X-and H-shape two dimensional conjugated oligomers with anthracene as the node

Article abstract of DOI:10.1002/asia.200900591

X-and H-shape two-dimensional (2D) conjugated oligomers (X-and H-mers) and relevant model compounds have been synthesized through the introduction of different conjugated segments at the 9,10 and 2,6-positions of anthracene, and their properties were stud

Full text of DOI:10.1002/asia.200900591

FULL PAPERS
DOI: 10.1002/asia.200900591
X- and H-Shape Two Dimensional Conjugated Oligomers with Anthracene
as the Node
Weibin Cui,[a] Yingying Fu,[a] Yao Qu,[a] Hongkun Tian,[a] Jingping Zhang,*[b]
Zhiyuan Xie,[a] Yanhou Geng,*[a] and Fosong Wang[a]
Abstract: X- and H-shape two-dimen-
sional (2D) conjugated oligomers (X-
and H-mers) and relevant model com-
pounds have been synthesized through
the introduction of different conjugat-
ed segments at the 9,10 and 2,6-posi-
tions of anthracene, and their proper-
ties were studied in detail. Comparing
with the model compounds, the X- and
H-mers are featured with broader ab-
sorption spectra and narrower energy
bandgaps. Computational studies on
the highest occupied molecular orbital
(HOMO) and the lowest unoccupied
molecular orbital (LUMO) also indi-
cate that these X- and H-mers are 2D
conjugated. Solution processed bulk
heterojunction (BHJ) solar cells with
[6,6]-phenyl-C61-butyric acid methyl
ester (PCBM) as the acceptor material
exhibited the power conversion effi-
ciency (PCE) up to 0.53%.
Keywords: absorption · anthracene ·
conjugated oligomers · two-dimen-
sional architecture
Introduction
However within the past few years, there is a growing inter-
est in developing conjugated molecules with two or three di-
mensional (2D or 3D) conjugation.[4–7] This extension of p-
electron delocalization may alter intra- and intermolecular
interactions, and finally result in novel or unique optoelec-
tronic properties. Furthermore, the development of 2D- or
3D-conjugated materials enriches the candidates for organic
optoelectronic devices and chemical sensors.[5,7–9]
One of the strategies to increase the structural dimension-
ality is to order several 1D segments into an aromatic
core.[6] Benzene is the most common core for this purpose,
and several 2D conjugated molecular systems with great
light-emitting or sensory properties have been demonstrat-
ed.[9,10] However, ortho substitution can cause great steric
hindrance and meta substitution is not favorable for effec-
tive conjugation.[11] This disadvantage limits benzene as an
ideal core in some 2D conjugated systems. For example,
Figure 1 shows 2D-conjugated cruciforms with four conju-
gated segments peripherally connected to the benzene core
through carbon–carbon single, double, and triple
bonds.[9,10,12–14] Compared with oligo(p-phenylene)s, oligo(p-
Organic semiconductors possessing a high degree of p con-
jugation have attracted considerable scientific and industrial
attention, owing to their potential applications in optoelec-
tronic devices, such as organic light-emitting diodes
(OLEDs), organic thin film transistors (OTFTs), and organ-
ic solar cells (OSCs).[1–3] One significant character of organic
semiconductors is that their properties can be tuned facilely
through the tailoring of molecular structures, including the
structures of aromatic units, substitution groups, conjugation
length and molecular geometry, and so forth.
Most of the reported conjugated molecules to date have
one-dimensional (1D) p-electron delocalization ready for
charge conduction and energy transport along the backbone.
[a] Dr. W. Cui, Y. Fu, Y. Qu, Dr. H. Tian, Prof. Z. Xie, Prof. Y. Geng,
Prof. F. Wang
State Key Laboratory of Polymer Physics and Chemistry
Changchun Institute of Applied Chemistry
Chinese Academy of Science
Changchun 130022 (P.R. China)
Fax : (+86)0431-8568-5653
E-mail: yhgeng@ciac.jl.cn
[b] Prof. J. Zhang
Faculty of Chemistry, Northeast Normal University
Changchun 130024 (P.R. China)
Fax : (+81)0431-8509-9521
E-mail: zhangjingping66@yahoo.com.cn
Figure 1. Chemical structures of cruciforms with benzene as the core.
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phenylenevinylene)s, and oligo(p-phenyleneethynylene)s,
which possess good one-dimensional conjugation, cruciforms
C1 and C2 exhibit unchanged or even hypochromatic-shifted
absorption maxima, not consistent with the extended conju-
gation.[13a,c,15] In contrast, ethynyl linkages can release steric
hindrance to render better conjugation for cruciform C3 and
C4,[9,12a,b,14g–i] and even more conjugated 2D molecules can
be obtained by locking the structures into planarity with the
diacetylene bridge.[12a,c] Some fused aromatic units, such as
hexabenzocoronenes and truxene, have also been used as
cores for the construction of 2D-conjugated systems. Their
2D-conjugated structures endow 2D-conjugated molecules
intriguing optoelectronic properties.[16,17]
model compounds is depicted in Scheme 1. The 9,10-disub-
stituted anthracene derivatives were synthesized in a proce-
dure similar to our previous reports.[23a,c] X0, H0, and X- and
H-mers were synthesized by typical Stille cross-coupling re-
actions.[24] To ensure purity, all of the above oligomers were
purified by preparative gel-permeation chromatography
(PGPC) after general chromatographic purification on silica
gel, and the yields of the oligomers were 30–45%. Chemical
structures of all these compounds were validated by using
NMR spectroscopy, matrix-assisted laser desorption ioniza-
tion time-of-flight (MALDI-TOF) mass spectrometry (MS),
and elemental analysis.
