, Y.; Xiong, T.; Yuan, Z.; Zhang,
Y.; Qian, S.; Xiao, Y. Chem. Commun. 2011, 47, 10749. (c) Xie, Y.;
Zhang, X.; Xiao, Y.; Zhang, Y.; Zhou, F.; Qu, J. Chem. Commun. 2012,
48, 4338. (d) Zhang, Y.; Zhao, Z.; Cheng, C.; Xiao, Y. RSC Adv. 2012,
2, 12644. (e) Li, Y.; Zheng, H.; Li, Y.; Wang, S.; Wu, Z.; Liu, P.; Gao,
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ASSOCIATED CONTENT
■
S
* Supporting Information
Detailed experimental procedures and characterization data for
1
all new compounds; H, 13C NMR, gCOSY, and mass spectra
of the products; and DPV and TGA data for 12 and 13. This
material is available free of charge via the Internet at http://
pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Fax: +(86)411-84986252. E-mail: xiaoyi@dlut.edu.cn.
■
Notes
(16) Stille, J. K.; Mainen, E. L. Macromolecules 1968, 1, 36.
(17) Fischer, M.; Georges, J. Chem. Phys. Lett. 1996, 260, 115.
(18) Thompson, B. C.; Kim, Y. G.; McCarley, T. D. J. Am. Chem. Soc.
2006, 128, 12714.
(19) Sharma, G. D.; Suresh, P.; Mikroyannidis, J. A.; Stylianakis, M.
M. J. Mater. Chem. 2010, 20, 561.
(20) Zhou, E.; Cong, J.; Wei, Q.; Tajima, K.; Yang, C.; Hashimoto, K.
Angew. Chem., Int. Ed. 2011, 50, 2799.
(21) Hubbard, R. D.; Bamaung, N. Y.; Fidanze, S. D.; Erickson, S. A.;
Palazzo, F.; Wilsbacher, J. L.; Zhang, Q.; Tucker, L. A.; Hu, X.; Kovar,
P.; Osterling, D. J.; Johnson, E. F.; Bouska, J.; Wang, J.; Davidsen, S.
K.; Bell, R. L.; Sheppard, G. S. Bioorg. Med. Chem. Lett. 2009, 19, 1718.
(22) Hu, J.; Zhang, D.; Harris, F. W. J. Org. Chem. 2005, 70, 707.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank National Natural Science Foundation of China
(21174022), the National Basic Research Program of China
(2013CB733702), and the Specialized Research Fund for the
Doctoral Program of Higher Education (20110041110009) for
financial support.
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