Swallow-tailed alkyl and linear alkoxy-substituted dibenzocoronene tetracarboxdiimide derivatives: Synthesis, photophysical properties, and thermotropic behaviors

Article abstract of DOI:10.1021/jo400425n

A series of dibenzocoronene tetracarboxdiimide derivatives decorated with alkyl swallow-tail and alkoxy moieties were synthesized, and their structures were characterized. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as an effective oxidant was first used in the benzannulation of perylene diimides with the almost quantitative yield. The thermotropic behavior was investigated using differential scanning calorimetry (DSC) and polarization optical microscopy (POM). The introduction of alkyl swallow-tail and alkoxy substituents facilitates thermotropic liquid crystalline behavior. The branching site of alkyl swallow-tail units at the α position and the longer alkoxy chains played a similar role in lowering the mesophase transition as well as isotropization transition temperatures. The UV-vis absorption spectra of all compounds appeared as absorption in 425-600 nm region, and POM images of certain compounds exhibited characteristic columnar hexagonal (Col_h) packing and readily self-assembled into a homeotropic alignment toward the substrate.

Full text of DOI:10.1021/jo400425n

Article
pubs.acs.org/joc
Swallow-Tailed Alkyl and Linear Alkoxy-Substituted
Dibenzocoronene Tetracarboxdiimide Derivatives: Synthesis,
Photophysical Properties, and Thermotropic Behaviors
Tengzhou Yang,† Jialing Pu,† Jun Zhang,‡ and Wenguang Wang*,†,‡
‡
†Laboratory of Information Recording Materials and Laboratory of Organic Functional Materials Research, Beijing Institute of
Graphic Communication, Beijing 102600, China
S
* Supporting Information
ABSTRACT: A series of dibenzocoronene tetracarboxdiimide derivatives decorated with alkyl swallow-tail and alkoxy moieties
were synthesized, and their structures were characterized. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as an effective
oxidant was first used in the benzannulation of perylene diimides with the almost quantitative yield. The thermotropic behavior
was investigated using differential scanning calorimetry (DSC) and polarization optical microscopy (POM). The introduction of
alkyl swallow-tail and alkoxy substituents facilitates thermotropic liquid crystalline behavior. The branching site of alkyl swallow-
tail units at the α position and the longer alkoxy chains played a similar role in lowering the mesophase transition as well as
isotropization transition temperatures. The UV−vis absorption spectra of all compounds appeared as absorption in 425−600 nm
region, and POM images of certain compounds exhibited characteristic columnar hexagonal (Colh) packing and readily self-
assembled into a homeotropic alignment toward the substrate.
PDIs with swallow-tailed oligosiloxane chains showing high
electron mobility and solubility. Futuremore, liquid crystalline
core-extended PDI derivatives42−44 can be prepared in different
shapes from disklike coronene tetracarboxdiimides (CDIs) to
elongated terrylene and quaterrylene tetracarboxdiimides, and
such liquid crystalline derivatives perform significant functional
properties as a result of different spectral absorption
characters.43,44 More important is that the management of
the molecular structure presents the opportunity to control the
spontaneous self-alignment such as elongated perylene
tetracarboxdiimides tend to edge-on arrangement on a surface
while disklike coronene tetracarboxdiimides to face-on. There-
fore, enlargement of the aromatic core is supposed to achieve a
more effective π−π interaction resulting in highly ordered
supramolecular structures and higher charge carrier mobilities;
for example, coronenemonoimide derivatives reported showed
a large intracolumnar charge carrier mobility of ca. 0.2 cm2 v−1
s−1 in the discotic mesophase.44
INTRODUCTION
■
Discotic liquid crystals (DLCs), comprising a planar rigid
aromatic core and flexible aliphatic side chains, are attractive
candidates for applications in organic electronic and optoelec-
tronic devices1−12 as they readily self-organize into ordered
columnar supramolecular architectures arising from strong
interactions between the aromatic cores and nanophase
separation.4,13−15 This column arrangement provides a one-
dimensional high-speed pathway for charge migration. The
charge carrier mobility is enhanced owing to large intermo-
lecular π-orbital overlaps in the columnar phase.16−18 Until
now, DLCs possessing large aromatic cores such as
hexabenzocoronene and phtalocyanine derivatives have ex-
hibited high carrier mobility in excess of 0.1 cm2 v−1 s−1.19−21
In the past few years, self-assembly of liquid crystalline
perylene diimides (PDIs) has attracted considerable attention
in organic electronics1,22−26 due to their favorable combination
of liquid crystalline, photophsical, semiconducting, and photo-
conducting properties.27−38 Generally, the simple approach to
inducing liquid crystallinity of PDIs28,36,39−41 is merging various
swallow-tail moieties as N-substituents for weakening π−π
stacking interactions of the perylene core. Very recently,
Funahashi41 reported on the thermotropic liquid crystalline
Disk-shaped dibenzocoronene tetracarboxdiimes (dibenzo-
CDIs) reported in the literature45−47,49 have a more extended
Received: February 27, 2013
© XXXX American Chemical Society
A
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
a
Scheme 1. Synthetic Routes of Dibenzo-CDIs 4
a
Reagents and conditions: (i) K2CO3, Pd(PPh3)4, THF, 80 °C, 24 h; (ii) BBr3, dry CH2Cl2, −78 °C, 12 h; (iii) R1Br, K2CO3, dry C2H5OH, acetone,
80 °C, 12 h; (iv) DDQ, dry CH2Cl2, 0 °C, 6 h.
planar π-system than CDIs, but to the best of our knowledge,
there is no liquid crystalline dibenzocoronene tetracarboxdiime
derivatives published up to date. The aim of this research here
is to provide new liquid crystalline derivatives with different
spectral properties and give a systematic investigation of
thermotropic liquid crystalline behaviors of them. A basic
question here is how to effectively weaken the strong degree of
crystallinity, which is intrinsic in dibenzo-CDIs, using a proper
synthetic strategy. Here, we report our successful method of
alkyl swallow-tail moieties as N-substituents and alkoxy chains
in core-extended phenyl substituents inducing liquid crystalline
phases to accomplish this goal. It could be expected that the
thermotropic behavior of dibenzo-CDIs may be fine-tuned
when decorated with diverse structures and length of swallow-
tailed N-side chains having different spatial dimensions as well
as a variety of alkoxy chains. In addition, the incorporation of
these flexible side chains not only controls over the dibenzo-
CDI derivatives thermotropic behavior but also induces high
solubility, both of which are essential for facile processing.50−56
For this purpose, we present two facile and effective synthetic
strategies of a series of dibenzo-CDIs decorated with four types
of swallow-tailed alkyl and linear alkoxy chains. Remarkably,
DDQ as an efficient oxidant was first employed in the
benzannulation of PDIs’ reaction with almost quantitative yield.
According to the literature, our synthetic methods and exclusive
products were first reported. By introduction of swallow-tailed
alkyl and alkoxy groups, a significant reduction in the
isotropization temperature was observed. The thermotropic
behavior was investigated using TGA, DSC, and POM.
RESULTS AND DISCUSSION
■
A series of dibenzo-CDI derivatives were efficiently synthesized,
and the routes 1 and 2 are illustrated in Scheme 1. Both
synthetic routes began from the corresponding 1,7-dibromo-
perylenetetracarboxdiimides 1, which were obtained by
imidization of 1,7-dibromoperylene bisanhydride57−59 with
four kinds of alkyl swallow-tail amines. However, the isomer
1,6-dibromoperylenetetracarboxdiimide derivative was also
formed while bromination of perylene 3,4,9,10-bisanhydride
led to 1,7-dibromoperylene bisanhydride. Thus, bis(3,4-
alkoxyphenyl)perylenetetracarboxdiimide derivatives 2 con-
tained the 1,7- and 1,6-isomers. The isomers 2 could be
observed and characterized by 1H NMR and 13C NMR.
Because of the symmetry of both isomers, an assignment of the
B
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
Figure 1. UV−vis spectra (a) and fluorescence emission spectra (b) of compound 4a2 and 4d2 in cloroform.
Figure 2. DSC curves of (a) compound 4a4, (b) compound 4b4, (c) compound 4d3, and (d) compound 4d4. The measurements were performed
under a nitrogen atmosphere with heating and cooling rates of 10 K/min.
signals to the individual isomers was not possible. For
symmetry reasons, even the mixtures were suitable to transfer
the appropriate only products 4 in the last case of
dehydrocyclization. In the benzannulation of PDIs’ reaction,
the DDQ/MeHSO3 system60 was effectively utilized for the
oxidative C−C bond formations instead of most common
oxidants such as FeCl3, MoCl5, or SbCl5. In this case, we
avoided problems such as chlorination of the phenyl entities
and the large excess use of oxidants. The almost quantitative
yield and ease of isolation of clean products are very
advantageous.
In route 1, 1,7-dibromoperylenetetracarboxdiimide 1 reacted
with 3,4-dialkoxyphenylboronic acid under Suzuki conditions to
afford the corresponding PDI derivatives 2 in 55−60% yield.
Then compounds 2 were dehydrocyclized with DDQ in dry
dichloromethane at 0 °C with almost quantitatively dibenzo-
CDI products 4. For this method, the fatal problem is that
different 3,4-dialkoxyphenylboronic acids must be synthesized
in order to acquire matching compounds 4.
compounds 3 were etherified under Williamson conditions with
four kinds of bromine alkyl leading to compounds 2 in around
85% yield. Finally, the benzannulation with DDQ under similar
reaction conditions as route 1 afforded the products 4.
Compared with synthetic route 1, synthetic route 2 reduced
the number of synthesized compounds 2 with different alkoxy
chains and avoided repeatedly preparation of various alkoxy-
substituted 3,4-dialkoxyphenylboronic acids. Compounds 3
were easily modified with different alkyl groups in better yield.
The yield of the last dehydrocyclization reaction was always
high and over 90%. All synthesized dibenzo-CDI products 4
were red in the solid state and highly soluble in common
organic solvents such as dichloromethane, chloroform, and
THF. The above synthesized molecular structures were
1
determined by the H and 13C NMR spectra, MALDI-TOF,
and elemental analysis .