Anthracene is one of the most important aromatic units
with a planar and rather bigger conjugated structure. Owing
to its promising light-emitting and charge-transporting prop-
erties, anthracene has been widely used as a building block
for conjugated small molecules, oligomers, and poly-
mers.[18–23] Particularly, substitu-
Photophysical and Electrochemical Properties
Solution UV/Vis absorption (Figure 3a,c,e) and photolumi-
nescence (PL) spectra (Figure 3b,d,f) of X- and H-mers and
the model compounds were recorded in chloroform with a
ents can be introduced at four
positions (2, 6, 9, and 10-posi-
tions) without spatial interfer-
ence. According to a previous
report,
poly(2,6-anthrylene)s
are well-conjugated polymers
and steric hindrance between
aryl substituents at 9,10-posi-
tions and anthracne can be re-
leased by using ethynyl linkag-
es.[23] All these features imply
that anthracene is an ideal core
candidate for the construction
of well conjugated 2D molecu-
lar systems. With this outlook
in mind, we herein report the
synthesis and characterization
of two series of 2D-conjugated
oligomers with anthracene as
the node, which exhibits the X
and
(named as X- and H-mers, re-
spectively), as shown in
H-shape
architectures
Figure 2. To release the steric
hindrance, substituents in 9,10-
positions
were
introduced
through ethynyl linkages.[23a]
Furthermore, five model com-
pounds, as shown in Figure 2,
were also synthesized and char-
acterized for comparison.
Results and Discussion
Synthesis
The synthesis of 2D conjugated
oligomers (X- and H-mers) and Figure 2. Structures of model compounds and 2D X- and H-shape conjugated oligomers.
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J. Zhang, Y. Geng et al.
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concentration
of
10À5
m
(Table 1). As some absorption
spectra are very complex, only
the absorption maxima at the
long wavelengths are listed for
the comparison of optical
bandgaps (DEOg pt). As shown in
Figure 3a,
the
absorption
maxima of the model com-
pounds M1, M2, and M3 at
long wavelengths red shift from
l=434 nm of M1 to l=467 nm
of M2 and then to l=496 nm
of M3 with the variation of the
substituents from alkynyl to
phenylethynyl and then to styr-
ylphenylethynyl,
respectively.
Their PL spectra exhibit a simi-
lar trend with emission maxima
of l=443, 497, and 534 nm for
M1, M2, and M3, respectively
(Figure 3b). The noticeable red
shifts of both absorption and
PL spectra with the increase of
the conjugation length of the
substituents imply the effective
conjugation between anthra-
cene and substituents. Different
from cruciforms that have ben-
zene as the core,[13a] both X-
and H-mers show the red shifts
of the long wavelength absorp-
tion maxima (Figure 3 and
Table 1) compared to the model
compounds, together with very
broad absorption spectra. For
example, the long wavelength
absorption maxima of X1 and
H1 are 65 and 22 nm red shift-
ed compared to that of M1.
With the increase of the conju-
gation length of the substituents
at the 9,10-positions of anthra-
cene, the long wavelength ab-
sorption maxima of both X-
and H-mers also exhibit notice-
able red shifts, which are l=
499, 519, and 537 nm for X1,
X2, and X3, respectively, and
l=456, 488, and 515 nm for
H1, H2, and H3, respectively.
Furthermore, both X- and H-
mers also exhibit noticeable red
shifts of absorption maxima
compared to X0 and H0, which
have no substituents at the
9,10-positions. All these details
Scheme 1. Synthetic route of model compounds and 2D X- and H-shape conjugated oligomers. Reagents and
Conditions: a) 1)nBuLi, THF, À308C; 2)Bu3SnCl or Me3SnCl, À308C to room temperature; b) Pd(PPh3)4,
DMF/toluene, 908C; c) 1)nBuLi, THF, 08C to room temperature; 2)SnCl2, 50% aqueous acetic acid/THF.
Figure 3. UV/Vis spectra (a,c,e) and photoluminescence spectra (b,d,f) of the oligomers and model compounds
in dilute solution (10À5 m, in chloroform).
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Chem. Asian J. 2010, 5, 932 – 940

Two Dimensional Conjugated Oligomers
Table 1. Photophysical properties of the oligomers and model compounds.
intermolecular interaction in
the solid state. Furthermore,
along with the bathochromic
shift, the absorption ranges of
X- and H-mers are further
broadened.
Cyclic voltammograms (CV)
of the X- and H-mers and the
model compounds were record-
ed in methylene chloride with
Bu4NPF6 as the supporting elec-
trolyte, to obtain the energy
levels (Figure 5). From the
onset of the oxidation potential,
their highest occupied molecu-
lar orbital (HOMO) levels can
Solution
max
Film
max
Compound
l
[nm][a]
l
[nm][b]
HOMO[d] [eV]
DEOg pt[e] [eV]
Absorption
Emission
Absorption
H0
H1
H2
H3
X0
X1
X2
X3
M1
M2
M3
437
456
488
515
454
499
519
537
434
467
496
532
565
601
605
526
572
604
613
443
497
534
524
558
ꢀ545[c]
ꢀ550[c]
533
541
591
603
–
À5.15
À5.09
À5.06
À5.05
À5.10
À5.13
À5.03
À5.01
À5.45
À5.37
À5.30
2.40
2.29
2.19
2.14
2.43
2.32
2.27
2.25
2.79
2.53
2.36
–
–
Solution
max
[a] Absorption and photoluminescence maxima (l
) in chloroform with a
concentration of 10À5 m.
