1,6-Diaminoperylene bisimide with a highly twisted perylene core

Article abstract of DOI:10.1007/s12039-017-1221-6

1,6-Diaminoperylene bisimide (1) was synthesized and characterized by single-crystal X-ray diffraction. To the best of our knowledge, this is the first time that the structure of 1,6-disubstituted perylene bisimide has been reported. The crystal belongs to triclinic, space group P-1, with a = 10.3966(10), b = 15.3398(16), c = 16.8495(17) ?, α = 79.490(4)^°, β = 87.055(3)^°, γ = 79.423(3)^°, and Z = 2. Compound 1 possesses two intramolecular C–H ?N hydrogen bonds, which generate two S(6) ring motifs. The central perylene core of 1 is twisted with dihedral angles of 19.48(2) ^° and 19.50(2) ^°; this twist configuration induces the axial chirality in this family of perylene bisimide chromophores. Density functional theory (DFT) calculations also show that the core twist angles of 1,6-diaminoperylene bisimide are larger than those of 1,7-diaminoperylene bisimide, which may account for the fact that the 1,7-regioisomer has a more extended effective conjugation length than the 1,6-regioisomer. [Figure not available: see fulltext.]

Full text of DOI:10.1007/s12039-017-1221-6

c
J. Chem. Sci. ꢀ Indian Academy of Sciences.
DOI 10.1007/s12039-017-1221-6
RAPID COMMUNICATION
1,6-Diaminoperylene bisimide with a highly twisted perylene core
CHE-WEI CHANG, FANG-YUN CHIEN, JIUN-WEI HU, HSING-YANG TSAI
and KEW-YU CHEN∗
Department of Chemical Engineering, Feng Chia University, 40724 Taichung, Taiwan, Republic of China
Email: kyuchen@fcu.edu.tw
MS received 27 July 2016; revised 22 September 2016; accepted 3 January 2017
Abstract. 1,6-Diaminoperylene bisimide (1) was synthesized and characterized by single-crystal X-ray
diffraction. To the best of our knowledge, this is the first time that the structure of 1,6-disubstituted pery-
lene bisimide has been reported. The crystal belongs to triclinic, space group P-1, with a = 10.3966(10),
b = 15.3398(16), c = 16.8495(17) Å, α = 79.490(4)◦, β = 87.055(3)◦, γ = 79.423(3)◦, and Z = 2. Com-
pound 1 possesses two intramolecular C–H· · · N hydrogen bonds, which generate two S(6) ring motifs. The
central perylene core of 1 is twisted with dihedral angles of 19.48(2)◦ and 19.50(2)◦; this twist configura-
tion induces the axial chirality in this family of perylene bisimide chromophores. Density functional theory
(DFT) calculations also show that the core twist angles of 1,6-diaminoperylene bisimide are larger than those
of 1,7-diaminoperylene bisimide, which may account for the fact that the 1,7-regioisomer has a more extended
effective conjugation length than the 1,6-regioisomer.
Keywords. Perylene bisimides; x-ray diffraction; axial chirality; density functional theory.
1. Introduction
theory (DFT) calculations of 1,6-diaminoperylene bisi-
mide (1). The results offer the potential to synthesize
1,6-disubstituted PBIs with extended molecular archi-
tectures and photophysical properties.
