1,6- and 1,7-regioisomers of dinitro- and diamino-substituted perylene bisimides: Synthesis, photophysical and electrochemical properties

Article abstract of DOI:10.1016/j.tetlet.2013.12.041

1,6- and 1,7-regioisomers of dinitro- (1,6-3 and 1,7-3) and diamino-substituted perylene bisimides (1,6-1 and 1,7-1) were synthesized. The regioisomers 1,6-3 and 1,7-3 were successfully separated by high performance liquid chromatography and characterized

Full text of DOI:10.1016/j.tetlet.2013.12.041

Tetrahedron Letters 55 (2014) 884–888
Contents lists available at ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
1,6- and 1,7-regioisomers of dinitro- and diamino-substituted
perylene bisimides: synthesis, photophysical and electrochemical
properties
⇑
Hsing-Yang Tsai, Che-Wei Chang, Kew-Yu Chen
Department of Chemical Engineering, Feng Chia University, 40724 Taichung, Taiwan, ROC
a r t i c l e i n f o
a b s t r a c t
Article history:
1,6- and 1,7-regioisomers of dinitro- (1,6-3 and 1,7-3) and diamino-substituted perylene bisimides (1,6-1
and 1,7-1) were synthesized. The regioisomers 1,6-3 and 1,7-3 were successfully separated by high per-
formance liquid chromatography and characterized by 500 MHz 1H NMR spectroscopy. Subsequently, the
reduction of 1,6-3 and 1,7-3 afforded the corresponding diaminoperylene bisimides 1,6-1 and 1,7-1,
respectively. This is the first time 1,6-regioisomers of dinitro- and diamino-substituted perylene bisi-
mides are obtained in pure form. The photophysical and electrochemical properties of 1,6-3 and 1,7-3
were found to be almost the same. However, the regioisomers 1,6-1 and 1,7-1 exhibit significant differ-
ences in their optical characteristics. The absorption spectrum of 1,6-1 covers a larger part of the visible
region compared to that of 1,7-1. Upon excitation, 1,6-1 also show larger dipole moment change than that
of 1,7-1. Time-dependent density functional theory calculations are reported on these dyes in order to
rationalize their electronic structure and absorption spectra.
Received 30 September 2013
Revised 2 December 2013
Accepted 10 December 2013
Available online 19 December 2013
Keywords:
1,6-Dinitroperylene bisimide
1,6-Diaminoperylene bisimide
Intramolecular charge transfer
Lippert–Mataga equation
Ó 2013 Elsevier Ltd. All rights reserved.
Perylene bisimides (PBIs) and related derivatives possess excel-
lent thermal, photochemical and photophysical stabilities with
high extinction coefficients.1 Their use has been explored for
potential applications in molecular electronic and optical devices,
such as photovoltaic cells,2 light-emitting diodes,3 organic field-ef-
fect transistors (OFETs),4 dye lasers,5 optical power limiters,6 LCD
color filters,7 light-harvesting arrays,8 electrophotographic
devices,9 photochromic materials,10 logic gates,11 and molecular
wires.12 They have also been utilized as building blocks to con-
struct supramolecular or artificial photosynthetic systems.13 In re-
cent years, more and more novel perylene bisimide derivatives
with either electron-donating or electron-withdrawing groups
were reported in the literature, such as (a) piperidinyl-substituted
PBIs,14 (b) pyrrolidinyl-substituted PBIs,15 (c) alkylamino-substi-
tuted PBIs,16 (d) amino-substituted PBIs,17 (e) alkoxy-substituted
PBIs,18 (f) hydroxy-substituted PBIs,19 (g) aryl-substituted PBIs,20
(h) ferrocenyl-substituted PBIs,21 (i) alkyl-substituted PBIs,22 (j)
perfluoroalkyl-substituted PBIs,23 (k) boryl-substituted PBIs,24 (l)
cyano-substituted PBIs,25 (m) nitro-substituted PBIs,26 etc. To date,
a general method for introducing substituents onto the PBIs’ core is
bromination or chlorination of perylene-3,4,9,10-tetracarboxylic
dianhydride (6). Nucleophilic substitutions and metal-catalyzed
cross-coupling reactions can then be executed and yield a regioiso-
meric mixture of 1,6- and 1,7-disubstituted PBIs. The most widely
reported molecules made from the above reaction were 1,7-disub-
stituted PBIs,27 rather than 1,6-disubstituted PBIs.14a Recently,
Dubey et al. have synthesized, separated, and characterized
1,6- and 1,7-regioisomers of diphenoxy and dipyrrolidinyl substi-
tuted PBIs.28 The results have shown that 1,6-dipyrrolidinylperyl-
ene bisimide covers a larger portion of the visible region (450–
750 nm) compared to that of 1,7-dipyrrolidinylperylene bisimide.