[b] Films were spin-cast from chloroform solution with a concentration of 3 mgmLÀ1 at 1000 rpm. [c] Unable
to identify accurately. [d] Estimated from the electrochemical oxidation onset. [e] Estimated from the onset of
the solution absorption spectra.
indicate that the extension of the conjugated framework
either along 9–10 or 2–6 directions of the anthracene unit
can increase the conjugation of the molecules, and solidify
the 2D-conjugation feature of X- and H-mers. Similarly, the
PL spectra of the X- and H-mers also show noticeable bath-
ochromic shifts relative to those of M1, M2, M3, X0, and
H0 (Figure 3b,d,f). Optical-band gaps (DEOg pt) of all the
compounds estimated from the absorption onsets are out-
lined in Table 1, which vary in the same trend as the absorp-
tion and PL maxima.
Displayed in Figure 4 are the film absorption spectra of
the X- and H-mers. From solution to film, all these com-
pounds exhibit a large red shift in the absorption spectra,
which indicates that the 2D-conjugated molecules adopt a
more planar molecular geometry or that they have a strong
Figure 5. Cyclic voltammograms of the oligomers and model compounds
in CH2Cl2 (10À3 m) with Bu4NPF6 (0.1m) as electrolyte at a scan rate of
80 mVsÀ1
.
be estimated (Table 1). The HOMO levels of M1, M2, M3,
H0, and X0 are À5.45, À5.37, À5.30, À5.15, and À5.10 eV,
respectively. The HOMO levels of X- and H-mers are in the
range of À5.13–5.01 eV and À5.09–5.05 eV, respectively,
which are close to or slightly higher than those of X0 and
H0, but are much higher than those of M1, M2, and M3.
These indicate the HOMO levels of X- and H-mers are
mainly determined by quarterthiophene segments.
Quantum Chemical Calculations
To gain further insight into the electronic structure of the X-
and H-mers, we performed quantum chemical calculations
(HF/3-21G) on model compounds M1, M2, M3, and X- and
H-mers. To simplify the calculation, all alkyl chains in the
molecules were replaced by methyl groups. As shown in
Figure 6, for the model compounds M1, M2, and M3, the
HOMOs and the lowest unoccupied molecular orbitals
(LUMOs) both localize over the whole molecule, which is
consistent with the red-shifts of absorption spectra as shown
in Figure 3a with the extension of the conjugation of the
substituents.
The molecular orbital plots and HOMO/LUMO positions
of X- and H-mers with alkyl chains replaced by methyl
groups are displayed in Figure 7. The HOMOs of the X-and
Figure 4. Film UV/Vis absorption spectra of the oligomers.
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J. Zhang, Y. Geng et al.
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introduced. The spatial separation of HOMO and LUMO
was also observed in cruciforms comprising donor and ac-
ceptor branches.[9d,f,12a] In the current cruciforms (X-mers),
the quarterthiophene segment is more electron-rich than al-
kynyl and arylethynyl groups, which may result in the spatial
separation of the HOMO and LUMO. Furthermore, quan-
tum chemical calculations also indicate that these X-and H-
mers have several strong transitions, which are responsible
for their broad absorption spectra. According to the previ-
ous reports on cruciforms, it is possible to further modulate
the distribution of the HOMO and LUMO of anthracene-
node 2D conjugated system by selecting branches with dis-
tinct donor–acceptor ability, and then to afford novel 2D-
conjugated oligomers with intriguing properties, such as
low-bandgap materials with wide absorption ranges.
Figure 6. Molecular orbital plots (LUMOs, top; HOMOs, bottom) of the
model compounds M1–M3 with alkyl chains replaced by methyl groups
for simplification. The calculations were performed at the HF/3-21G
level.
Photovoltaic Properties
As discussed above, all 2D X- and H-mers exhibit broad ab-
sorption spectra. It is well known that the wide-range ab-
sorption of the materials may favor the improvement of
OSC efficiency to better harvest sunlight. To evaluate the
OSC performance of the current X- and H-mers, bulk heter-
ojunction OSCs were fabricated by using the X- and H-mers
as the donor, and [6,6]-phenyl-C61-butyric acid methyl ester
(PCBM) as the acceptor, with a device structure of ITO/
poly(3,4-ethylene dioxythiophene):poly(styrene sulphonate)
(PEDOT:PSS)/oligomers:PCBM (1:2, w/w)/LiF/Al. Current
density–voltage curves of the devices under the illumination
of white light (100 mWcmÀ2) are shown in Figure 8. The
photovoltaic properties are summarized in Table 2. The
moderate power conversion efficiencies (PCE) of 0.40–
0.53% were achieved.
Figure 7. Molecular orbital plots (LUMOs, top; HOMOs, bottom) of the
X- and H-mers with alkyl chains replaced by methyl groups. The calcula-
tions were performed at the HF/3-21G level.