Photophysical Properties. UV−vis spectra and fluores-
cence emission spectra of dibenzo-CDI compounds 4 were
recorded in chloroform. The spectra of compounds 4 with the
same N-alkyl and different alkoxy groups were almost identical
to each other. Figure 1 showed the representative absorption
and emission spectra of compound 4a2 and 4d2. Both
compounds showed absorption bands from 300 to 650 nm
with two distinct absorption peaks in Figure 1a. According to
The synthetic route 2 was carried out with the same
procedure as the synthetic route 1 leading to preparation of 1,7-
bis(3′,4′-dipentyloxyphenyl)perylene tetracarboxdiimide 2a1,
2b1, 2c1, and 2d1 first. Then compounds 2a1, 2b1, 2c1, and
2d1 in the presence of BBr3 yielded the intermediate 3. Then
C
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
Figure 3. Optical microscopy images of compound 4b4 cooled at 1 °C/min from the isotropic phase between two glass slides (a) 87 °C with and (b)
without cross-polarizers (the arrows indicate defects in the homeotropic organization).
Figure 4. Optical microscopy images of compound 4d4 cooled at 1 °C/min from the istropic phase between two glass slides (a) 195 °C with and (b)
without coss-polarizers (dashed lines indicate the propagation direction of the dendritic structures) (the arrows indicate defects in the homeotropic
organization).
the literature,46,48 in the region of shorter wavelengths (up to
400 nm), a maximum absorbance of 361 nm in the spectrum of
compounds 4a2 and 4d2 is correlated with a defined structure.
The absorption for the four compounds displayed bath-
ochromic shift, which was ascribed to introduction of
electron-donating alkoxy groups. The bathochromic shift
absorption showed differences in the long-wavelength region
with different branching site positions of the N-alkyl
substituents: compound 4a2, with an N-alkyl substituent
branching site at the α position, showed a strong peak at
about 511 nm and one weak peak at about 577 nm; compound
4d2 at the β position showed a strong peak at about 500 nm
and one weak peak at about 557 nm. The fluorescence
spectrum of compounds 4a2, 4d2 (Figure 2b) showed emission
maxima difference about 20 nm.
Thermal Behaviors and Thermotropic Properties.
Thermal behaviors and thermotropic properties of compounds
4 were investigated by TGA, DSC, and POM. TGA
measurements revealed that all compounds 4 were thermally
stable up to 300 °C with a 5% weight loss under nitrogen; see
S74 (Supporting Information). Through DSC and POM, the
majority of compounds 4 did not evidently exhibit endothermic
peaks in DSC curves and optical textures in POM images. So
here only compounds 4a4, 4b4, 4d3, and 4d4 allowing a melting
process and an investigation of their morphology from
isotropization to crystallization were discussed in detail. It
was observed that before reaching the decomposition temper-
ature an expected isotropization transition of compound 4c4
was not obtained because of its short butyl branched chain of
N-alkyl substituent offering weak limit of the face-to-face π−π
stacking compared to compound 4d4.
The DSC curves of compounds 4a4, 4b4, and 4d4 showed
two endothermic peaks on heating and two exothermic peaks
on the cooling process, which indicated that they all exhibit an
enantiotropic mesophase, while there was no obvious
endothermic peak in the heating and cooling cycle in DSC
curve of compoud 4d3 possibly owing toa small enthalpy
change between the crystalline (Cr) phase and a liquid
crystalline (Colh) phase (see Figure 2c). This indicated that
the thermal behavior of compounds appears to have a strong
dependence on the length of alkoxy side chains and the
structures of branched alkyl chains. Compound 4d4 showed the
lowest isotropization temperature at 201.6 °C upon heating,
while the others at about 250 °C (see Figure 2). Compared
with compounds 4a4 and 4b4, the branching sites of N-alkyl
substituents at the α position greatly lower the isotropization
temperature than that at the β position for the large steric
hindrance spacer requirement. For compounds 4d3 and 4d4
there was a decrease in clearing temperature with an increase of
the alkoxy chain length; the longer alkyl chains at the N,N′-
imide position played the same role in clearing the temperature
as well as the melting temperature parallel with compounds 4a4
and 4b4.
The four dibenzo-CDI derivatives 4a4, 4b4, 4d3, and 4d4
were sandwiched between two glass slides and slowly cooled
from the isotropic phase, and a small hysteresis of about 10−15
°C between DSC and POM measurement for the isotropization
temperatures was observed because of higher heating rates.
Four compounds 4a4, 4b4, 4d3, and 4d4 showed similar
D
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
129.4, 128.5, 128.3, 126.4, 121.5, 121.3, 121.2, 114.4, 113.7, 69.5, 69.1,
44.8, 36.8, 31.8, 31.7, 30.1, 29.7, 29.6, 29.3, 29.0, 28.2, 26.5, 22.6, 22.5,
14.0. MALDI-TOF MS m/z: [M + Na]+ calcd for C88H122N2O8Na
1357.91, found 1358.1. Anal. Calcd for C88H122N2O8: C, 79.12; H,
9.20; N, 2.10. Found: C, 78.74; H, 9.23; N, 2.07.
morphological behaviors. Representative optical microscopy
images of 4b4 and 4d4 are presented in Figures 3 and 4,
respectively.
In local areas, upon slowly cooling at rate 1 °C/min,
dendritic structures with negligible distinction in relation to the
disturbing organization were observed in nonpolarized light.
But when cross-polarizers were added, the images became black
with some small birefringence indicating that there existed
homeotropic phase where the columnar axes were mostly
perpendicular to the glass substrate. The uniform and
symmetrical structure in disk-shaped molecules enjoyed a
face-on manner and resulted in the homeotropic orientation as
reported.43,61,62 On the other hand, the introduction of ether
groups probably enhanced the molecular affinity toward
substrate and further promoted the homeotropic arrange-
ment.61 As displayed in Figure 4b, the dendritic textures formed
with the angle between the branching almost 60°, which
implied the hexagonal packing.
N,N′-Bis(2-octyldodecyl)-1,7-bis-(3,4-dipentyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2b1). The reaction of 1b
(2.2 g, 2 mmol), 3,4-dipentyloxyphenyl boronic acid (0.74 g, 2.5
mmol), and Pd(PPh3)4 (0.12 g, 0.1 mmol) in 45 mL of THF and 30
mL of 1 M K2CO3 aqueous solution under nitrogen atmosphere at 80
°C for 24 h followed by column chromatography purification on silica
gel using dichloromethane−petroleum ether (v/v = 1:1.5) as eluent
produced compound 2b1 (1.73 g, 60%) as dark purple solid: 1H NMR
(CDCl3, 400 MHz): δ ppm 8.60 (s, 2H), 8.17 (d, 2H), 7.90 (d, 2H),
6.99 (m, 6H), 4.05−4.16 (m, 12H), 1.76−1.92 (m, 10H), 1.21−1.58
(m, 78H), 0.82−0.99 (m, 24H); 13C NMR (CDCl3, 75 MHz): δ ppm
163.5, 163.1, 150.5, 149.7, 140.5, 134.5, 134.0, 133.8, 131.0, 129.4,
128.5, 128.3, 126.4, 121.5, 121.3, 121.2, 114.4, 113.8, 69.5, 69.1, 44.8,
36.8, 31.9, 31.8, 30.1, 29.7, 29.6, 29.3, 29.0, 28.2, 26.6, 22.5, 14.0.
MALDI-TOF MS m/z: [M]+ calcd for C96H138N2O8 1447.05, found
1448.2. Anal. Calcd for C96H138N2O8: C, 79.62; H, 9.61; N, 1.93.
Found: C, 79.77; H, 9.38; N, 1.87.
N,N′-Bis(1-butylpentadecyl)-1,7-bis(3,4-dipentyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2c1). The reaction of 1c
(1.94 g, 2 mmol), 3,4-dipentyloxyphenyl boronic acid (0.74 g, 2.5
mmol), Pd(PPh3)4 (0.12 g, 0.1 mmol) in 45 mL of THF and 30 mL of
1 M K2CO3 aqueous solution under nitrogen atmosphere at 80 °C for
24 h followed by column chromatography purification on silica gel
using dichloromethane−petroleum ether (v/v = 1:2) as eluent
produced compound 2c1 (1.52 g, 57%) as dark purple solid. 1H
NMR (CDCl3, 400 MHz): δ ppm 8.63 (d, 2H), 8.17 (m, 2H), 7.93
(m, 2H), 7.05 (m, 6H), 5.15 (s, 2H), 4.07−4.10 (m, 8H), 1.78−2.24
(m, 16H), 1.19−1.55 (m, 60H), 0.82−0.99 (m, 24H). 13C NMR
(CDCl3, 75 MHz): δ ppm 164.8, 164.6, 163.7, 163.5, 150.3, 149.8,
149.2, 148.4, 140.9, 135.8, 135.0, 134.6, 134.3, 132.4, 129.8, 129.7,
129.3, 129.1, 127.7, 122.6, 122.2, 121.9, 121.6, 121.5, 119.2, 114.5,
114.4, 114.1, 113.1, 69.6, 69.5, 69.4, 69.1, 54.5, 32.3, 32.0, 31.8, 29.6,
29.5, 29.3, 29.1, 29.0, 28.9, 28.8, 28.2, 28.1, 26.9, 22.6, 22.5, 22.4, 14.0.
MALDI-TOF MS m/z: [M]+ calcd for C88H122N2O8 1334.92, found
1335.4. Anal. Calcd for C88H122N2O8: C, 79.12; H, 9.20; N, 2.10.
Found: C, 79.25; H, 9.28; N, 2.06.
N,N′-Bis(1-heptyloctyl)-1,7-bis(3,4-dipentyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2d1). The reaction of 1d
(1.93 g, 2 mmol), 3,4-dipentyloxyphenyl boronic acid (0.74 g, 2.5
mmol), and Pd(PPh3)4 (0.12 g, 0.1 mmol) in 45 mL of THF and 30
mL of 1 M K2CO3 aqueous solution under nitrogen atmosphere at 80
°C for 24 h followed by column chromatography purification on silica
gel using dichloromethane−petroleum ether (v/v = 1:2) as eluent
produced compound 2d1 (1.44 g, 55%) as dark purple solid. 1H NMR
(CDCl3, 600 MHz): δ ppm 8.64 (d, 2H), 8.17 (m, 2H), 7.93 (m, 2H),
7.06 (m, 6H), 5.15 (s, 2H), 3.97−4.09 (m, 8H), 1.80−2.23 (m, 16H),
1.20−1.55 (m, 56H), 0.79−0.99 (m, 24H). 13C NMR (CDCl3, 75
MHz): δ ppm 164.7, 164.6, 163.7, 163.5, 150.4, 149.9, 149.7, 142.0,
140.9, 135.7, 135.0, 134.6, 132.6, 132.3, 129.7, 129.5, 129.2, 128.7,
128.4, 127.7, 127.0, 122.6, 122.2, 121.9, 121.6, 121.3, 114.6, 114.4,
69.5, 69.1, 54.5, 32.3, 31.7, 29.6, 29.5, 29.2, 28.9, 28.8, 28.2, 28.1, 26.9,
22.5, 22.4, 14.0. MALDI-TOF MS m/z: [M]+ calcd for C86H118N2O8
1329.88, found 1329.9. Anal. Calcd for C86H118N2O8: C, 78.98; H,
9.09; N, 2.14. Found: C, 78.72; H, 8.82; N, 2.18.