Therefore, the 1,6-regioisomer may be of particular interest for
organic photovoltaic applications. To expand the scope of the
PBI-based dyes available for designing systems for OFETs and
photovoltaic cells, the present research reports the synthesis,
separation, characterization, photophysical and electrochemical
properties of 1,6- and 1,7-regioisomers of dinitro- and diamino-
substituted PBIs.
Scheme 1 shows the chemical structures and synthetic routes of
nitro-substituted (3 and 4) and amino-substituted PBIs (1 and 2).
The synthesis starts from an imidization of perylene-3,4,9,10-tetra-
carboxylic dianhydride (6) by reacting with cyclohexylamine. The
nitration of perylene bisimide can then be achieved by the reaction
of 5 with cerium (IV) ammonium nitrate (CAN) and HNO3 under
ambient temperature. Both mono- and di-substituted nitroperyl-
ene bisimides (4 and 3) were obtained by controlling the reaction
time,29 and the regioisomeric 1,6- and 1,7-dinitroperylene
bisimides (1,6-3 and 1,7-3) were successfully separated by high
⇑
Corresponding author. Tel.: +886 4 24517250x3683; fax: +886 4 24510890.
E-mail address: kyuchen@fcu.edu.tw (K.-Y. Chen).
0040-4039/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2013.12.041

H.-Y. Tsai et al. / Tetrahedron Letters 55 (2014) 884–888
885
R
N
R
N
R
N
O
O
O
O
O
O
O
O
O
O
O
O
O
SnCl2.2H2O
THF
RNH2
CAN, HNO3
CH2Cl2, 2 h
NO2
NH2
NMP, HOAc
O
6
N
R
O
5
O
N
R
O
4
N
R
O
2
CAN, HNO3
CH2Cl2, 48 h
R = cyclohexyl
NO2
NH2
O
O
O
N
O
O
SnCl2.2H2O (6 eq.)
THF, 6 h
R
N
O
R
R
N
O
N
R
O
NO2
NH2
1
1,6-
1,6-3
+
NO2
NH2
O
N
O
O
N
O
O
N
O
O
N
O
SnCl2.2H2O (6 eq.)
THF, 6 h
R
R
R
R
O2N
H2N
3
1,7-
1,7-1
Scheme 1. Synthetic routes of 1–4.