H-mers spread almost over the whole anthracene-quater-
thiophene along the 2,6-direction of anthracene. The sub-
stituents at the 9,10-positions of anthracene contribute little
to the HOMO levels. This is consistent with the electro-
chemical analysis on the HOMO levels, which are only
slightly enhanced with an increase of the conjugation length
of the substituents at the 9,10-positions. The LUMOs of X-
mers mainly locate on the anthracene-centered fragments
but those of H-mers spread mainly along the anthracene–
quaterthiophene segments. Nevertheless, LUMO energy
levels are more significantly affected by the substituents at
9,10-positions, and the HOMO–LUMO gaps of X- and H-
mers shrink while the long substituents at 9,10-positions are
Figure 8. I–V curves of the oligomer solar cells based on X- and H-mers
under the illumination of 100 mWcmÀ2 white light.
Conclusions
In conclusion, two series of oligomers possessing X- and H-
shapes with anthracene as the node were synthesized by
means of the Stille cross-coupling reaction. Optical, electro-
chemical, and computational studies confirmed their 2D
conjugated features. It was found that the introduction of
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Two Dimensional Conjugated Oligomers
Table 2. Open circuit voltages (Voc), short circuit current densities (Jsc),
fill factors (FF) and power conversion efficiencies (PCE) of the organic
solar cells based on X- and H-mers with the device structure of ITO/PE-
DOT:PSS (30 nm)/oligomer:PCBM (1:2 w/w, 70–100 nm)/LiF/Al.
Model compound X0: A mixture of 3 (0.10 g, 0.28 mmol), 2a (0.60 g,
0.63 mmol), DMF/toluene (3 mL/12 mL) and [Pd(PPh3)4] (3 mg) was
AHCTUNGTRENNUNG
heated at 908C for 30 h. Then the mixture was poured into water and ex-
tracted with chloroform. The organic layer was washed with brine and
dried over anhydrous MgSO4. On removal to the solvent, the residue was
first purified with column chromatography on silica gel (PE/methylene
chloride (DCM)=6:1). Further purification was performed with PGPC
to yield X0 (0.16 g, 37%) as an orange solid. 1H NMR (300 MHz,
CDCl3): d=0.86–0.94 (m, 12H), 1.26–1.37 (m, 64H), 1.61–1.78 (m, 16H),
2.77–2.87 (m, 8H), 6.95 (d, J=5.4 Hz, 1H), 7.04 (d, J=3.3 Hz, 1H), 7.12
(d, J=3.9 Hz, 1H), 7.15–7.20 (m, 4H), 7.34 (s, 1H), 7.74 (dd, J1 =
8.85 Hz, J2 =1.65 Hz, 1H), 7.99 (d, J=9.0 Hz, 1H), 8.15 (s, 1H), 8.37 ppm
(s, 1H); 13C NMR (100 MHz, CDCl3): d=14.12, 22.70, 29.29, 29.37, 29.51,
29.68, 30.57, 30.67, 31.93, 123.59, 123.88, 124.09, 126.31, 126.36, 126.54,
126.75, 128.80, 130.10, 130.32, 130.39, 130.83, 131.46, 131.87, 135.28,
135.43, 136.74, 136.82, 139.91, 140.90, 141.94 ppm; MALDI-TOF MS (re-
flectron mode): m/z (%): 1506.7 (100); elemental analysis calcd (%) for
C94H122S8: C 74.84, H 8.15; found: C 74.40, H 9.05.
Oligomer
Voc [V]
Jsc [mAcmÀ2
]
FF
PCE [%]
X1
X2
X3
H1
H2
H3
0.71
0.68
0.69
0.75
0.79
0.66
1.92
1.66
1.25
1.80
1.22
1.40
0.30
0.47
0.59
0.29
0.47
0.57
0.41
0.53
0.51
0.40
0.45
0.52
the conjugated segments along 2,6 and 9,10-directions of an-
thracene both resulted in shrinkage of the bandgaps of the
oligomers, and all 2D oligomers exhibited broad absorption
spectra comprising multiple absorption bands. These indi-
cate that anthracene is a promising core-candidate for 2D-
conjugated oligomers. The potential of the oligomers as
donor materials for organic solar cells has also been evaluat-
ed. The best maximum power conversion efficiency up to
0.53% was achieved.
Model compound H0: A mixture of 4 (0.28 g, 1.1 mmol), 2b (0.49 g,
0.49 mmol), DMF/toluene (3 mL/12 mL) and [PdACTHUNRTGNEUNG(PPh3)4] (7 mg) was
heated at 908C for 36 h. Then the mixture was poured into water and ex-
tracted with chloroform. The organic layer was washed with brine and
dried over anhydrous MgSO4. On removal to the solvent, the residue was
purified with column chromatography on silica gel (PE/DCM=4:1) and
then PGPC to yield H0 (0.26 g, 42%) as an orange solid. 1H NMR
(300 MHz, CDCl3): d=0.87 (m, 6H), 1.26–1.52 (m, 36H), 1.73–1.78 (m,
4H), 2.86 (t, J=7.77 Hz, 4H), 7.12 (d, J=3.78H, 2H), 7.17 (d, J=
3.78 Hz, 2H), 7.34 (s, 2H), 7.45–7.48 (m, 4H), 7.73 (dd, J1 =8.82 Hz, J2 =
1.56 Hz, 2H), 7.98–8.02 (m, 6H), 8.19 (s, 2H), 8.40 ppm (d, J=10.3 Hz,
4H); 13C NMR (100 MHz, CDCl3): d=14.12, 22.70, 29.38, 29.51, 29.69,
30.58, 31.93, 123.59, 123.82, 124.00, 125.50, 125.68, 126.19, 126.40, 126.74,
128.13, 128.23, 128.87, 130.71, 130.88, 131.71, 131.85, 132.28, 135.39,
136.77, 140.93, 142.07 ppm; MALDI-TOF MS (reflectron mode): m/z
(%): 1018.5 (100); elemental analysis calcd (%) for C68H74S4: C 80.10,
H 7.32; found: C 80.01, H 7.91.