Perylene bisimides (PBIs) and their derivatives have
attracted an increasing interest due to their poten-
tial applications in molecular optoelectronic devices,
such as LCD color filters,1 light-emitting diodes,2
photovoltaic cells,3,4 light-harvesting arrays,5 photo-
chromic materials,6 and organic field-effect transis-
tors (OFETs).7 This family of organic chromophores
is advantageous due to their large electron mobility,
high photoluminescence quantum yields and molar
absorptivities, excellent thermal and optical stabilities,
reversible redox properties, self-assembly behaviors,
and ease of synthetic modification.8 30 To date, a useful
method for introducing substituents onto the PBIs core
is bromination or chlorination of perylene-3,4,9,10-
tetracarboxylic dianhydride. Nucleophilic substitutions
and metal-catalyzed cross-coupling reactions can then
be performed which yield a regioisomeric mixture of
1,6- and 1,7-disubstituted PBIs. However, only a few
reports of isolation and characterization of both 1,6- and
2. Experimental
2.1 Chemicals and instruments
The starting materials, such as 3,4,9,10-perylenetetracarbo-
xylic dianhydride, acetic acid, cyclohexylamine, cerium
(IV) ammonium nitrate (CAN), tin(II) chloride dihydrate
(SnCl2.2H2O), sodium hydride (NaH), 1-iodohexane (C6H13I),
tetrahydrofuran (THF), and N-methyl-2-pyrrolidinone (NMP)
were purchased from Merck, ACROS and Sigma–Aldrich.
Column chromatography was performed using silica gel
Merck Kieselgel si 60 (40–63 mesh).
1H and 13C NMR spectra were recorded in CDCl3 on
a Bruker 400 MHz. Mass spectra were recorded on a
VG70-250S mass spectrometer. The absorption and emis-
sion spectra were measured using a Jasco V-570 UV–Vis
1,7-disubstituted PBIs have been reported, and still very spectrophotometer and a Hitachi F-7000 fluorescence spec-
trophotometer, respectively. Cyclic voltammetry (CV) was
performed with a CH instruments at a potential scan rate
of 200 mV/s in a 0.1 M solution of tetrabutylammonium
hexafluorophosphate (TBAPF6) in dichloromethane. Plat-
inum and Ag/AgNO3 electrodes were used as counter and
reference electrodes, respectively. The single crystal X-ray
diffraction data were collected on a Bruker Smart 1000CCD
area-detector diffractometer.
little is known about the molecular structures and spec-
troscopic properties of 1,6-disubstituted PBIs.31 33 To
reveal the structure-property relationship of PBI mol-
ecules, we herein report the single-crystal X-ray diffrac-
tion structure and complementary density functional
∗For correspondence

Che-Wei Chang et al.
N2 for 30 min. 1-iodohexane (890 mg, 4.20 mmol) was then
2.2 Synthesis and characterization
added and the resulting mixture was stirred for 6 h. The
resulting mixture was diluted with 75 mL of water and
2.2a Synthesis of 5 and 6: Compound 7 (1.0 g, 1.8 mmol),
CAN (4.8 g, 8.8 mmol), nitric acid (8.0 g, 131.1 mmol) and extracted with CH2Cl2. The crude product was purified
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 chroma-
tography with eluent CH2Cl2 to afford a mixture of 1,6-
and 1,7-dinitroperylene bisimides, and 1H-NMR (400 MHz)
analysis revealed a 1:3 ratio. Separation of the 1,6 and
1,7 isomers was performed on a preparative HPLC sys-
tem equipped with a refractive index detector and fitted
with a macro-HPLC column (Si, 8 μm, 250 × 22 mm). The
eluent was 8:1 hexane/ethyl acetate flowing at 12 mL/min.
Two fractions were collected from the column; the first was
pure 1,6-isomer (Rf = 0.42, 242 mg, yield = 21%), and the
second was pure 1,7-isomer (Rf = 0.38, 682 mg, yield =
59%). Characterization data: 5: 1H NMR (400 MHz, CDCl3)
δ 8.78 (2H, s), 8.63 (2H, d, J = 8.0 Hz), 8.30 (2H, d, J =
8.0 Hz), 5.01 (2H, m), 2.52 (4H, m), 1.90 (4H, m), 1.74 (6H,
m), 1.46 (4H, m), 1.36 (2H, m); MS (FAB): m/z (relative
intensity) 645 [M+H+, 100]; HRMS calcd. for C36H29O8N4
by silica gel column chromatography with eluent ethyl
acetate/n-hexane (1/2) to afford 1 (2) in 85% (82%) yield.