performance liquid chromatography (HPLC). Subsequently, the
reduction of 1,6-3 and 1,7-3 by tin (II) chloride dihydrate (SnCl2-
ꢀ2H2O) in refluxing THF obtained the 1,6- and 1,7-diaminoperylene
bisimides (1,6-1 and 1,7-1), respectively.30 It is to be noted that the
characteristic signals of the regioisomers 1,6-3 and 1,7-3 in the 1H
NMR spectra (Fig. S1), one singlet and two doublets of perylene
core protons, exhibit very small differences in the chemical shift
values (0.01 and 0.04 ppm for the doublets at 8.26–8.68). However,
a convenient unequivocal assignment of the NMR spectrum to the
individual regioisomers 1,6-3 and 1,7-3 was performed on the
basis of the signal of methanetriyl protons next to the imide nitro-
gen at 5.01 ppm. Because of the same chemical environment, both
methanetriyl protons of major regioisomer 1,7-3 appear as one
common multiplet at 5.01 ppm, but the signal splits into double
multiplets for minor regioisomer 1,6-3. In this way, an unambigu-
ous characterization has been made successfully on the basis of
500 MHz 1H NMR.
Figure 1 shows the steady state absorption spectra of 1–3 in
dichloromethane. The longest wavelength absorption band of both
1,6-3 and 1,7-3 appears at 515 nm, which is assigned to the
Figure 1. Normalized absorption spectra of 1–3 in dichloromethane solution.
p–
p⁄
transitions localized on the perylene core.26a In addition, the
absorption spectra of all nitro-substituted PBIs (1,6-3, 1,7-3 and
4) are nearly identical with the spectrum of the non-substituted
perylene bisimide (5), but they are non-fluorescent chromophores.
On the other hand, the reduction of 1,6-3 (1,7-3) to 1,6-1 (1,7-1)
switches the substituent from an electron-withdrawing group to
an electron-donating group and causes a large red shift. The spec-
tra of monoamino-substituted (2) and diamino-substituted PBIs
(1,6-1 and 1,7-1) are dominated by very broad absorption bands
that span a large part of the visible spectrum (400–750 nm). These
broad bands are characteristic of perylene bisimide derivatives
N-substituted at the bay-core positions, due to charge transfer
absorption.31 In contrast to 1,6-3 and 1,7-3, the diamino-substi-
tuted PBIs 1,6-1 and 1,7-1 display significant differences in their
absorptive features. In the case of 1,7-1, the longest wavelength
absorption band is centered at 620 nm. Whereas for regioisomer
1,6-1, this lowest energy band is slightly broader and blue-shifted
by ca. 6 nm with respect to that of 1,7-1 and has a small shoulder
at ca. 520 nm. The longest wavelength absorption band of both 1,6-
1 and 1,7-1 is red-shifted relative to that of the mono-substituted
compound (2: 578 nm), which can be explained by the fact that the

886
H.-Y. Tsai et al. / Tetrahedron Letters 55 (2014) 884–888
addition of amino (electron-donating) groups at the perylene core
increases the HOMO energy level and hence decreases the energy
gap. This viewpoint can be further supported by a theoretical ap-
proach based on density functional theory (vide infra). Moreover,
the longest wavelength absorption band of 1,6-1 and 1,7-1 exhibits
a red shift when the solvent polarity increases (Table 1), which is
consistent with previous studies.31
The fluorescence spectra of 1,6-1 in various solvents with differ-
ent polarity are shown in Figure 2 and summarized in Table 1,
whereas those of 1,7-1 and 2 can be found in the Supplementary
data (Figs. S2 and S3). Unlike the small shift in absorption spectra,
the fluorescence spectra of amino-substituted PBIs (1 and 2) are
largely red-shifted along with the increase of the solvent polarity,
which indicates strong intramolecular charge transfer (ICT) charac-
teristics for the excited states of 1,6-1, 1,7-1 and 2. We used the
well-established fluorescence solvatochromic shift method32 to
measure the stabilization of the excited states of 1,6-1 and com-
pared these results to those of 1,7-1 and 2. The change of magni-
Figure 2. Normalized emission spectra of 1,6-1 in cyclohexane (black line), ethyl
acetate (blue line), dichloromethane (green line), and acetonitrile (red line).