Experimental Section
Materials
Tetrahydrofuran (THF) and toluene were distilled over sodium/benzo-
phenone. N,N-Dimethylformamide (DMF) was distilled over CaH2 under
reduced pressure. Other reagents were obtained from commercial resour-
ces and used without further purification. 3,3’’’-Didodecyl-2,2’:5’,2’’:5’’,2’’’-
quaterthiophene (1), 2-bromoanthracene (3), 2,6-dibromoanthracene (4),
2,6-dibromo-9,10-di(oct-1-ynyl)anthracene (5), 2,6-dibromo-9,10-bis((4-
dodecylphenyl)-1-ethynyl)anthracene (6), 2,6-dibromo-9,10-bis(2-(4-((E)-
3,4-bis(2-ethylhexyloxy)styryl)phenyl)ethynyl) anthracene (7), 2-bromo-
9,10-di(oct-1-ynyl)anthracene (8), 9,10-di(oct-1-ynyl)anthracene (M1), 1-
dodecyl-4-ethynylbenzene (9), and 11 were synthesized according to the
literature.[25, 19d,23a,c] PGPC purification was carried out by using a JAILC-
9104 recycling preparative high-performance liquid chromatography
(JAIGEL 2H/3H column assembly) with toluene as the eluent.
X-mer X1: The procedure for the synthesis of X0 was followed to pre-
pare X1 from 5 and 2a as an orange solid in a yield of 29%. 1H NMR
(300 MHz, CDCl3): d=0.85–0.89 (m, 18H), 1.26–1.47 (m, 84H), 1.65–1.75
(m. 8H), 1.89 (m. 4H), 2.76–2.87 (m, 12H), 6.95 (d, J=5.19 Hz, 2H),
7.03 (d, J=3.78 Hz, 2H), 7.11 (d, J=3.81 Hz, 2H), 7.14–7.16 (m, 4H),
7.19 (d, J=5.19 Hz, 2H), 7.36 (s, 2H), 7.79 (dd, J1 =9.03 Hz, J2 =1.68 Hz,
2H), 8.52 (d, J=9.00 Hz, 2H), 8.70 ppm (d, J=1.47 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=14.12, 20.37, 22.69, 28.94, 29.11, 29.29, 29.37,
29.53, 29.67, 30.61, 30.66, 31.55, 31.93, 103.90, 118.52, 122.86, 123.87,
124.66, 126.41, 126.52, 126.97, 127.97, 130.09, 130.32, 130.66, 131.58,
131.86, 132.27, 135.29, 135.42, 136.76, 136.85, 139.90, 140.95, 142.08 ppm;
MALDI-TOF MS (reflectron mode): m/z (%): 1724.4 (100); elemental
analysis calcd (%) for C110H146S8: C 76.60, H 8.53; found: C 76.57, H 8.24.
5-Tributylstannyl-3,3’’’-didodecyl-2,2’:5’,2’’:5’’,2’’’-quaterthiophene (2a): To
a solution of 1 (0.667 g, 1.00 mmol) in THF (20 mL) was added nBuLi
(0.40 mL, 1.0 mmol, 2.5m in hexane) dropwise at À308C. One hour later,
tributyltin chloride (0.25 mL, 1.2 mmol) was added at this temperature.
The mixture was stirred at room temperature overnight, poured into
water and extracted with petroleum ether (PE). The organic layer was
washed with brine and dried over anhydrous MgSO4. On removal of the
solvent, 2a (0.95 g) was obtained as brown-yellow oil, which was used di-
rectly without further purification. 1H NMR (300 MHz, CDCl3) d=0.87–
0.94 (m, 15H), 1.14–1.39 (m, 54H), 1.61–1.64 (m, 4H), 2.77–2.80 (m,
4H), 6.95 (d, J=7.95 Hz, 1H), 6.96 (s, 1H), 6.70–7.02 (m, 2H), 7.10–7.13
(m, 2H), 7.18 ppm (dd, J1 =5.20 Hz, J2 =1.63 Hz, 1H).