1
Characterization data for 1: H NMR (400 MHz, CDCl3) δ
9.40 (d, J = 8.0 Hz, 2H), 8.55 (d, J = 8.0 Hz, 2H), 8.32 (s,
2H), 5.06, (m, 2H), 3.35 (m, 4H), 3.01 (m, 4H), 2.57 (m, 4H),
1.90 (m, 4H), 1.15–1.77 (m, 44H), 0.78 (t, J = 6.4 Hz, 12H);
13C NMR (100 MHz, CDCl3) δ 164.5, 164.3, 151.0, 135.8,
131.9, 130.9, 128.9, 128.0, 123.7, 123.2, 123.1, 123.0, 120.3,
54.0, 53.6, 52.8, 31.5, 29.2, 29.1, 27.3, 26.9, 26.6, 25.5, 22.5,
13.9; MS (FAB): m/z (relative intensity) 921 (M+H+, 100);
HRMS calcd. for C60H81O4N4 921.6256, found 921.6247.
Purple parallelepiped-shaped crystals suitable for the crystal-
lographic studies reported here were isolated over a period
of six weeks by slow evaporation from a dichloromethane
solution. Selected data for 2: 1H NMR (400 MHz, CDCl3) δ
9.21 (d, J = 8.0 Hz, 2H), 8.45 (s, 2H), 8.38 (d, J = 8.0 Hz,
2H), 5.03, (m, 2H), 3.45 (m, 4H), 3.15 (m, 4H), 2.57 (m,
4H), 1.87 (m, 4H), 1.15–1.75 (m, 44H), 0.82 (t, J = 6.4 Hz,
12H); 13C NMR (100 MHz, CDCl3) δ 164.5, 164.2, 148.5,
135.4, 130.3, 128.2, 125.3, 124.3, 122.9, 122.7, 122.6, 121.1,
53.8, 52.5, 31.4, 29.1, 27.5, 26.9, 26.6, 25.5, 22.5, 13.9; MS
(FAB): m/z (relative intensity) 921 (M+H+, 100); HRMS
calcd. for C60H81O4N4 921.6256, found 921.6250.
1
645.1985, found 645.1983. Selected data for 6: H NMR
(400 MHz, CDCl3) δ 8.78 (2H, s), 8.68 (2H, d, J = 8.4
Hz), 8.28 (2H, d, J = 8.4 Hz), 5.01 (2H, m), 2.51 (4H, m),
1.92 (4H, m), 1.74 (6H, m), 1.46 (4H, m), 1.36 (2H, m); MS
(FAB): m/z (relative intensity) 645 [M+H+, 100]; HRMS
calcd. for C36H29O8N4 645.1985, found 645.1977.
2.2d Crystal structural determination: A single crystal of
1 with dimensions of 0.35 mm × 0.33 mm × 0.08 mm was
selected. The lattice constants and diffraction intensities were
measured with a Bruker Smart 1000CCD area detector radi-
ation (λ = 0.71073 Å) at 156(2) K. An ω-2θ scan mode was
2.2b Synthesis of 3 and 4: Tin(II) chloride dihydrate
(1.0 g, 4.8 mmol), 1,6- or 1,7-dinitroperylene diimides (0.5 g,
0.8 mmol) were suspended in THF (50 mL), and stirred at used for data collection in the range of 3.02 ≤ θ ≤ 26.45◦.