CONCLUSION
■
We designed and successfully synthesized a series of novel
dibenzo-CDI derivatives with α- or β-branched alkyl and
different alkoxy groups. DDQ was first employed in the PDI’s
core-extension reaction as the oxidant and the reaction could
obtain almost quantitative yield. Introduction of alkyl and
alkoxy resulted that the isotropic-phase temperatures of
compounds 4 were largely lower, especially for compound
4d4 (∼201 °C). The morphological behaviors of compounds
4a4, 4b4, 4d3, and 4d4 after crystallization from isotropic phase
implied the homeotropic alignment toward surface, which
further indicated that symmetrical disk-shaped compounds
preferred a face-on arrangement upon cooling from the
isotropization for the increase of molecular affinity toward
surface by the influence of ether group.
EXPERIMENTAL SECTION
■
N,N′-Bis(swallow-tail alkyl)-1,7-dibromoperylene-3,4,9,10-tetracarbox-
ydiimide 1a, 1b, 1c, and 1d were prepared following the literature38
methods. All other chemicals were purchased from commercial source.
Solvents were of analytical grade and were purified by the standard
method if necessary.
Compounds 2a1, 2b1, 2c1, and 2d1. These compounds were
prepared according to the general method. To a three-neck round-
bottom flask under nitrogen atmosphere were dissolved N,N′-
bis(swallow-tail alkyl)-1,7-dibromoperylene-3,4,9,10-tetracarboxydii-
mides 1a, 1b, 1c, and 1d and 3,4-dipentyloxyphenylboronic acid in
THF. To this reaction mixture were added 1 M K2CO3 aqueous
solution and catalyst Pd(PPh3)4 in sequence. The resulting suspension
was stirred for 24 h at 80 °C under nitrogen atmosphere. The reaction
mixture was allowed to cool to room temperature and extracted with
dichloromethane. The collected organic layer was dried over
anhydrous sodium sulfate. The solvent was removed under reduced
pressure. The residue was purified by silica gel column chromatog-
raphy, eluting with dichloromethane−petroleum ether.
N,N′-Bis(2-hexyldecyl)-1,7-bis(3,4-dipentyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2a1). The reaction of 1a
(1.94 g, 2 mmol), 3,4-dipentyloxyphenyl boronic acid (0.74 g, 2.5
mmol), and Pd(PPh3)4 (0.12 g, 0.1 mmol) in 45 mL of THF and 30
mL of 1 M K2CO3 aqueous solution under nitrogen atmosphere at 80
°C for 24 h followed by column chromatography purification on silica
gel using dichloromethane−petroleum ether (v/v = 1:1.5) as eluent
Compounds 3a, 3b, 3c, and 3d. These compounds were
prepared according to the general method. To a solution of
compounds 2a1, 2b1, 2c1, and 2d1 in dry dichloromethane at −78
°C was added dropwise BBr3. The stirred reaction mixture was allowed
to warm to room temperature. After 12 h, it was poured into ice, the
product was extracted with ethyl acetate, and the organic extracts were
dried and filtered. The crude product was purified by silica gel column
chromatography using acetone−petroleum ether as eluent.
1
produced compound 2a1 (1.54 g, 58%) as a dark purple solid. H
NMR (CDCl3, 400 MHz): δ ppm 8.45 (s, 2H), 8.13(d, 2H), 7.77 (d,
2H), 7.04 (m, 6H), 4.02−4.15 (m, 12H), 1.80−1.93 (m, 10H), 1.24−
1.56 (m, 62H), 0.82−0.99 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ
ppm 163.5, 163.2, 150.5, 149.6, 140.5, 134.5, 134.0, 133.8, 131.0,
N,N′-Bis(2-hexyldecyl)-1,7-bis-(3,4-dihydroxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (3a). The reaction of 2a1
(5.34 g, 4 mmol) and BBr3 (4.4 g, 4.4 × 4 mmol) in 100 mL dry
E
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
dichloromethane at −78 °C for 12 h followed by column
chromatography purification on silica gel using acetone−petroleum
ether (v/v = 1:3) as eluent produced compound 3a (4.20 g, 90%) as a
dark blue solid. 1H NMR (acetone-d6, 400 MHz): δ ppm 8.32 (s, 2H),
8.12 (d, 2H), 8.03 (s, 2H), 7.72 (d, 2H), 6.90 (m, 6H), 4.14 (d, 2H),
2.91 (m, 4H), 2.05 (m, 4H), 1.24−1.47 (m, 44H), 0.79−0.95 (m,
12H). 13C NMR (acetone-d6, 75 MHz): δ ppm 163.2, 162.8, 146.5,
146.0, 140.4, 134.0, 133.7, 131.3, 131.1, 130.3, 129.8, 128.4, 128.3,
127.1, 126.1, 121.0, 120.6, 116.8, 115.5, 44.4, 36.3, 31.7, 31.6, 29.9,
29.5, 29.4, 29.3, 29.1, 28.9, 28.7, 28.5, 28.4, 26.3, 22.4, 13.5. MALDI-
TOF MS m/z: [M]+ calcd for C68H82N2O8 1504.61, found 1055.1.
Anal. Calcd for C68H82N2O8: C, 77.39; H, 7.83; N, 2.65. Found: C,
77.44; H, 8.10; N, 2.58.
N,N′-Bis(2-octyldodecyl)-1,7-bis-(3,4-dihydroxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (3b). The reaction of 2b1
(5.80 g, 4 mmol) and BBr3 (4.4 g, 4.4 × 4 mmol) in 100 mL of dry
dichloromethane at −78 °C for 12 h followed by column
chromatography purification on silica gel using acetone−petroleum
ether (v/v = 1:3) as eluent produced compound 3b (4.20 g, 90%) as a
dark blue solid. 1H NMR (acetone-d6, 400 MHz): δ ppm 8.29 (s, 2H),
8.13 (d, 2H), 8.03 (s, 2H), 7.72 (d, 2H), 6.90 (m, 4H), 6.71 (s, 2H),
4.14 (d, 2H), 2.94 (m, 4H), 2.04 (m, 4H), 1.28−1.43 (m, 60H), 0.79−
0.99 (m, 12H). 13C NMR (acetone-d6, 75 MHz): δ ppm 163.1, 162.8,
146.5, 146.1, 140.4, 134.0, 133.7, 133.6, 131.1, 129.7, 128.7, 128.4,
128.2, 126.1, 121.5, 116.8, 115.5, 64.9, 50.6, 44.4, 41.3, 36.3, 31.7, 31.6,
29.8, 29.7, 29.4, 29.1, 28.9, 28.6, 28.4, 28.1, 26.8, 26.2, 24.7, 22.4, 18.9,
13.4. MALDI-TOF MS m/z: [M]+ calcd for C76H98N2O8 1166.73,
found 1167.3. Anal. Calcd for C76H98N2O8: C, 78.18; H, 8.46; N, 2.40.
Found: C, 77.98; H, 8.38; N, 2.38.
N,N′-Bis(1-butylpentadecyl)-1,7-bis(3,4-dihydroxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (3c). The reaction of 2c1
(5.34 g, 4 mmol) and BBr3 (4.4 g, 4.4 × 4 mmol) in 100 mL of dry
dichloromethane at −78 °C for 12 h followed by column
chromatography purification on silica gel using acetone−petroleum
ether (v/v = 1:3) as eluent produced compound 3c (3.92 g, 93%) as a
dark blue solid. 1H NMR (acetone-d6, 400 MHz): δ ppm 8.43 (s, 4H),
8.18 (m, 4H), 8.01 (s, 2H), 7.05 (m, 6H), 5.17 (d, 2H), 2.89 (m, 6H),
2.31 (m, 2H), 1.84 (m, 2H), 1.18−1.33 (m, 42H), 0.80−0.95 (m,
12H). 13C NMR (acetone-d6, 75 MHz): δ ppm 144.2, 143.6, 138.6,
132.5, 131.7, 129.7, 127.3, 126.8, 125.0, 118.2, 114.5, 113.4, 51.4, 29.6,
29.4, 29.3, 27.3, 27.0, 26.7, 26.5, 26.2, 26.0, 25.7, 24.2, 19.9,11.0.
MALDI-TOF MS m/z: [M]+ calcd for C68H82N2O8 1504.61, found
1505.1. Anal. Calcd for C68H82N2O8: C, 77.39; H, 7.83; N, 2.65.
Found: C, 77.66; H, 7.76; N, 2.58.
N,N′-Bis(1-heptyloctyl)-1,7-bis(3,4-dihydroxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (3d). The reaction of 2d1
(5.23 g, 4 mmol) and BBr3 (4.4 g, 4.4 × 4 mmol) in 100 mL of dry
dichloromethane at −78 °C for 12 h followed by column
chromatography purification on silica gel using acetone−petroleum
ether (v/v = 1:3) as eluent produced compound 3d (3.73 g, 91%) as a
dark blue solid. 1H NMR (acetone-d6, 400 MHz): δ ppm 8.40 (s, 4H),
8.11 (m, 4H), 7.95 (s, 2H), 7.01 (m, 4H), 6.94 (s, 2H), 5.18 (d, 2H),
2.89 (m, 6H), 2.66 (m, 2H), 1.88 (m, 2H), 1.21−1.32 (m, 38H),
0.79−0.95 (m, 12H). 13C NMR (acetone-d6, 75 MHz): δ ppm 146.6,
146.0, 140.9, 134.0, 131.0, 129.6, 129.6, 128.7, 127.3, 120.5, 116.9,
115.7, 64.9, 53.9, 32.5, 32.0, 31.7, 31.6, 30.4, 29.7, 29.4, 29.3, 29.1,
29.0, 28.9, 28.4, 28.1, 26.7, 24.0, 22.4, 22.3, 19.1, 18.9, 13.4, 13.0.