X-mer X2: The procedure for the synthesis of X0 was followed to pre-
pare X2 from 6 and 2a as a dark red solid in a yield of 30%. 1H NMR
(300 MHz, CDCl3): d=0.85–0.88 (m, 18H), 1.26–1.35 (m, 108H), 1.64–
1.75 (m, 12H), 2.69 (t, J=7.65 Hz, 4H), 2.77–2.85 (m, 8H), 6.95 (d, J=
5.16 Hz, 2H), 7.03 (d, J=3.75 Hz, 2H), 7.10 (d, J=3.78 Hz, 2H), 7.14–
7.16 (m, 4H), 7.19 (d, J=5.19 Hz, 2H), 7.29 (d, J=8.16 Hz, 4H), 7.35 (s,
2H), 7.72 (d, J=8.07 Hz, 2H), 7.78 (dd, J1 =8.94 Hz, J2 =1.62 Hz, 2H),
8.55 (d, J=8.97 Hz, 2H), 8.73 ppm (s, 2H); 13C NMR (100 MHz, CDCl3):
d=14.12, 22.70, 29.38, 29.51, 29.64, 29.72, 30.51, 30.67, 31.39, 31.94, 36.14,
86.07, 103.24, 118.19, 120.72, 122.62, 123.05, 123.81, 123.88, 124.75, 126.25,
126.47, 126.85, 127.79, 128.72, 130.10, 130.37, 130.76, 131.52, 131.63,
132.01, 135.38, 136.71, 136.80, 138.61, 138.70, 139.84, 140.82, 141.77,
143.93 ppm; MALDI-TOF MS (reflectron mode): m/z (%): 2044.7 (100);
5,5’’’-Bis(trimethylstannyl)-3,3’’’-didodecyl-2,2’:5’,2’’:5’’,2’’’-quaterthio-
phene (2b): To a solution of 1 (0.600 g, 0.90 mmol) in THF (20 mL) was
added nBuLi (0.80 mL, 2.0 mmol, 2.5m in hexane) dropwise at À308C.
One hour later, trimethyltin chloride (0.37 g, 1.8 mmol) was added at this
temperature. After stirred at room temperature overnight, the mixture
was poured into water and extracted with Et2O. The organic layer was
washed with brine and dried over anhydrous MgSO4. On removal of the
solvent, the residue was further purified by recrystallization from ethanol
to yield 2b (0.85 g, 76%) as a yellow solid. 1H NMR (300 MHz, CDCl3)
d=0.28–0.47 (m, 18H), 0.85–0.89 (m, 6H), 1.25–1.34 (m, 36H), 1.61–1.70
(m, 4H), 2.78 (t, J=7.87 Hz, 4H), 6.99–7.00 (m, 4H), 7.11 ppm (d, J=
3.75 Hz, 2H).
elemental analysis calcd (%) for
C 78.48, H 8.66.
C134H178S8: C 78.69, H 8.77; found:
X-mer X3: The procedure for the synthesis of X0 was followed to pre-
pare X3 from 7 and 2a as a dark red solid in a yield of 31%. 1H NMR
(300 MHz, CDCl3): d=0.84–0.98 (m, 36H), 1.25–1.36 (m, 90H), 1.51–1.55
(m, 18H), 1.77–1.81 (m, 8H), 2.78 (t, J=7.65 Hz, 8H), 3.89 (dd, J1 =
19.5 Hz, J2 =5.7 Hz, 8H), 6.79 (d, J=8.28 Hz, 2H), 6.91–7.00 (m, 9H),
Chem. Asian J. 2010, 5, 932 – 940
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
937

J. Zhang, Y. Geng et al.
FULL PAPERS
7.07–7.17 (m, 13H), 7.53 (d, J=8.01 Hz, 4H), 7.68–7.70 (m, 6H), 8.40 (d,
J=8.94 Hz, 2H), 8.57 ppm (s, 2H); 13C NMR (100 MHz, CDCl3): d=
11.24, 14.12, 22.70, 23.11, 23.92, 29.19, 29.37, 29.50, 29.56, 29.71, 29.78,
30.49, 30.64, 31.93, 39.60, 39.67, 71.56, 71.70, 87.59,103.52, 111.24, 113.34,
118.13, 120.35, 121.91, 122.60, 123.75, 123.85, 123.92, 124.72„ 125.70,
126.25, 126.37, 126.46, 126.87, 127.73, 129.88, 130.00, 130.10, 130.39,
130.80, 131.46, 131.68, 131.96, 135.41, 136.74, 138.07, 139.79, 140.82,
141.72, 149.66, 149.90 ppm; MALDI-TOF MS (reflectron mode): m/z
(%): 2425.1 (100); elemental analysis calcd (%) for C158H206O4S8:
C 78.23, H 8.56; found: C 78.20, H 9.26.
4H), 7.76 (d, J=8.28 Hz, 4H), 8.70–8.73 ppm (m, 4H); MALDI-TOF
MS (reflectron mode): m/z (%): 1094.7 (100); elemental analysis calcd
(%) for C78H94O4: C 85.51, H 8.65; found: C 85.30, H 8.15.
2-Bromo-9,10-bis(2-(4-((E)-3,4-bis(2-ethylhexyloxy)styryl)phenyl)ethyn-
yl) anthracene (12): The procedure for the synthesis of M2 was followed
to prepare 12 from 11 and 2-bromoanthraquinone as an orange solid in a
1
yield of 55%. H NMR (300 MHz, CDCl3): d=0.89–1.00 (m, 24H), 1.33–
1.38 (m, 16H), 1.48–1.56 (m, 16H), 1.74–1.82 (m, 4H), 3.89–3.96 (m,
8H), 6.87 (d, J=8.31 Hz, 2H), 6.97–7.17 (m, 8H), 7.58 (dd, J1 =8.43 Hz,
J2 =2.22 Hz, 4H), 7.65–769 (m, 7H), 7.72 (d, J=4.8 Hz, 2H), 7.75 (d, J=
4.3 Hz, 2H), 8.55 (d, J=9 Hz, 1H), 8.65–8.68 (m, 2H), 8.82 ppm (d, J=
1.77 Hz, 1H); MALDI-TOF MS (reflectron mode): m/z (%): 1172.6
(100).