25◦C under N2 for 20 min. The solvent was refluxed 80◦C
with stirring for 6 h. THF was removed at the rotary evap-
orator, and the residue was dissolved in ethyl acetate and
washed with 10% sodium hydroxide solution and brine. The
organic layer was dried over anhydrous MgSO4 and the fil-
trate 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 3 (4) in
A total of 77973 reflections were collected and 10645 were
independent (Rint = 0.0595), of which 6504 were considered
to be observed with I > 2σ(I) and used in the succeeding
refinement. The structure was solved by direct methods
with SHELXS-9734 and refined on F2 by full-matrix least-
squares procedure with Bruker SHELXL-97 packing.35 All
non-hydrogen atoms were refined with anisotropic thermal
parameters. The hydrogen atoms refined with riding model
position parameters isotropically were located from dif-
ference Fourier map and added theoretically. At the final
cycle of refinement, R = 0.1001 and wR = 0.2669 (w =
1
80% (82%) yield. Characterization data: 3: H NMR (400
MHz, CDCl3) δ 8.77 (2H, d, J = 8.0 Hz), 8.51 (2H, d,
J = 8.0 Hz), 7.85 (2H, s), 5.05 (2H, m), 4.98 (4H, s), 2.59
(4H, m), 1.92 (4H, m), 1.76 (6H, m), 1.27–1.56 (6H, m);
MS (FAB): m/z (relative intensity) 585 [M+H+, 100];
HRMS calcd. for C36H33O4N4 585.2502, found 585.
2508. Selected data for 4: 1H NMR (400 MHz, CDCl3)
δ 8.90 (2H, d, J = 8.0 Hz), 8.25 (2H, d, J = 8.0 Hz),
8.14 (2H, s), 5.04, (2H, m), 4.94 (4H, s), 2.61 (4H, m),
1.93 (4H, m), 1.74 (6H, m), 1.36–1.54 (6H, m); MS (FAB):
m/z (relative intensity) 585 (M+H+, 100); HRMS calcd. for
C36H33O4N4 585.2502, found 585.2504.
1/[σ2(Fo2) + (0.1983P)2 + 2.9730P], where P = (Fo2
+
2Fc2)/3). S = 1.078, (ꢀ/σ)max = 0.001, (ꢀ/ρ)max = 0.726
and (ꢀ/ρ)min = −1.159 e/Å3. Crystallographic data for the
structural reported in this article have been deposited with
the Cambridge Crystallographic Data Center as supplemen-
tary publication number CCDC 1486032. Copies of these
information can be obtained free of charge from the Direc-
tor, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax:
+44 1223 336 033; e-mail: deposit@ccdc.cam.ac.uk).
2.3 Computational methods
2.2c Synthesis of 1 and 2: A mixture of solution of 3
or 4 (410 mg, 0.70 mmol), sodium hydride (97%, 200 mg, The Gaussian 03 program was used to perform the ab
8.00 mmol) and dry THF (25 mL) was stirred at 0◦C under initio calculation on the molecular structure.36 Geometry

1,6-Diaminoperylene bisimide
optimizations for 1,6-diaminoperylene bisimide (1) and 1,7-
separated by high performance liquid chromatogra-
phy (HPLC). Next, the reduction of 1,6-dinitroperylene
bisimide (5) by tin(II) chloride dihydrate (SnCl2·2H2O)
gave 1,6-diaminoperylene bisimide (3). Finally, 1,6-
dialkylamino-substituted perylene bisimide (1) was
synthesized by the alkylation of 3 with 1-iodohexane.
To confirm its structure, a single crystal of 1 was
obtained from a dichloromethane solution, and the mol-
ecular structure was determined by X-ray diffraction
analysis. Additionally, its X-ray structure is compared
with that of other PBI derivatives.27,29
Figure 1 shows the ORTEP (Oak Ridge Thermal
Ellipsoid Plot) diagram of 1 and the numbering of the
atoms. Compound 1 crystallizes in the triclinic space
group P -1, with a = 10.3966(10), b = 15.3398(16),
diaminoperylene bisimide (2) were carried out with the
6-31G* basis set to the B3LYP functional. Vibrational frequen-
cies were also performed to check whether the optimized
geometrical structures for both compounds were at energy
minima, transition states, or higher order saddle points. After
obtaining the converged geometries, the TD-B3LYP/6-31G*
was used to calculate the vertical excitation energies.