Lippert–Mataga plots (inset) for 1,6-1 (black line), 1,7-1 (blue line), and 2 (purple
line).
tudes for dipole moments between ground and excited states,
ƒ! ƒ!
that is, Dl ¼ j le ꢁ lg j, can be calculated by the Lippert–Mataga
equation and expressed as:
2
hc
2
ꢀ
ta
ꢀ
tf
ꢁ
¼
ðle
ꢁ
lgÞ aꢁ0 3
D
f þ const:
ð1Þ
where h is the Planck constant, c is the speed of light, and a0 denotes
the cavity radius in which the solute resides, calculated to be 7.0 Å
via Hartree–Fock theories with 6-31G(d0,p0) basis, ta
ꢁ
tf is the
Stokes shift of the absorption and emission peak maximum, and
f is the orientation polarizability defined as:
ꢀ
ꢀ
D
e
ꢁ 1
n2 ꢁ 1
D
f ¼ fð
e
Þ ꢁ fðn2Þ ¼
ꢁ
ð2Þ
2
e
þ 1 2n2 þ 1
ꢀ
ꢀ
The plot of the Stokes shift ta
ꢁ
tf as a function of
D
f is suffi-
2 (Fig. 2). Accordingly,
ciently linear for 1,6-1, 1,7-1 and
ƒ! ƒ!
D
l ¼ j le ꢁ lg j was calculated to be 5.2 D, 6.1 D and 7.4 D for
1,7-1, 1,6-1 and 2, respectively. These values indicate that the
asymmetric compound 2 has a larger dipole moment change than
that of the symmetric compound 1,6-1 (1,7-1), which are in good
agreement with previous Letters.33 The results also show that
1,6-1 (6.1 D) has a larger dipole moment change than that of 1,7-
1 (5.2 D). By combining the 1H NMR spectral data (vide supra) with
Figure 3. Cyclic voltammograms of 1–3 measured in dichloromethane solution
with ferrocenium/ferrocene, at 200 mV/s.
the Dl data, we may conclude that the chemical structure of 1,6-1
is more asymmetric than that of 1,7-1.
reduction potentials are shifted toward more negative values with
increasing numbers of substituted amino groups. The two revers-
ible one-electron oxidations of 1,7-1 occur at 0.79 and 1.17 V,
whereas for 1,6-1, both first and second oxidations are slightly
shifted to more positive values by 0.05 and 0.07 V, respectively.
The results clearly indicate that the removal of electrons from
1,6-1 is more difficult in comparison to 1,7-1; these findings are
in good agreement with previous reports.28 Table 2 summarizes
the redox potentials and the HOMO and LUMO energy levels esti-
mated from cyclic voltammetry (CV) for 1–5. It appears that the
The cyclic voltammograms of 1–3 are illustrated in Figure 3. The
two regioisomers of dinitro-substituted PBIs (1,6-3 and 1,7-3),
which are mainly known for their electron-accepting capabilities,
showed very similar redox characteristics. Both the isomers exhibit
two quasi-reversible one-electron reductions; these are ꢁ0.09 and
ꢁ0.34 V for 1,7-3 and ꢁ0.11 and ꢁ0.37 V for 1,6-3. On the other
hand, the amino-substituted PBIs (1,6-1, 1,7-1 and 2), which are
mainly known for their electron-donating capabilities, undergo
two quasi-reversible one-electron oxidations and two quasi-
reversible one-electron reductions in dichloromethane at modest
potentials. It is apparent that both the first oxidation and the first
Table 2
Summary of half-wave redox potentials, HOMO and LUMO energy levels for 1–5
a
a
a
a
Compound
E+
E2+
Eꢁ
E2ꢁ
1/2
EHOMO/ELUMO (eV)b
1/2
1/2
1/2
Table 1
Summary of optical absorption and emission properties of 1,6-1 and 1,7-1 in various
solvents
1,6-1
1,7-1
2
1,6-3
1,7-3
4
0.84
0.79
0.97
–
–
–
1.24
1.17
1.36
–
–
–
ꢁ1.13
ꢁ1.15
ꢁ0.97
ꢁ0.11
ꢁ0.09
ꢁ0.19
ꢁ0.46
ꢁ1.23
ꢁ1.24
ꢁ1.09
ꢁ0.37
ꢁ0.34
ꢁ0.51
ꢁ0.76
ꢁ5.44/ꢁ3.31
ꢁ5.39/ꢁ3.28
ꢁ5.57/ꢁ3.33
ꢁ6.73/ꢁ4.33
ꢁ6.75/ꢁ4.35
ꢁ6.64/ꢁ4.25
ꢁ6.36/ꢁ3.98
a
1,6-1/1,7-1
kabs (nm)
kem (nm)
Ub
Cyclohexane
Ethyl acetate
Dichloromethane
Acetonitrile
582/587
604/613
612/620
615/624
634/638
669/675
681/693
692/701
0.15/0.18
0.11/0.13
0.07/0.09
0.04/0.04
5
–
–
a
Measured in a solution of 0.1 M tetrabutylammonium hexafluorophosphate
(TBAPF6) in dichloromethane versus SCE (in V).