H-mer H1: The procedure for the synthesis of H0 was followed to pre-
pare H1 from 8 and 2b as a dark red solid in a yield of 31%. 1H NMR
(300 MHz, CDCl3): d=0.85–0.98 (m, 18H), 1.26–1.55 (m, 48H), 1.74–1.87
(m, 24H), 2.75–2.87 (m, 12H), 7.15 (d, J=3.75 Hz, 2H), 7.20–7.21 (d, J=
3.75 Hz, 2H), 7.39 (s, 2H), 7.53–7.59 (m, 4H), 7.82 (dd, J1 =9.07 Hz, J2 =
1.77 Hz, 2H), 8.56 (m, 6H), 8.76 ppm (d, J=1.44 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=14.11, 20.25, 20.37, 22.65, 28.84, 28.92, 29.03,
29.10, 29.38, 29.54, 29.68, 29.72, 30.62, 31.43, 31.55, 31.93, 103.33, 103.99,
118.59, 122.87, 123.96, 124.47, 126.32, 126.45, 126.51, 126.99, 127.25,
127.31, 128.03, 129.16, 130.62, 131.42, 131.53, 132.15, 132.27, 132.60,
135.39, 136.81, 140.98, 142.17 ppm; MALDI-TOF MS (reflectron mode):
m/z (%): 1451.9 (100); elemental analysis calcd (%) for C100H122S4:
C 82.70, H 8.47; found: C 82.70, H 8.47.
H-mer H3: The procedure for the synthesis of H0 was followed to pre-
pare H3 from 12 and 2b as a dark red solid in a yield of 41%. 1H NMR
(300 MHz, CDCl3): d=0.82–0.98 (m, 60H), 1.23–2.79 (m, 106H), 2.74–
2.79 (m, 4H), 3.71–3.73 (m, 4H), 3.84–3.96 (m, 12H), 6.69 (d, J=8.37 Hz,
2H), 6.85–7.21 (m, 24H), 7.51–7.60 (m, 12H), 7.65 (d, J=8.25 Hz, 4H),
7.72 (d, J=8.22 Hz, 6H), 8.46 (d, J=8.94 Hz, 2H), 8.50–8.58 (m, 4H),
8.72 ppm (s, 2H); 13C NMR (100 MHz, CDCl3): d=11.12, 11.21, 14.11,
22.69, 23.02, 23.09, 23.79, 23.92, 29.07, 29.16, 29.40, 29.63, 29.78, 30.49,
30.60, 31.93, 39.48, 39.62, 39.67, 71.41, 71.69, 87.39, 87.71, 102.74, 103.79,
111.26, 113.19, 113.41, 118.35, 120.27, 120.40, 121.85, 122.68, 124.07,
124.53, 125.57, 125.72, 126.29, 126.83, 127.20, 127.80, 129.84, 130.05,
130.83, 131.21, 131.74, 131.95, 132.24, 135.51, 136.75, 138.09, 140.79,
141.70, 149.54, 149.70, 149.87 ppm; MALDI-TOF MS (reflectron mode):
m/z (%): 2853.9 (100); elemental analysis calcd (%) for C196H242O8S4:
C 82.48, H 8.55; found: C 82.11, H 9.30.
9,10-Bis((4-dodecylphenyl)-1-ethynyl)anthracene (M2): To a solution of
1-dodecyl-4-ethynylbenzene (9) (0.89 g, 2.2 mmol) in dry THF (10 mL)
was added n-butyllithium (0.80 mL, 2.2 mmol, 2.5m in hexane) at 08C.
After 1 hour, anthraquinone (0.21 g, 1.0 mmol) was added. After stirring
at room temperature for 8 h, the mixture was poured into water and ex-
tracted with PE. The organic layer was washed with brine and dried over
anhydrous MgSO4. On removal of the solvent, the residue was dissolved
in THF (20 mL), and then added dropwise to a solution of SnCl2·2H2O
(1.13 g, 5.00 mmol) in 50% acetic acid (20 mL). The mixture was stirred
at room temperature overnight. The precipitate was collected, washed
with a large amount of 1m HCl and water, and then dried on vacuum.
M2 was obtained as a yellow solid in a yield of 71% (0.50 g) after recrys-
tallization from chloroform. 1H NMR (300 MHz, CDCl3): d=0.86–0.90
(m, 6H), 1.27–1.33 (m, 36H), 1.54–1.66 (m, 4H), 2.67 (t, J=7.65 Hz,
4H), 7.27 (d, J=7.32 Hz, 4H), 7.62–7.65 (m, 4H), 7.69 (d, J=8.13 Hz,
4H), 8.68–8.71 ppm (m, 4H); MALDI-TOF MS (reflectron mode): m/z
(%): 714.4 (100); elemental analysis calcd (%) for C54H66: C 90.70,
H 9.30; found: C 90.30, H 9.30.