3. Results and Discussion
Scheme 1 shows the chemical structure and the syn-
thetic route of 1. In brief, the synthesis of 1 started from
a dinitration of perylene bisimide (7), giving 1,6- and
1,7-dinitroperylene bisimides (5 and 6).26,31 The regioi-
someric 1,6- and 1,7-dinitroperylene bisimides can be
Scheme 1. The synthetic routes for 1 and 2.

Che-Wei Chang et al.
Figure 1. Molecular structure of 1 (left) and viewed along the N–N axis showing the twisted perylene backbone (right, all
hydrogen atoms are omitted for clarity). Displacement ellipsoids are drawn at the 50% probability level.
Figure 2. (a) Crystal structure of 1 in the unit cell. (b) The black-colored
molecule is the M enantiomer and the red-colored one is the P enantiomer. For
clarity, only the PBI scaffold and the alkyl amino groups are shown.
c = 16.8495(17) Å, α = 79.490(4)◦, β = 87.055(3)◦,
γ = 79.423(3)◦, and Z = 2. The central perylene core
of 1 is twisted with dihedral angles of 19.48(2)◦ and
19.50(2)◦ associated with bay area carbon atoms C11–
C12–C13–C14 and C5–C6–C19–C20, respectively,
these values being larger than those of unsubstituted
and mono-substituted PBIs.30 This twist configura-
tion also induces the axial chirality in this family of
PBI chromophores. As shown in Figure 2, there are
two molecules with opposite chirality in the unit cell.
Nevertheless, the enantiomers are only observed in the
crystalline state due to the low barrier of rotation in
solution. Furthermore, all C–C bond lengths of the
perylene backbone range between 1.363 and 1.480 Å,
which indicates the presence of π-conjugation for all
C–C bonds. The longest bonds in the perylene moiety
are the C6–C19 and C12–C13 bonds that connect the
two naphthalene rings at a distance of ∼1.47 Å. The
bond length is slightly different to the lengths observed
for other PBIs.27,29,30 The results show that the degree
of conjugation of the perylene scaffold is similar but
different in unsubstituted and core-substituted PBIs.
Compound 1 possesses two intramolecular C–H· · · N
hydrogen bonds (Table 1), which generate two S(6) ring
motifs (red dashed lines in Figure 3). In good agree-
1
ment with this observation, the H NMR spectrum (in
CDCl3) revealed a significantly downfield signal at δ
9.38 ppm (H14A and H20A), giving a clear indica-
tion of the six-membered ring intramolecular hydrogen
bonds formation. The molecule is further stabilized by
six different intramolecular C–H· · · O hydrogen bonds
(green dashed lines in Figure 3 and Table 1). In addi-
tion, intermolecular C–H· · · π interactions (2.82 Å of
H(60A)· · · Cg1 distance and 115◦ of C(60)–H(60A)–
Cg1, symmetry code: –X, 1–Y, 2–Z) is also observed
in the crystal structure (blue dashed lines in Figure 3),
which links a pair of molecules into a cyclic centrosym-
metric dimer. Careful examination of the crystal struc-
ture also shows that there is no substantial π–π stacking
between the perylene plane and its adjacent one. As a
result, we can ascertain that the bulky n-hexyl groups
not only largely increase the solubility of 1 compared
with 3, but also reduce intermolecular contact and
aggregation.

1,6-Diaminoperylene bisimide
Table 1. Hydrogen-bond geometry (Å, ◦).