a
Measured at 2 ꢂ 10ꢁ5 M.
b
b
Determined with N,N0-dioctyl-3,4,9,10-perylenedicarboximide as reference.13b
Calculated from EHOMO = ꢁ4.88 ꢁ (Eoxd ꢁ EFc/Fc+), ELUMO = EHOMO + Eg.

H.-Y. Tsai et al. / Tetrahedron Letters 55 (2014) 884–888
887
first reduction (oxidation) potential is shifted toward a more posi-
tive (negative) value with increasing numbers of substituted nitro
(amino) groups, while both the HOMO and LUMO energy levels de-
crease (increase) with the trend. The HOMO/LUMO energy levels of
1,6-1, 1,7-1, 2, 1,6-3 and 1,7-3 are estimated to be ꢁ5.44/ꢁ3.31,
ꢁ5.39/ꢁ3.28, ꢁ5.57/ꢁ3.33, ꢁ6.73/ꢁ4.33 and ꢁ6.75/ꢁ4.35 eV,
respectively. As a result, the trend of the HOMO–LUMO energy
gap is 3 > 2 > 1, which is in good agreement with the theoretical
calculations (vide infra).
nificant differences in their optical characteristics. In addition to
the longest wavelength absorption band at around 620 nm, 1,6-1
exhibits another shoulder band at ca. 520 nm, and consequently,
covers a large part of the visible region relative to that of 1,7-1.
Upon excitation, 1,6-1 also shows
a larger dipole moment
change than that of 1,7-1; the dipole moments of both com-
pounds have been estimated using the Lippert–Mataga equation.
The results offer the potential for synthesizing 1,6-disubstituted
perylene bisimide derivatives with extended optical and electro-
chemical properties. Working toward their applications on n-
type organic semiconductors (1,6-3 and 1,7-3) and organic pho-
tovoltaic devices (1,6-1 and 1,7-1) is in progress.
For a deeper insight into the molecular structures and electronic
properties of 1–5, quantum chemical calculations were performed
using density functional theory (DFT) at the B3LYP/6-31G⁄⁄ level.
The highest occupied molecular orbitals (HOMOs) and the lowest
unoccupied molecular orbitals (LUMOs) of 1,6-1, 1,7-1 and 2 are
shown in Figure S5. The HOMO of all amino-substituted PBIs
(1,6-1, 1,7-1 and 2) is delocalized mainly on the amino group
and the perylene core, while the LUMO is extended from the cen-
tral perylene core to the bisimide groups. The calculated and
experimental parameters for perylene bisimide derivatives 1–5
are summarized in Table 3. The results indicate that both the
HOMO and LUMO energy levels increase (decrease) as the number
of amino (nitro) groups increases, and the calculated band gap
energies are in good agreement with experimental data. The
absorption and emission spectra of 1,6-1, 1,7-1 and 2 were also cal-
culated by time-dependent DFT calculations (Franck–Condon prin-
ciple, Table S1). The calculated excitation/fluorescence
wavelengths for the S0 ? S1/S1 ? S0 transitions are 558/633 nm
for 1,6-1, 579/646 nm for 1,7-1, and 547/616 nm for 2, which is
very close to the experimental results. Furthermore, DFT (B3LYP/
6-31G⁄⁄) calculations show that the ground-state geometries of
the perylene core have two core twist angles, that is, approximate
dihedral angles between the two naphthalene subunits attached to
the central benzene ring; these are ꢃ20.09 and ꢃ20.10° for 1,6-1,
ꢃ19.20° and ꢃ19.38° for 1,7-1, ꢃ9.18° and ꢃ17.46° for 2, ꢃ17.22
and ꢃ17.34° for 1,6-3, ꢃ17.02° and ꢃ17.12° for 1,7-3, and ꢃ7.89°
and ꢃ15.87° for 4 (Table 3 and Fig. S6). The core twist angles of
the amino-substituted (1,6-disubstituted) PBIs are generally larger
than those of nitro-substituted (1,7-disubstituted) compounds.