Measurements
1H NMR and 13C NMR were recorded by using a Bruker 300 MHz spec-
trometer or 400 MHz spectrometer in CDCl3, with tetramethylsilane
(TMS) as an internal standard. Elemental analyses were performed by
using an Eager 300 elemental analyzer. MALDI-TOF mass spectra were
recorded by using a Voyager-DE STR mass spectrometer with 2-(4-hy-
droxyphenylazo)-benzoic acid as the matrix. Absorption spectra were ob-
tained by using a PerkinElmer Lambda35 UV/Vis spectrometer. Photolu-
minescence spectra were recorded in CHCl3 by using a PerkinElmer
LS50B luminescence spectrometer. Cyclic voltammetry (CV) was per-
formed by using a CHI660a electrochemical analyzer with a three-elec-
trode cell in a solution 0.1m tetrabutylammonium hexafluorophosphate
(Bu4NPF6) as supporting electrolyte dissolved in methylene chloride at a
scan rate of 80 mVsÀ1. A Pt disk was used as the working electrode, a Pt
wire as the counter electrode, and an Ag/AgCl electrode as the reference
electrode. The potential was calibrated by the ferrocene/ferrocenium
2-Bromo-9,10-bis((4-dodecylphenyl)-1-ethynyl)anthracene (10): The pro-
cedure for the synthesis of M2 was followed to prepare 10 from 9 and 2-
bromoanthraquinone as an orange solid in a yield of 79%. 1H NMR
(300 MHz, CDCl3): d=0.86–0.90 (m, 6H), 1.27–1.34 (m, 36H), 1.53–1.66
(m, 4H), 2.68 (t, J=7.52 Hz, 4H), 7.26–7.29 (m, 6H), 7.61–7.70 (m, 5H),
8.54 (d, J=9.18 Hz, 1H), 8.64–8.67 (m, 2H), 8.53 ppm (d, J=1.83 Hz,
1H); MALDI-TOF MS (reflectron mode): m/z (%): 792.4 (100).
standard. HOMO energy levels were estimated by the equation:
onset
oxd
HOMO=À
(4.80+DE ).[25] The structural optimizations of investigated
molecules were carried out at the HF/3-21G level using Gaussian 03
package.[26]
H-mer H2: The procedure for the synthesis of H0 was followed to pre-
pare H2 from 10 and 2b as a dark red solid in a yield of 45%. 1H NMR
(300 MHz, CDCl3): d=0.83–0.91 (m, 18H), 1.24–1.52 (m, 108H), 1.65–
1.67 (m, 8H), 1.76–1.78 (m, 4H), 2.68 (t, J=7.35 Hz, 8H), 2.87 (t, J=
7.80 Hz, 4H), 7.15 (d, J=3.78 Hz, 2H), 7.21 (d, J=3.72 Hz, 2H), 7.30 (d,
J=7.44 Hz, 8H), 7.42 (s, 2H), 7.60–6.63 (m, 4H), 7.69 (d, J=8.07 Hz,
4H), 7.74 (d, J=8.07 Hz, 4H), 7.85 (dd, J1 =9.04 Hz, J2 =1.75 Hz, 2H),
8.62–8.66 (m, 6H), 8.87 ppm (s, 2H); 13C NMR (100 MHz, CDCl3): d=
14.11, 22.70, 29.37, 29.71, 30.52, 31.33, 31.94, 36.04, 36.11, 85.87, 86.21,
102.50, 103.38, 118.35, 120.61, 120.75, 122.61, 123.90, 124.56, 126.28,
126.57, 126.77, 126.92, 127.20, 127.88, 128.64, 128.71, 130.84, 131.22,
131.61, 131.92, 132.11, 132.32, 135.43, 136.76, 140.80, 141.79, 143.92 ppm;
MALDI-TOF MS (reflectron mode): m/z (%): 2093.1 (100); elemental
analysis calcd (%) for C148H186S4: C 84.92, H 8.96; found: C 84.54, H 9.44.
OSC Device Fabrication and Characterization
OSCs were fabricated with the device structure of ITO/PEDOT:PSS
(30 nm)/oligomer:PCBM (1:2 w/w, 70–100 nm)/LiF (1 nm)/Al (100 nm).
The ITO glass was pre-cleaned and modified by PEDOT:PSS (Baytron
P4083). Then the active layer was prepared by spin-coating. Finally LiF/
Al cathode was deposited at a vacuum level of 4ꢁ10À4 Pa. The effective
area of the unit cell is 12 mm2. The current–voltage (I–V) measurement
of the devices was conducted by using a computer-controlled Keithley
236 Source Measure Unit. A Xenon lamp (500 W) with AM 1.5 filter
was used as the white light source, and the optical power at the sample
was 100 mWcmÀ2. The external quantum efficiency (EQE) was measured
by using a Model SR830 DSP Lock-in Amplifier coupled with SBP500
monochromator, DSC102 data acquisition system and Model SR540
chopper controller. The light intensity at each wavelength was calibrated
by using a standard single-crystal Si photodiode.
9,10-Bis(2-(4-((E)-3,4-bis(2-ethylhexyloxy)styryl)phenyl)ethynyl)anthra-
cene (M3): The procedure for the synthesis of M2 was followed to pre-
pare 10 from 11 and anthraquinone as a red solid in a yield of 69%.
1H NMR (300 MHz, CDCl3): d=0.91–1.00 (m, 24H), 1.34–1.38 (m, 16H),
1.48–1.56 (m, 16H), 1.79–1.83 (m, 4H), 3.89–3.96 (m, 8H), 6.88 (d, J=
8.13 Hz, 2H), 6.98–7.17 (m, 8H), 7.58 (d, J=8.37 Hz, 4H), 7.65–7.69 (m,
938
www.chemasianj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 932 – 940

Two Dimensional Conjugated Oligomers
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Acknowledgements
This work is supported by NSFC (Nos. 20674083 and 20525415), Science
Fund for Creative Research Groups of NSFC (No. 20921061), MOST of
China (2009CB930603), and Chinese Academy of Sciences (KJCX2-YW-
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