MALDI-TOF MS m/z: [M]+ alcd for C66H78N2O8 1026.58, found
1027.1. Anal. Calcd for C66H78N2O8: C, 77.28; H, 7.74; N, 2.69.
Found: C, 77.33; H, 7.60; N, 2.73.
compound 3a (0.53 g, 0.5 mmol) in 20 mL of dry ethanol and 20 mL
of acetone were added bromooctane (0.58 g, 3 mmol) and K2CO3(0.3
g, 2.2 mmol). The mixture was refluxed at 80 °C for 12 h and then
poured into ice. The product was extracted with dichloromethane, and
the organic extracts were dried and filtered. The crude product was
purified by silica gel column chromatography using dichloromethane−
petroleum ether (v/v = 1:1.5) as eluent, and compound 2a2 (0.64 g,
1
85%) was obtained as a dark purple solid. H NMR (CDCl3, 600
MHz): δ ppm 8.49 (s, 2H), 8.13 (d, 2H), 7.79 (d, 2H), 7.04 (m, 6H),
4.08−4.14 (m, 12H), 1.88−1.91 (m,10H), 1.24−1.55 (m, 86H), 0.83−
0.92 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm 163.6, 163.3,
150.5, 149.7, 140.6, 134.7, 134.1, 131.1, 129.5, 128.7, 128.5, 126.6,
121.6, 121.4, 121.2, 114.5, 113.9, 69.5, 69.1, 44.7, 36.7, 31.9, 31.8, 31.7,
30.1, 29.7, 29.6, 29.5, 29.3, 26.5, 26.1, 26.0, 22.6, 14.0. MALDI-TOF
MS m/z: [M]+ calcd for C100H146N2O8 1053.11, found 1054.4. Anal.
Calcd for C100H146N2O8: C, 79.85; H, 9.78; N, 1.86. Found: C, 79.53;
H, 9.64; N, 1.83.
N,N′-Bis(2-hexyldecyl)-1,7-bis-(3,4-didodecyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2a3). The reaction of 3a
(0.53 g, 0.5 mmol), bromododecane (0.75 g, 3 mmol), and K2CO3
(0.3 g, 2.2 mmol) at 80 °C for 12 h followed by column
chromatography purification on silica gel using dichloromethane−
petroleum ether (v/v = 1:1.5) as eluent produced compound 2a3 (0.72
1
g, 84%) as a dark purple solid. H NMR (CDCl3, 400 MHz): δ ppm
8.44 (s, 2H), 8.12 (d, 2H), 7.75 (d, 2H), 6.99 (m, 6H), 4.07−4.15 (m,
12H), 1.87−1.91 (m, 10H), 1.24−1.59 (m, 118H), 0.85−0.90 (m,
24H). 13C NMR (CDCl3, 75 MHz): δ ppm 163.6, 163.5, 150.4, 149.8,
140.7, 134.9, 134.4, 134.2, 131.7, 129.6, 128.9, 126.9, 121.7, 121.4,
114.5, 114.0, 69.5, 69.2, 44.7, 36.7, 31.9, 31.8, 31.7, 30.0, 29.7, 29.6,
29.5, 29.3, 26.5, 26.1, 26.0, 22.6, 14.0. MALDI-TOF MS m/z: [M +
Na]+ calcd for C116H178N2O8Na 1750.35, found 1751.5. Anal. Calcd
for C116H178N2O8: C, 80.60; H, 10.38; N, 1.62. Found: C, 80.57; H,
10.20; N, 1.56.
N,N′-Bis(2-hexyldecyl)-1,7-bis-(3,4-dihexadecyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2a4). The reaction of 3a
(0.53 g, 0.5 mmol), bromohexadecane (0.92 g, 3 mmol), and K2CO3
(0.3 g, 2.2 mmol) at 80 °C for 12 h followed by column
chromatography purification on silica gel using dichloromethane−
petroleum ether (v/v = 1:1.5) as eluent produced compound 2a4 (0.83
1
g, 85%) as dark purple solid. H NMR (CDCl3, 400 MHz): δ ppm
8.46 (s, 2H), 8.13 (d, 2H), 7.76 (d, 2H), 6.99 (m, 6H), 4.06−4.13 (m,
12H), 1.79−1.96 (m, 10H), 1.23−1.58 (m, 150H), 0.84−0.87 (m,
24H). 13C NMR (CDCl3, 125 Hz): δ ppm 163.9, 163.3, 150.4, 149.7,
140.6, 134.7, 134.1, 134.0, 131.3, 129.5, 128.6, 128.5, 126.6, 121.6,
121.4, 121.2, 114.5, 113.8, 69.5, 69.1, 44.7, 36.7, 31.9, 31.8, 31.7, 30.1,
29.7, 29.6, 29.5, 29.3, 26.5, 26.1, 26.0, 22.6, 14.0. MALDI-TOF MS m/
z: [M]+ calcd for C132H210N2O8 1951.61, found 1951.8. Anal. Calcd
for C132H210N2O8: C, 81.17; H, 10.84; N, 1.43. Found: C, 81.07; H,
10.68; N, 1.38.
N,N′-Bis(2-octyldodecyl)-1,7-bis(3,4-dioctyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2b2). The reaction of 3b
(0.74 g, 0.5 mmol), bromooctane (0.58 g, 3 mmol), and K2CO3 (0.3 g,
2.2 mmol) at 80 °C for 12 h followed by column chromatography
purification on silica gel using dichloromethane-petroleum ether (v/v
= 1:1.5) as eluent produced compound 2b2 (0.69 g, 85%) as dark
1
purple solid. H NMR (CDCl3, 600 MHz): δ ppm 8.44 (s, 2H), 8.12
(d, 2H), 8.11 (d, 2H), 6.99 (m, 6H), 4.07−4.16 (m, 12H), 1.88−1.91
(m, 10H), 1.22−1.55 (m, 102H), 0.83−0.92 (m, 24H). 13C NMR
(CDCl3, 125 Hz): δ ppm 163.6, 163.3, 150.5, 149.7, 140.6, 134.7,
134.1, 131.4, 129.5, 128.7, 128.6, 126.7, 121.6, 121.4, 121.3, 114.5,
113.9, 69.5, 69.1, 44.7, 36.7, 31.9, 31.8, 30.1, 29.6, 29.3, 29.2, 26.5,
26.0, 22.6, 14.0. MALDI-TOF MS m/z: [M + Na]+ calcd for
C108H162N2O8Na 1638.22, found 1639.5. Anal. Calcd for
C108H162N2O8: C, 80.25; H, 10.10; N, 1.73. Found: C, 80.06; H,
9.89; N, 1.67.
N,N′-Bis(2-octyldodecyl)-1,7-bis-(3,4-didodecyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2b3). The reaction of 3b
(0.74 g, 0.5 mmol), bromododecane (0.75 g, 3 mmol), and K2CO3
(0.3 g, 2.2 mmol) at 80 °C for 12 h followed by column
chromatography purification on silica gel using dichloromethane−
Compounds 2a2−2a4, 2b2−2b4, 2c2−2c4, and 2d2−2d4. These
compounds were prepared according to the general method. To a
solution of compounds 3a−d in dry ethanol and acetone-d6 were
added bromooctane and K2CO3. The mixture was refluxed at 80 °C
for 12 h and then poured into crushed ice. The product was extracted
with dichloromethane, and the organic extracts were dried and filtered.
The crude product was purified by silica gel column chromatography
using dichloromethane−petroleum ether as eluent.
N,N′-Bis(2-hexyldecyl)-1,7-bis(3,4-dioctyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2a2). To a solution of
F
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
petroleum ether (v/v = 1:1.5) as eluent produced compound 2b3
(0.76 g, 84%) as a dark purple solid. H NMR (CDCl3, 400 MHz): δ
8.63 (m, 2H), 8.17 (m, 2H), 7.92 (m, 2H), 7.05 (m, 6H), 5.17 (m,
2H), 3.96−4.18 (m, 8H), 1.81−2.23 (m, 16H), 1.19−1.53 (m, 148H),
0.82−0.99 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm 164.8,
164.6, 163.7, 163.5, 150.4, 149.9, 149.7, 142.0, 140.9, 135.7, 135.0,
134.6, 134.4, 132.6, 132.4, 129.7, 129.5, 129.3, 128.7, 128.4, 127.7,
127.0, 122.6, 122.3, 121.6, 121.3, 114.6, 114.5, 114.3, 69.6, 69.2, 54.6,
54.5, 54.4, 32.3, 32.0, 31.9, 31.8, 30.2, 29.6, 29.5, 29.4, 29.3, 29.2, 29.1,
26.9, 26.1, 26.0, 22.6, 22.4, 14.1, 14.0, 13.8. MALDI-TOF MS m/z: [M
+ Na]+ calcd for C132H210N2O8Na 1974.6, found 1975.5. Anal. Calcd
for C132H210N2O8: C, 81.17; H, 10.84; N, 1.43. Found: C, 81.09; H,
10.55; N, 1.40;
1
ppm 8.41 (s, 2H), 8.11 (d, 2H), 7.71 (d, 2H), 6.91 (m, 6H), 4.06−
4.15 (m, 12H), 1.79−1.96 (m, 10H), 1.25−1.53 (m, 134H), 0.84−
0.89 (m, 24H). 13C NMR (CDCl3, 100 Hz): δ ppm 163.6, 163.4,
150.5, 149.8, 140.6, 134.8, 134.2, 131.5, 129.6, 128.8,126.8, 121.7,
121.5, 121.3, 114.5, 69.6, 69.2, 44.7, 36.7, 31.9, 31.8, 30.1, 29.7, 29.6,
29.5, 29.4, 29.3, 26.6, 26.5, 26.1, 26.0, 22.7, 22.6, 14.1. MALDI-TOF
MS m/z: [M]+ calcd for C124H194N2O8 1839.48, found 1839.9. Anal.
Calcd for C124H194N2O8: C, 80.90; H, 10.62; N, 1.52. Found: C, 80.78;
H, 10.49; N, 1.54.
N,N′-Bis(1-heptyloctyl)-1,7-bis(3,4-dioctyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2d2). The reaction of 3d
(0.53 g, 0.5 mmol), bromooctane (0.58 g, 3 mmol), and K2CO3 (0.3 g,
2.2 mmol) at 80 °C for 12 h followed by column chromatography
purification on silica gel using dichloromethane−petroleum ether (v/v
= 1:2) as eluent produced compound 2d2 (0.63 g, 85%) as a dark
purple solid. 1H NMR (CDCl3, 600 MHz): δ ppm 8.63 (m, 2H), 8.16
(m, 2H), 7.93 (m, 2H), 7.06 (m, 6H), 5.15 (s, 2H), 3.97−4.08 (m,
8H), 1.81−2.23 (m, 16H), 1.20−1.56 (m, 80H), 0.81−0.92 (m, 24H).