In summary, we have successfully synthesized, separated, and
characterized 1,6- and 1,7-regioisomers of dinitro- and diamino-
substituted PBIs. The regioisomers of dinitro-substituted PBIs
were separated by conventional high performance liquid chro-
matography. Subsequently, the reduction of 1,6- and 1,7-dinitr-
Acknowledgment
We thank the National Science Council (No. NSC 101-2113-M-
035-001-MY2) for the financial support.
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.tetlet.2013.
12.041.
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(1,6-3
and
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afforded
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14. (a) Fan, L.; Xu, Y.; Tian, H. Tetrahedron Lett. 2005, 46, 4443; (b) Rajasingh, P.;
Cohen, R.; Shirman, E.; Shimon, L. J. W.; Rybtchinski, B. J. Org. Chem. 2007, 72,
5973.
Calculated and experimental parameters for perylene bisimide derivatives
a
b
Compound
HOMOa
LUMOa
Eg
Eg
Twisting angle (°)
1,6-1
1,7-1
2
1,6-3
1,7-3
4
ꢁ5.43
ꢁ5.33
ꢁ5.62
ꢁ6.55
ꢁ6.57
ꢁ6.25
ꢁ5.94
ꢁ3.03
ꢁ3.05
ꢁ3.21
ꢁ4.07
ꢁ4.11
ꢁ3.84
ꢁ3.46
2.40
2.28
2.41
2.48
2.46
2.41
2.48
2.13
2.11
2.24
2.40
2.40
2.39
2.38
20.09, 20.10
19.20, 19.38
9.18, 17.46
17.22, 17.34
17.02, 17.12
7.89, 15.87
0.00, 0.00
5
15. (a) Ma, Y. S.; Wang, C. H.; Zhao, Y. J.; Yu, Y.; Han, C. X.; Qiu, X. J.; Shi, Z.
Supramol. Chem. 2007, 19, 141; (b) Zhao, Y.; Wasielewski, M. R. Tetrahedron
Lett. 1999, 40, 7047.
a
Calculated by DFT/B3LYP (in eV).
At absorption maxima (Eg = 1240/kmax, in eV).
b

888
H.-Y. Tsai et al. / Tetrahedron Letters 55 (2014) 884–888
16. Wang, H.; Kaiser, T. E.; Uemura, S.; Würthner, F. Chem. Commun. 2008, 10,
1181.
HPLC system equipped with a refractive index detector and fitted with a
macro-HPLC column (Si, 8
m, 250 ꢂ 22 mm). The eluent was 8:1 hexane/ethyl
l
17. (a) Chen, K.-Y.; Fang, T.-C.; Chang, M.-J. Dyes Pigm. 2011, 92, 517; (b) Tsai, H.-Y.;
Chen, K.-Y. Dyes Pigm. 2013, 96, 319.
acetate flowing at 12 mL/min. Two fractions were collected from the column;
the first was pure 1,6 isomer, and the second was pure 1,7 isomer.
Characterization data: 1,6-3: 1H NMR (500 MHz, CDCl3) d 8.78 (s, 2H), 8.63
(d, J = 8.0 Hz, 2H), 8.30 (d, J = 8.0 Hz, 2H), 5.02 (m, 2H), 2.52 (m, 4H), 1.90 (m,
4H), 1.74 (m, 6H), 1.46 (m, 4H), 1.36 (m, 2H); MS (FAB): m/z (relative intensity)
645 (M+H+, 100); HRMS calcd. for C36H29O8N4 645.1985, found 645.1983.
Selected data for 1,7-3: 1H NMR (500 MHz, CDCl3) d 8.78 (s, 2H), 8.68 (d,
J = 8.5 Hz, 2H), 8.28 (d, J = 8.5 Hz, 2H), 5.01 (m, 2H), 2.51 (m, 4H), 1.92 (m, 4H),
1.74 (m, 6H), 1.46 (m, 4H), 1.36 (m, 2H); MS (FAB): m/z (relative intensity) 645
(M+H+, 100); HRMS calcd for C36H29O8N4 645.1985, found 645.1981.
30. General procedure for reduction: Tin chloride dihydrate (1.0 g, 4.8 mmol) and
1,6- or 1,7-dinitroperylene bisimides (0.5 g, 0.8 mmol) were suspended in
50 ml of THF, and stirred at 25 °C under N2 for 20 min. The solvent was refluxed
80 °C with stirring for 6 h. THF is removed at the rotary evaporator, and the
residue was dissolved in ethyl acetate and washed with 10% sodium hydrate
solution and brine. The organic layer was dried over anhydrous MgSO4 and the
filtrate was concentrated under reduced pressure. The crude product was
purified by silica gel column chromatography with eluent ethyl acetate/n-
hexane (4/5) to afford 1,6- or 1,7-diaminoperylene bisimides (1,6-1 or 1,7-1) in
82% yield. Characterization data: 1,6-1: 1H NMR (400 MHz, CDCl3) d 8.76 (d,
J = 8.4 Hz, 2H), 8.64 (d, J = 8.4 Hz, 2H), 7.88 (s, 2H), 5.05, (m, 2H), 4.98 (s, 4H),
2.59 (m, 4H), 1.92 (m, 4H), 1.76 (m, 6H), 1.27–1.56 (m, 6H); MS (FAB): m/z
(relative intensity) 585 (M+H+, 100); HRMS calcd for C36H33O4N4 585.2502,
found 585.2508. Selected data for 1,7-1: 1H NMR (400 MHz, CDCl3) d 8.86 (d,
J = 8.4 Hz, 2H), 8.42 (d, J = 8.4 Hz, 2H), 8.13 (s, 2H), 5.04, (m, 2H), 4.94 (s, 4H),
2.61 (m, 4H), 1.93 (m, 4H), 1.74 (m, 6H), 1.36–1.54 (m, 6H); MS (FAB): m/z
(relative intensity) 585 (M+H+, 100); HRMS calcd for C36H33O4N4 585.2502,
found 585.2504.
_
18. (a) Dinçalp, H.; Kızılok, Sß.; Içli, S. Dyes Pigm. 2010, 86, 32; (b) Ren, H.; Li, J.;
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29. General procedure for nitration: Compound
5 (1.8 mmol), cerium (IV)
ammonium nitrate (CAN) (4.8 g, 8.8 mmol), nitric acid (8.0 g, 131.1 mmol)
and dichloromethane (250 ml) were stirred at 25 °C under N2 for 48 h. The
mixture was neutralized with 10% KOH and extracted with CH2Cl2. After the
solvent was removed, the crude product was purified by silica gel column
chromatography with eluent CH2Cl2 to afford a mixture of 1,7- and 1,6-
dinitroperylene bisimides, and 1H NMR (500 MHz) analysis revealed a 3:1
ratio. Separation of the 1,6 and 1,7 isomers was performed on a preparative
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