13C NMR (CDCl3, 75 MHz): δ ppm 164.8, 164.6, 163.7, 163.5, 150.4,
149.9, 149.7, 142.0, 140.9, 135.7, 135.0, 134.6, 134.4, 132.6, 132.3,
129.8, 129.7, 129.5, 129.3, 129.1, 128.7, 128.4, 127.7, 127.0, 122.6,
122.3, 121.9, 121.6, 121.3, 114.6, 114.5, 114.3, 114.2, 69.6, 69.5, 69.4,
69.2, 54.7, 54.5, 54.4, 32.3, 31.9, 31.7, 31.5, 29.6, 29.5, 29.4, 29.3, 29.2,
26.9, 26.1, 26.0, 22.6, 14.0. MALDI-TOF MS m/z: [M + Na]+ calcd
for C98H142N2O8Na 1498.07, found 1499.1. Anal. Calcd for
C98H142N2O8: C, 79.74; H, 9.70; N, 1.90. Found: C, 79.78; H, 9.44;
N, 1.92.
N,N′-Bis(2-octyldodecyl)-1,7-bis-(3,4-dihexadecyloxy-
phenyl)perylene-3,4,9,10-tetracarboxydiimide (2b4). The reac-
tion of 3b (0.74 g, 0.5 mmol), bromohexadecane (0.92 g, 3 mmol),
and K2CO3 (0.3 g, 2.2 mmol) at 80 °C for 12 h followed by column
chromatography purification on silica gel using dichloromethane−
petroleum ether (v/v = 1:1.5) as eluent produced compound 2b4
1
(0.88 g, 85%) as a dark purple solid. H NMR (CDCl3, 400 MHz): δ
ppm 8.51 (s, 2H), 8.14 (d, 2H), 7.81 (d, 2H), 7.01 (m, 6H), 4.07−
4.13 (m, 12H), 1.78−1.91 (m, 10H), 1.21−1.58 (m, 166H), 0.83−
0.90 (m, 24H). 13C NMR (CDCl3, 125 Hz): δ ppm 163.5, 163.2,
150.6, 149.7, 140.5, 134.7, 134.1, 133.9,131.1, 129.4, 128.6, 128.4,
126.5, 121.5, 121.3, 121.2, 114.5, 69.5, 69.1, 44.8, 36.8, 31.9, 31.8, 31.7,
30.1, 29.7, 29.6, 29.5, 29.3, 26.6, 26.5, 26.1, 26.0, 22.6, 14.0. MALDI-
TOF MS m/z: [M]+ calcd for C140H226N2O8 2063.73, found 2064.0.
Anal. Calcd for C140H226N2O8: C, 81.42; H, 11.03; N, 1.36. Found: C,
81.10; H, 11.10; N, 1.34.
N,N′-Bis(1-butylpentadecyl)-1,7-bis(3,4-dioctyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2c2). The reaction of 3c
(0.53 g, 0.5 mmol), bromooctane (0.58 g, 3 mmol), and K2CO3 (0.3 g,
2.2 mmol) at 80 °C for 12 h followed by column chromatography
purification on silica gel using dichloromethane−petroleum ether (v/v
= 1:2) as eluent produced compound 2c2 (0.67 g, 87%) as a dark
purple solid. 1H NMR (CDCl3, 300 MHz): δ ppm 8.63 (m, 2H), 8.18
(m, 2H), 7.94 (m, 2H), 7.07 (m, 6H), 5.19 (m, 2H), 3.97−4.14 (m,
8H), 1.79−2.24 (m, 16H), 1.21−1.44 (m, 82H), 0.82−0.91 (m, 24H).
13C NMR (CDCl3, 75 MHz): δ ppm 164.8, 164.6, 163.7, 163.5, 150.4,
149.9, 149.7, 142.0, 140.9, 135.7, 135.0, 134.6, 134.4, 132.6, 132.4,
129.7, 129.5, 129.3, 128.7, 128.4, 127.7, 127.0, 122.7, 122.3, 121.9,
121.6, 121.3, 114.6, 114.5, 114.3, 69.6, 69.2, 54.6, 54.5, 54.4, 37.0, 34.0,
32.7, 32.3, 32.0, 31.8, 31.7, 31.4, 30.1, 29.6, 29.5, 29.4, 29.3, 29.2, 29.1,
28.3, 26.9, 26.0, 25.9, 24.8, 22.6, 14.1, 14.0. MALDI-TOF MS m/z: [M
+ Na]+ calcd for C100H146N2O8Na 1526.1, found 1526.2. Anal. Calcd
for C100H146N2O8: C, 79.85; H, 9.78; N, 1.86. Found: C, 79.62; H,
9.92; N, 1.79.
N,N′-Bis(1-heptyloctyl)-1,7-bis(3,4-didodecyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2d3). The reaction of 3d
(0.53 g, 0.5 mmol), bromododecane (0.75 g, 3 mmol), and K2CO3
(0.3 g, 2.2 mmol) at 80 °C for 12 h followed by column
chromatography purification on silica gel using dichloromethane−
petroleum ether (v/v = 1:2) as eluent produced compound 2d3 (0.72
1
g, 85%) as a dark purple solid. H NMR (CDCl3, 600 MHz): δ ppm
8.63 (m, 2H), 8.17 (m, 2H), 7.93 (m, 2H), 6.94 (m, 6H), 5.15 (s, 2H),
3.97−4.08 (m, 8H), 1.80−2.25 (m, 16H), 1.21−1.56 (m, 112H),
0.81−0.90 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm 164.8,
164.6, 163.7, 163.5, 150.4, 149.9, 149.7, 149.2, 148.4, 142.0, 140.9,
135.7, 135.0, 134.6, 134.4, 132.6, 132.4, 130.0, 129.9, 129.7, 129.5,
129.3, 129.1, 128.7, 128.4, 127.7, 127.0, 122.6, 122.3, 121.9, 121.6,
121.3, 119.3, 114.6, 114.5, 114.2, 113.2, 69.6, 69.4, 69.2, 54.6, 54.5,
54.4, 32.3, 31.8, 31.7, 31.5, 29.6, 29.5, 29.4, 29.3, 29.2, 26.9, 26.1, 26.0,
22.6, 14.0. MALDI-TOF MS m/z: [M + Na]+ calcd for
C114H174N2O8Na 1722.32, found 1723.5. Anal. Calcd for
C114H174N2O8: C, 80.51; H, 10.31; N, 1.65. Found: C, 80.39; H,
10.42; N, 1.67.
N,N′-Bis(1-butylpentadecyl)-1,7-bis-(3,4-didodecyloxy-
phenyl)perylene-3,4,9,10-tetracarboxydiimide (2c3). The reac-
tion of 3c (0.53 g, 0.5 mmol), bromododecane (0.75 g, 3 mmol), and
K2CO3 (0.3 g, 2.2 mmol) at 80 °C for 12 h followed by column
chromatography purification on silica gel using dichloromethane−
petroleum ether (v/v = 1:2) as eluent produced compound 2c3 (0.72
N,N′-Bis(1-heptyloctyl)-1,7-bis(3,4-dihexadecyloxyphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (2d4). The reaction of 3d
(0.53 g, 0.5 mmol), bromohexadecane (0.92 g, 3 mmol), and K2CO3
(0.3 g, 2.2 mmol) at 80 °C for 12 h followed by column
chromatography purification on silica gel using dichloromethane−
petroleum ether (v/v = 1:2) as eluent produced compound 2d4 (0.82
1
g, 84%) as a dark purple solid. H NMR (CDCl3, 600 MHz): δ ppm
8.63 (m, 2H), 8.17 (m, 2H), 7.93 (m, 2H), 7.06 (m, 6H), 5.20 (m,
2H), 3.92−4.09 (m, 8H), 1.78−2.23 (m, 16H), 1.20−1.55 (m, 116H),
0.83−0.90 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm 164.8,
164.6, 163.7, 163.5, 150.4, 149.9, 149.7, 142.0, 140.9, 135.7, 135.0,
134.6, 134.6, 134.4, 132.9, 132.6, 132.3, 130.0, 129.7, 129.5, 129.3,
129.1, 128.7, 128.4, 127.7, 127.0, 122.6, 122.3, 121.9, 121.8, 121.6,
121.3, 114.6, 114.5, 114.3, 69.6, 69.2, 69.0, 54.6, 54.5, 54.4, 32.3,
32.0,31.9, 31.8, 29.7, 29.6, 29.5, 29.4, 29.3, 29.2, 29.1, 26.9, 26.1, 22.6,
14.1. MALDI-TOF MS m/z: [M + Na]+ calcd for C116H178N2O8Na
1750.35, found 1750.4. Anal. Calcd for C116H178N2O8: C, 80.60; H,
10.38; N, 1.62. Found: C, 80.29; H, 10.40; N, 1.60.
1
g, 85%) as a dark purple solid. H NMR (CDCl3, 400 MHz): δ ppm
8.58 (d, 2H), 8.14 (m, 2H), 7.90 (m, 2H), 7.06 (m, 6H), 5.14 (s, 2H),
3.96−4.07 (m, 8H), 1.81−2.25 (m, 16H), 1.20−1.55 (m, 142H),
0.80−0.89 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm 164.8,
164.6, 163.7, 163.5, 150.4, 149.9, 149.7, 142.0, 140.9, 135.7, 135.0,
134.6, 132.6, 132.3, 129.9, 129.7, 129.5, 129.3, 129.1, 128.7, 128.4,
127.7, 127.0, 122.6, 122.3, 121.9, 121.6, 121.3, 114.6, 114.5, 114.3,
69.6, 69.2,54.5, 32.3, 31.9, 31.7, 29.7, 29.6, 29.5, 29.4, 29.3, 29.2, 26.9,
26.7, 26.1, 26.0, 22.6, 14.0. MALDI-TOF MS m/z: [M]+ Calcd for
C130H206N2O8 1923.58, found 1923.8. Anal. Calcd for C130H206N2O8:
C, 81.11; H, 10.79; N, 1.46. Found: C, 80.89; H, 10.59; N, 1.44.
Compounds 4a1−4d4. These compounds were prepared
according to the general method. To a solution of compounds 4a1−
4d4 in dry dichloromethane and methanesulfonic acid (v/v = 9:1) was
added DDQ at 0 °C.The stirred reaction mixture was allowed to warm
to room temperature. After 6 h, it was poured into ice, the product was
N,N′-Bis(1-butylpentadecyl)-1,7-bis(3,4-dihexadecyloxy-
phenyl)perylene-3,4,9,10-tetracarboxydiimide (2c4). The reac-
tion of 3c (0.53 g, 0.5 mmol), bromohexadecane (0.92 g, 3 mmol),
and K2CO3 (0.3 g, 2.2 mmol) at 80 °C for 12 h followed by column
chromatography purification on silica gel using dichloromethane−
petroleum ether (v/v = 1:2) as eluent produced compound 2c4 (0.83
1
g, 85%) as a dark purple solid. H NMR (CDCl3, 400 MHz): δ ppm
G
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
extracted with dichloromethane, and the organic extracts were dried
and filtered. The residue was purified by silica gel column
chromatography, eluting with dichloromethane−petroleum ether.
N,N′-Bis(2-hexyldecyl)-5,6:11,12-bis(3,4-dipentyloxybenzo)-
coronene-2,3,8,9-tetracarboxydiimide (4a1). The reaction of 2a1
(0.66 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for 6 h
followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v =1:1) as eluent produced
31.9, 31.8, 31.7, 30.1, 29.6, 29.5, 29.3, 29.2,28.8, 26.7, 22.9, 22.5, 14.2,
13.9. MALDI-TOF MS m/z: [M]+ calcd for C96H134N2O8 1443.01,
found 1443.3. Anal. Calcd for C96H134N2O8: 79.84; H, 9.35; N, 1.94.
Found: 79.72; H, 9.12; N, 1.89.
N,N′-Bis(2-octyldodecyl)-5,6:11,12-bis(3,4-dioctyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4b2). The reac-
tion of 2b2 (0.81 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for
6 h followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
1
compound 4a1 (0.61g, 92%) as a red solid. H NMR (CDCl3, 400
1
MHz): δ ppm 9.76 (s, 4H), 8.44 (s, 4H), 4.87 (m, 4H), 4.58 (m, 4H),
4.27 (d, 4H), 2.27−2.30 (m, 8H), 1.70−1.93 (m, 18H), 1.14−1.55 (m,
60H), 0.78−0.819 (m, 12H). 13C NMR (CDCl3, 75 MHz): δ ppm
164.5, 151.0, 126.1, 124.3, 123.9, 121.1, 121.0, 120.9, 120.1, 104.8,
69.2, 44.6, 36.8, 31.9, 31.8, 30.1, 29.8, 29.6, 29.4, 29.3, 28.8, 26.6, 22.9,
22.6, 22.5, 14.2, 14.0, 13.9. MALDI-TOF MS m/z: [M]+ calcd for
C88H118N2O8 1330.89, found 1331.5. Anal. Calcd for C88H118N2O8: C,
79.36; H, 8.93; N, 2.10. Found: C, 79.13; H, 8.82; N, 2.07.
compound 4b2 (0.74 g, 92%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.78 (s, 4H), 8.46 (s, 4H), 4.88 (m, 4H), 4.57 (m, 4H),
4.26 (d, 4H), 2.25−2.29 (m, 8H), 1.63−1.96 (m, 18H), 1.12−1.56 (m,
88H), 0.73−1.08 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm
164.6, 151.0, 126.1, 124.4, 123.9, 121.1, 120.9, 120.1, 104.8, 69.2, 36.8,
32.0, 31.9, 31.8, 30.2, 29.9, 29.8, 29.7, 29.6, 29.5, 29.3, 26.7, 22.8, 22.5,
14.2, 13.9. MALDI-TOF MS m/z: [M]+ calcd for C108H158N2O8
1611.2, found 1612.4. Anal. Calcd for C108H158N2O8: C, 80.45; H,
9.88; N, 1.74. Found: C, 80.27; H, 9.72; N, 1.70.
N,N′-Bis(2-hexyldecyl)-5,6:11,12-bis(3,4-dioctyloxybenzo)-
coronene-2,3,8,9-tetracarboxydiimide (4a2). The reaction of 2a2
(0.75 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for 6 h
followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
N,N′-Bis(2-octyldodecyl)-5,6:11,12-bis(3,4-didodecyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4b3). The reac-
tion of 2b3 (0.92 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for
6 h followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
1
compound 4a2 (0.69 g, 92%) as a red solid. H NMR (CDCl3, 400
1
MHz): δ ppm 9.77 (s, 4H), 8.45 (s, 4H), 4.88 (m, 4H), 4.57 (m, 4H),
4.26 (d, 4H), 2.25−2.29 (m, 8H), 1.64−1.95 (m, 18H), 1.15−1.57
(m,72H), 0.81−1.02 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm
164.5, 151.0, 126.1, 124.3, 123.9, 121.1, 120.9, 120.1, 104.8, 69.2, 44.6,
36.8, 32.0, 31.9, 31.8, 30.2, 29.9, 29.8, 29.6, 29.5, 29.3, 26.7, 26.6, 22.8,
22.6, 22.5, 14.2, 14.0, 13.9. MALDI-TOF MS m/z: [M]+ calcd for
C100H142N2O8 1499.08, found 1500.3. Anal. Calcd for C100H142N2O8:
C, 80.06; H, 9.54; N, 1.87. Found: C, 79.81; H, 9.41; N, 1.84.
N,N′-Bis(2-hexyldecyl)-5,6:11,12-bis(3,4-didodecyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4a3). The reac-
tion of 2a3 (0.86 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for
6 h followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
compound 4b3 (0.84 g, 91%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.78 (s, 4H), 8.45 (s, 4H), 4.88 (m, 4H), 4.57 (m, 4H),
4.25 (d, 4H), 2.25−2.27 (m, 8H), 1.65−1.96 (m, 18H), 1.15−1.54
(m,120H), 0.73−1.08 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm
164.6, 151.0, 126.1, 124.3, 123.9, 121.1, 120.9, 120.1, 104.8, 69.2, 44.6,
36.8, 32.0, 31.8, 30.2, 29.9, 29.8, 29.7, 29.6, 29.5, 29.3, 29.2, 26.7, 22.7,
22.5, 14.1, 14.0, 13.9. MALDI-TOF MS m/z: [M]+ calcd for
C124H190N2O8 1835.45, found 1837.3. Anal. Calcd for
C124H190N2O8: C, 81.08; H, 10.43; N, 1.53. Found: C, 79.92; H,
10.21; N, 1.48.
N,N′-Bis(2-octyldodecyl)-5,6:11,12-bis(3,4-dihexadecyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4b4). The reac-
tion of 2b4 (1.03 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for
6h followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
1
compound 4a3 (0.79 g, 92%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.77 (s, 4H), 8.45 (s, 4H), 4.88 (m, 4H), 4.56 (m, 4H),
4.26 (d, 4H), 2.25−2.29 (m, 8H), 1.65−1.97 (m, 18H), 1.15−1.54 (m,
104H), 0.72−0.91 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm
164.6, 151.0, 126.1, 124.3, 123.9, 121.1, 120.9, 120.1, 104.8, 69.2, 44.6,
36.8, 32.0, 31.9, 31.8, 30.2, 29.9, 29.8, 29.6, 29.5, 29.3, 26.6, 22.9, 22.6,
22.5, 14.1, 14.0, 13.9. MALDI-TOF MS m/z: [M]+ calcd for
C116H173N2O8 1722.32, found 1723.7. Anal. Calcd for
C116H173N2O8: C, 80.83; H, 10.12; N, 1.63. Found: C, 80.77; H,
9.98; N, 1.59.
1
compound 4b4 (0.96 g, 93%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.77 (s, 4H), 8.45 (s, 4H), 4.88 (m, 4H), 4.57 (m, 4H),
4.25 (d, 4H), 2.25−2.28 (m, 8H), 1.63−1.96 (m, 18H), 1.12−1.59
(m,152H), 0.73−1.08 (m, 24H). 13C NMR (CDCl3, 100 Hz): δ ppm
164.5,151.0, 126.1, 124.3, 123.9, 121.0, 120.1, 104.8, 69.3, 44.6, 36.9,
31.9, 30.2, 29.9, 29.8, 29.7, 29.4, 26.7, 22.7, 22.6, 14.1, 14.0. MALDI-
TOF MS m/z: [M]+ calcd for C140H222N2O8 2059.7, found 2059.9.
Anal. Calcd for C140H222N2O8: C, 81.58; H, 10.86; N, 1.36. Found: C,
81.27; H, 10.93; N, 1.33.
N,N′-Bis(2-hexyldecyl)-5,6:11,12-bis(3,4-dihexadecyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4a4). The reac-
tion of 2a4 (0.98 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for
6 h followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
N,N′-Bis(1-butylpentadecyl)-5,6:11,12-bis(3,4-dipentyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4c1). The reaction
of 2c1 (0.67 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for 6 h
followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
1
compound 4a4 (0.90 g, 91%) as a red solid. H NMR (CDCl3, 400
1
MHz): δ ppm 9.77 (s, 4H), 8.45 (s, 4H), 4.87 (m, 4H), 4.56 (m, 4H),
4.25 (d, 4H), 2.25−2.28 (m, 8H), 1.63−1.95 (m, 18H), 1.14−1.54
(m,136H), 0.79−0.88 (m, 24H). 13C NMR (CDCl3,100 Hz): δ ppm
164.5, 151.0, 126.0, 124.5, 123.9, 120.9, 120.0, 104.8, 69.3, 36.9, 32.0,
31.9, 30.3, 30.0, 29.9, 29.8, 29.7, 29.4, 26.8, 22.7, 22.6, 14.1. MALDI-
TOF MS m/z: [M]+ calcd for C132H206N2O8 1947.58, found 1947.9.
Anal. Calcd for C132H206N2O8: C, 81.34; H, 10.65; N, 1.44. Found: C,
81.27; H, 10.46; N, 1.42.
compound 4c1 (0.63 g, 94%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.64 (d, 4H), 8.26 (s, 4H), 5.26 (m, 2H), 4.61 (m, 8H),
2.27−2.62 (m, 16H), 1.14−1.80 (m, 60H), 0.76−1.03 (m, 24H). 13C
NMR (CDCl3, 75 MHz): δ ppm 165.3, 164.3, 151.0, 126.1, 123.9,
123.5, 121.6, 120.8, 120.6, 119.8, 105.0, 69.3, 55.1, 32.8, 32.5, 31.8,
29.9, 29.8, 29.7, 29.3, 29.0, 28.5, 28.3, 27.7, 22.9, 22.8, 22.5, 14.2, 14.1,
13.9. MALDI-TOF MS m/z: [M]+ calcd for C88H118N2O8 1330.89,
found 1331.5. Anal. Calcd for C88H118N2O8: C, 79.36; H, 8.93; N,
2.10. Found: C, 79.11; H, 9.12; N, 2.03.
N,N′-Bis(2-octyldodecyl)-5,6:11,12-bis(3,4-dipentyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4b1). The reac-
tion of 2b1 (0.72 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for
6 h followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
N,N′-Bis(1-butylpentadecyl)-5,6:11,12-bis(3,4-dioctyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4c2). The reaction
of 2c2 (0.75 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for 6 h
followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
1
compound 4b1 (0.66g, 93%) as a red solid. H NMR (CDCl3, 400
1
MHz): δ ppm 9.78 (s, 4H), 8.46 (s, 4H), 4.88 (m, 4H), 4.58 (m, 4H),
4.27 (d, 4H), 2.25−2.28 (m, 8H), 1.70−1.95 (m, 18H), 1.14−1.57 (m,
64H), 0.73−1.11 (m, 24H). 13C NMR (CDCl3, 75 MHz): δ ppm
164.6, 151.0, 126.1, 124.4, 123.9, 121.1, 121.0, 120.1, 104.8, 69.2, 36.8,
compound 4c2 (0.71 g, 95%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.74 (d, 4H), 8.31 (s, 4H), 5.47 (m, 2H), 4.57 (m, 8H),
2.20−2.59 (m, 16H), 1.12−1.83 (m, 84H), 0.76−0.99 (m, 24H). 13C
NMR (CDCl3, 75 MHz): δ ppm 165.4, 164.4, 151.0, 126.3, 124.0,
H
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
123.6, 121.7, 121.0, 120.9, 120.0, 105.0, 69.4, 55.1, 32.8, 32.5, 32.0,
31.8, 29.8, 29.7, 29.6, 29.5, 29.3, 27.7, 26.3, 22.9, 22.8, 22.5, 14.2, 14.0.
MALDI-TOF MS m/z: [M]+ calcd for C100H142N2O8 1499.08, found
1500.2. Anal. Calcd for C100H142N2O8: C, 80.06; H, 9.54; N, 1.87.
Found: C, 79.98; H, 9.37; N, 1.83.
NMR (CDCl3, 100 Hz): δ ppm 165.2, 164.4, 151.0, 126.0, 123.9,
123.4, 121.5, 120.7, 119.8, 105.0, 69.4, 55.3, 33.0, 32.0, 30.0, 29.9, 29.6,
29.5, 27.9, 26.4, 22.7, 14.1. MALDI-TOF MS m/z: [M]+ calcd for
C114H170N2O8 1695.3, found 1695.5. Anal. Calcd for C114H170N2O8: C,
80.70; H, 10.10; N, 1.65. Found: C, 80.58; H, 9.97; N, 1.63.
N,N′-Bis(1-heptyloctyl)-5,6:11,12-bis(3,4-didodecyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4d4). The reac-
tion of 2d4 (0.96 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for
6 h followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
N,N′-Bis(1-butylpentadecyl)-5,6:11,12-bis(3,4-didodecyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4c3). The reaction
of 2c3 (0.86 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for 6 h
followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
1
1
compound 4d4 (0.91 g, 95%) as a red solid. H NMR (CDCl3, 400
compound 4c3 (0.79 g, 92%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.83 (d, 4H), 8.37 (t, 4H), 5.48 (m, 2H), 4.56 (m, 8H),
2.20−2.58 (m, 16H), 1.25−1.61 (m, 144H), 0.81−0.88 (m, 24H). 13C
NMR (CDCl3, 75 MHz): δ ppm 165.4, 164.5, 151.1, 126.4, 124.1,
121.8, 121.1, 121.0, 120.1, 105.0, 69.4, 58.4, 55.2, 32.8, 31.9, 29.9, 29.8,
29.7, 29.4, 29.3, 27.7, 22.7, 22.6, 18.4, 14.0. MALDI-TOF MS m/z:
[M]+ calcd for C130H202N2O8 1919.55, found 1920.7. Anal. Calcd for
C130H202N2O8: C, 81.28; H, 10.60; N, 1.46. Found: C, 81.13; H, 10.37;
N, 1.42.
MHz): δ ppm 9.62 (d, 4H), 8.24 (s, 4H), 5.49 (m, 2H), 4.63 (m, 8H),
2.27−2.64 (m, 16H), 1.18−1.86 (m, 116H), 0.77−0.95 (m, 24H). 13C
NMR (CDCl3, 75 MHz): δ ppm 165.4, 164.5, 151.1, 126.4, 124.1,
121.8, 121.2, 121.0, 105.1, 69.4, 58.4, 55.1, 32.8, 32.5, 31.9, 31.8, 31.2,
29.9, 29.8, 29.6, 29.5, 29.3, 27.6, 26.3, 22.9, 22.7, 22.5, 18.4, 14.2, 14.1,
13.9. MALDI-TOF MS m/z: [M]+ calcd for C116H173N2O8 1722.32,
found 1723.3. Anal. Calcd for C116H173N2O8: C, 80.83; H, 10.12; N,
1.63; Found: C, 80.75; H, 9.93; N, 1.66.
N,N′-Bis(1-butylpentadecyl)-5,6:11,12-bis(3,4-didodecyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4c4). The reaction
of 2c4 (0.97 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for 6 h
followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
ASSOCIATED CONTENT
■
S
* Supporting Information
1H NMR and 13C NMR spectra of compound 2−4; TGA
curves of comoupoud 4, the optical images of compound 4a4
and 4d3. This material is available free of charge via the Internet
at http://pubs.acs.org.
1
compound 4d4 (0.93 g, 95%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.72 (d, 4H), 8.29 (s, 4H), 5.46 (m, 2H), 4.57 (m, 8H),
2.22−2.59 (m, 16H), 1.14−1.80 (m, 148H), 0.77−0.98 (m, 24H). 13C
NMR (CDCl3, 100 Hz): δ ppm 165.2, 151.0, 126.0, 123.9, 121.5,
120.6, 119.8, 105.0, 69.4, 55.1, 32.8, 32.5, 31.9, 30.0, 29.9, 29.8, 29.4,
27.9, 26.4, 23.0, 22.7, 22.6, 14.3, 14.1, 14.0. MALDI-TOF MS m/z:
[M]+ calcd for C132H206N2O8 1947.58, found 1947.9. Anal. Calcd for
C132H206N2O8: C, 81.34; H, 10.65; N, 1.44. Found: C, 81.23; H, 10.55;
N, 1.43.
AUTHOR INFORMATION
Corresponding Author
*E-mail: wangwenguang@bigc.edu.cn.
Notes
■
N,N′-Bis(1-heptyloctyl)-5,6:11,12-bis(3,4-dipentyloxybenzo)-
coronene-2,3,8,9-tetracarboxydiimide (4d1). The reaction of 2d1
(0.65 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for 6 h
followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank Mr. Hou Keyue for his help with NMR measure-
ments. This work was supported by the National Science
Foundation of China (Approval No: 60007004) and by
financial support from Discipline Construction of Beijing
Institute of Graphic Communication.
1
compound 4d1 (0.62 g, 95%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.79 (d, 4H, PerH), 8.34 (s, 4H, ArH), 5.47 (m, 2H,
NH), 4.59 (m, 8H, OCH3), 2.22−2.58 (m, 16H, CH2), 1.14−1.79 (m,
56H, CH2), 0.78−1.12 (m, 24H, CH3). 13C NMR (CDCl3, 75 MHz):
δ ppm 165.4, 164.4, 151.0, 126.4, 124.1, 123.7, 121.9, 121.2, 121.1,
120.8, 120.1, 105.0, 69.3, 58.4, 55.2, 32.8, 31.9, 29.8, 29.6, 29.4, 29.3,
28.5, 27.6, 22.7, 22.6, 18.3, 14.2, 14.0. MALDI-TOF MS m/z: [M]+
calcd for C86H114N2O8 1302.86, found 1303.0. Anal. Calcd for
C86H114N2O8: C, 79.22; H, 8.81; N, 2.15. Found: C, 79.08; H, 8.68; N,
2.17.
REFERENCES
■
(1) Schmidt-Mende, L.; Fechtenk O Tter, A.; Mullen, K.; Moons, E.;
̈
Friend, R. H.; MacKenzie, J. D. Science 2001, 293, 1119−1122.
(2) Kopitzke, J.; Wendorff, J. H. Chem. Unserer Zeit 2000, 34, 4−16.
(3) Nelson, J. Science 2001, 293, 1059−1060.
(4) Sergeyev, S.; Pisula, W.; Geerts, Y. H. Chem. Soc. Rev. 2007, 36,
1902−1929.
(5) Freudenmann, R.; Behnisch, B.; Hanack, M. J. Mater. Chem.
2001, 11, 1618−1624.
(6) Seguy, I.; Destruel, P.; Bock, H. Synth. Met. 2000, 111−112, 15−
18.
N,N′-Bis(1-heptyloctyl)-5,6:11,12-bis(3,4-dioctyloxybenzo)-
coronene-2,3,8,9-tetracarboxydiimide (4d2). The reaction of 2d2
(0.74 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for 6 h
followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
1
compound 4d2 (0.70 g, 95%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.67 (d, 4H), 8.33 (t, 4H), 5.48 (m, 2H), 4.61 (m, 8H),
2.24−2.60 (m, 16H), 1.13−1.81 (m, 80H), 0.79−1.00 (m, 24H). 13C
NMR (CDCl3, 75 MHz): δ ppm 165.3, 164.4, 151.0, 126.2 123.9,
123.5, 121.6, 120.8, 120.6, 119.9, 105.0, 69.4, 55.2, 32.9, 32.0, 29.9,
29.8, 29.7, 29.5, 27.8, 26.4, 22.8, 22.7, 14.2, 14.1. MALDI-TOF MS m/
z: [M]+ calcd for C98H138N2O8 1471.05, found 1471.5. Anal. Calcd for
C98H138N2O8: C, 79.95; H, 9.45; N, 1.90. Found: C, 79.78; H, 9.37; N,
1.87.
(7) Pisula, W.; Menon, A.; Stepputat, M.; Lieberwirth, I.; Kolb, U.;
Tracz, A.; Sirringhaus, H.; Pakula, T.; Mullen, K. Adv. Mater. 2005, 17,
̈
684−689.
(8) Laschat, S.; Baro, A.; Steinke, N.; Giesselmann, F.; Hagele, C.;
̈
Scalia, G.; Judele, R.; Kapatsina, E.; Sauer, S.; Schreivogel, A.; Tosoni,
M. Angew. Chem., Int. Ed. 2007, 46, 4832−4887.
(9) Christ, T.; Greiner, A.; Sander, R.; Stumpflen, V.; Wendorff, J. H.
̈
Adv. Mater. 1997, 9, 219−222.
N,N′-Bis(1-heptyloctyl)-5,6:11,12-bis(3,4-didodecyloxy-
benzo)coronene-2,3,8,9-tetracarboxydiimide (4d3). The reac-
tion of 2d3 (0.85 g, 0.5 mmol) and DDQ (0.23 g, 1 mmol) at 0 °C for
6 h followed by column chromatography purification on silica gel using
dichloromethane−petroleum ether (v/v = 1:1) as eluent produced
(10) Kumar, S. Liq. Cryst. 2004, 31, 1037−1059.
(11) Li, L.; Kang, S. W.; Harden, J.; Sun, Q.; Zhou, X.; Dai, L.; Jakli,
A.; Kumar, S.; Li, Q. Liq. Cryst. 2008, 35, 233−239.
(12) Sun, Q.; Dai, L.; Zhou, X.; Li, L.; Li, Q. Appl. Phys. Lett. 2007,
91, 253505−3.
1
compound 4d3 (0.80 g, 94%) as a red solid. H NMR (CDCl3, 400
MHz): δ ppm 9.78 (d, 4H), 8.33 (t, 4H), 5.47 (m, 2H), 4.59 (m, 8H),
(13) Zhou, X.; Kang, S.; Kumar, S.; Li, Q. Liq. Cryst. 2009, 36, 269−
274.
2.22−2.59 (m, 16H), 1.30−1.79 (m, 112H), 0.77−0.91 (m, 24H). 13C
I
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(14) Zhou, X.; Kang, S.; Kumar, S.; Kulkarni, R. R.; Cheng, S. Z. D.;
Li, Q. Chem. Mater. 2008, 20, 3551−3553.
(15) Liquid Crystals Beyond Displays: Chemistry, Physics, and
Applications; Li, Q., Ed.; John Wiley & Sons: New York, 2012.
(16) van de Craats, A. M.; Warman, J. M. Adv. Mater. 2001, 13, 130−
133.
(46) Avlasevich, Y.; Muller, S.; Erk, P.; Mullen, K. ChemEur. J.
̈
̈
2007, 13, 6555−6561.
(47) Muller, S.; Mullen, K. Chem. Commun. 2005, 4045−4046.
(48) Avlasevich, Y.; Li, C.; Mullen, K. J. Mater. Chem. 2010, 20,
̈
3814−3826.
(49) Muller, S.; Mullen, K. Chem. Commun. 2005, 4045−4046.
(50) Pisula, W.; Kastler, M.; Wasserfallen, D.; Pakula, T.; Mullen, K.
(17) Pisula, W.; Tomovic, Z.; Simpson, C.; Kastler, M.; Pakula, T.;
̈
J. Am. Chem. Soc. 2004, 126, 8074−8075.
Mullen, K. Chem. Mater. 2005, 17, 4296−4303.
̈
̌
́
(51) Pisula, W.; Tomovic, Z.; Stepputat, M.; Kolb, U.; Pakula, T.;
(18) Chen, Z.; Debije, M. G.; Debaerdemaeker, T.; Osswald, P.;
Mullen, K. Chem. Mater. 2005, 17, 2641−2647.
̈
Wurthner, F. ChemPhysChem 2004, 5, 137−140.
̈
(52) Tracz, A.; Jeszka, J. K.; Watson, M. D.; Pisula, W.; Mullen, K.;
̈
(19) Craats, A. M. V. D.; Warman, J. M.; Fechtenkotter, A.; Brand, J.
̈
Pakula, T. J. Am. Chem. Soc. 2003, 125, 1682−1683.
(53) Pisula, W.; Menon, A.; Stepputat, M.; Lieberwirth, I.; Kolb, U.;
D.; Harbison, M. A.; Mullen, K. Adv. Mater. 1999, 11, 1469−1472.
̈
(20) Funahashi, M.; Hanna, J. I. Adv. Mater. 2005, 17, 594−598.
(21) Oikawa, K.; Monobe, H.; Takahashi, J.; Tsuchiya, K.; Heinrich,
B.; Guillon, D.; Shimizu, Y. Chem. Commun. 2005, 5337−5339.
(22) Struijk, C. W.; Sieval, A. B.; Dakhorst, J. E. J.; van Dijk, M.;
Kimkes, P.; Koehorst, R. B. M.; Donker, H.; Schaafsma, T. J.; Picken,
S. J.; van de Craats, A. M.; et al. J. Am. Chem. Soc. 2000, 122, 11057−
11066.
Tracz, A.; Sirringhaus, H.; Pakula, T.; Mullen, K. Adv. Mater. 2005, 17,
̈
684−689.
(54) van de Craats, A. M.; Stutzmann, N.; Bunk, O.; Nielsen, M. M.;
Watson, M.; Mullen, K.; Chanzy, H. D.; Sirringhaus, H.; Friend, R. H.
̈
Adv. Mater. 2003, 15, 495−499.
(55) Piris, J.; Debije, M. G.; Stutzmann, N.; Laursen, B. W.; Pisula,
W.; Watson, M. D.; Bjørnholm, T.; Mullen, K.; Warman, J. M. Adv.
̈
(23) Malenfant, P. R. L.; Dimitrakopoulos, C. D.; Gelorme, J. D.;
Kosbar, L. L.; Graham, T. O.; Curioni, A.; Andreoni, W. Appl. Phys.
Lett. 2002, 80, 2517−2519.
Funct. Mater. 2004, 14, 1053−1061.
(56) Langhals, H.; Ismael, R.; Yuruk, O. Tetrahedron 2000, 56,
̈
̈
5435−5441.
(24) Jones, B. A.; Ahrens, M. J.; Yoon, M.; Facchetti, A.; Marks, T. J.;
Wasielewski, M. R. Angew. Chem., Int. Ed. 2004, 43, 6363−6366.
(25) Facchetti, A.; Mushrush, M.; Katz, H. E.; Marks, T. J. Adv.
Mater. 2003, 15, 33−38.
(57) Wurthner, F.; Stepanenko, V.; Chen, Z.; Saha-Moller, C. R.;
̈
̈
Kocher, N.; Stalke, D. J. Org. Chem. 2004, 69, 7933−7939.
(58) Jones, B. A.; Ahrens, M. J.; Yoon, M.; Facchetti, A.; Marks, T. J.;
Wasielewski, M. R. Angew. Chem., Int. Ed. 2004, 43, 6363−6366.
(59) Rajasingh, P.; Cohen, R.; Shirman, E.; Shimon, L. J. W.;
Rybtchinski, B. J. Org. Chem. 2007, 72, 5973−5979.
(26) Jones, B. A.; Ahrens, M. J.; Yoon, M.; Facchetti, A.; Marks, T. J.;
Wasielewski, M. R. Angew. Chem., Int. Ed. 2004, 43, 6363−6366.
(27) Wurthner, F. Chem. Commun. 2004, 1564−1579.
̈
(60) Zhai, L.; Shukla, R.; Rathore, R. Org. Lett. 2009, 11, 3474−3477.
(28) Cormier, R. A.; Gregg, B. A. Chem. Mater. 1998, 10, 1309−
1319.
̌
(61) Pisula, W.; Tomovic,
́
Z.; El Hamaoui, B.; Watson, M. D.; Pakula,
T.; Mullen, K. Adv. Funct. Mater. 2005, 15, 893−904.
(62) Hatsusaka, K.; Ohta, K.; Yamamoto, I.; Shirai, H. J. Mater. Chem.
2001, 11, 423−433.
̈
(29) Huang, C.; Barlow, S.; Marder, S. R. J. Org. Chem. 2011, 76,
2386.
(30) Iverson, I. K.; Tam-Chang, S. W. J. Am. Chem. Soc. 1999, 121,
5801−5802.
(31) Gregg, B. A.; Cormier, R. A.; et al. J. Am. Chem. Soc. 2001, 123,
7959.
(32) An, Z.; Yu, J.; Jones, S. C.; Barlow, S.; Yoo, S.; Domercq, B.;
Prins, P.; Siebbeles, L. D. A.; Kippelen, B.; Marder, S. R. Adv. Mater.
2005, 17, 2580−2583.
(33) Neuteboom, E. E.; Meskers, S. C. J.; Meijer, E. W.; Janssen, R.
A. J. Macromol. Chem. Phys. 2004, 205, 217−222.
(34) Hoeben, F. J. M.; Jonkheijm, P.; Meijer, E. W.; Schenning, A.;
et al. Chem. Rev. 2005, 105, 1491−1546.
(35) Chen, Z.; Stepanenko, V.; Dehm, V.; Prins, P.; Siebbeles, L. D.
A.; Seibt, J.; Marquetand, P.; Engel, V.; Wurthner, F. ChemEur. J.
̈
2007, 13, 436−449.
(36) Hansen, M. R.; Schnitzler, T.; Pisula, W.; Graf, R.; Mullen, K.;
̈
Spiess, H. W. Angew. Chem., Int. Ed. 2009, 48, 4621−4624.
(37) Lemaur, V.; Da Silva Filho, D. A.; Coropceanu, V.; Lehmann,
M.; Geerts, Y.; Piris, J.; Debije, M. G.; van de Craats, A. M.;
Senthilkumar, K.; Laurens, D.; et al. J. Am. Chem. Soc. 2004, 126,
3271−3279.
(38) Kirkpatrick, J.; Marcon, V.; Nelson, J.; Kremer, K.; Andrienko,
D. Phys. Rev. Lett. 2007, 98, 227402.
(39) Wicklein, A.; Lang, A.; Muth, M.; Thelakkat, M. J. Am. Chem.
Soc. 2009, 131, 14442−14453.
(40) Cormier, R. A.; Gregg, B. A. J. Phys. Chem. B 1997, 101, 11004−
11006.
(41) Funahashi, M.; Sonoda, A. Org. Electron. 2012, 13, 1633−1640.
(42) Rohr, U.; Schlichting, P.; B O Hm, A.; Gross, M.; Meerholz, K.;
Br A Uchle, C.; Mullen, K. Angew. Chem., Int. Ed. 1998, 37, 1434−
̈
1437.
(43) Nolde, F.; Pisula, W.; Muller, S.; Kohl, C.; Mullen, K. Chem.
̈
̈
Mater. 2006, 18, 3715−3725.
(44) Rohr, U.; Kohl, C.; Mullen, K.; van de Craats, A.; Warman, J. J.
Mater. Chem. 2001, 11, 1789−1799.
(45) Lutke Eversloh, C.; Li, C.; Mullen, K. Org. Lett. 2011, 13, 4148−
̈
̈
̈
4150.
J
dx.doi.org/10.1021/jo400425n | J. Org. Chem. XXXX, XXX, XXX−XXX