D–H· · · A
d(D–H)
d(H· · · A)
d(D· · · A)
∠DHA
C(14)–H(14A)· · · N(3)
C(20)–H(20A)· · · N(2)
C(25)–H(25A)· · · O(1)
C(26)–H(26B)· · · O(2)
C(30)–H(30B)· · · O(2)
C(55)–H(55A)· · · O(4)
C(56)–H(56B)· · · O(3)
C(60)–H(60A)· · · O(3)
0.95
0.95
1.00
0.99
0.99
1.00
0.99
0.99
2.37
2.35
2.11
2.51
2.56
2.22
2.38
2.58
2.916(4)
2.907(4)
2.661(16)
3.067(7)
3.112(18)
2.717(5)
2.955(5)
3.116(5)
116.0(3)
116.7(6)
112.6(7)
115.0(3)
115.1(4)
109.3(4)
116.4(6)
113.9(7)
Figure 4. Normalized absorption (solid lines) and emis-
sion (dashed lines) spectra of 1 (1,6-isomer) and 2 (1,7-
isomer) in dichloromethane.
Figure 3. (a) Crystal structure of 1. Red and Green dashed
lines denote intramolecular C–H· · · N and C–H· · · O hydro-
gen bonds, respectively. (b) A packing view of 1. Blue dashed
lines denote intermolecular C–H· · · π interactions. Cg1 (red
circles) is the centroid of the C3–C8 ring. Hexyl groups are
omitted for clarity.
effective conjugation length than 1. As for the steady-
state emission, both compounds emit in the near-infra-
red region (>700 nm). As a result, the 1,6-regioisomer
may be of particular interest for organic photovoltaic
and near-infrared fluorescent dye applications.
To gain more insight into the molecular structures
of 1,6-diaminoperylene bisimide (1) and 1,7-diamino-
perylene bisimide (2), quantum mechanical calcula-
tions were performed using density functional theory
(DFT) at the B3LYP/6-31G* level. DFT calculations
show that the ground-state geometries of the perylene
core have different core twist angles (Figure 5), i.e.,
approximate dihedral angles between the two naph-
thalene subunits attached to the central benzene ring;
these are ∼19.0◦ and ∼19.1◦ for 1 (1,6-) and ∼17.6◦
and ∼17.7◦ for 2 (1,7-). The core twist angles of 1,6-
disubstituted PBI are slightly larger than those of 1,7-
disubstituted PBI. The results may account for the fact
that the 1,7-regioisomer has a more extended effective
conjugation length than the 1,6-regioisomer.32,33
Figure 4 shows the steady state absorption and emis-
sion spectra of 1,6-diaminoperylene bisimide (1) and
1,7-diaminoperylene bisimide (2) in dichloromethane.
The absorption spectra of both regioisomers are domi-
nated by very broad absorption bands that cover a large
part of the visible spectrum (300–800 nm). These broad
bands are typical for perylene bisimide derivatives N-
substituted at the bay-core positions, due to charge
transfer absorption.16 The 1,6- and 1,7-regioisomers
show significant differences in their optical characteris-
tics. In addition to the longest wavelength absorption
band at around 657 nm, 1 exhibits another shoulder band
at ca. 595 nm, and consequently, cover a large part of
the visible region relative to that of 1,7-diaminopery-
lene bisimide (2). Interestingly, the longest wavelength
absorption band (702 nm) of 2 (1,7-) is 45 nm red-shif-
ted relative to that of 1 (1,6-), which can be explained by
Figure 6 shows the highest occupied molecular
orbitals (HOMOs) and the lowest unoccupied molecu-
the fact that the 1,7-regioisomer has a more extended lar orbitals (LUMOs) of 1 and 2. The HOMO of both

Che-Wei Chang et al.
Figure 5. DFT (B3LYP/6-31G*)geometry-optimized structures of 1 (left) and
2 (right) shown with view along the long perylene axis. For computational
purposes, methyl groups replace the cyclohexyl and hexyl groups.
Figure 7. The cyclic voltammograms of 1 and 2 mea-
sured in dichloromethane solution (versus SCE) with fer-
rocenium/ferrocene as an internal standard, at 200 mV/s.
shifted to more positive values by 0.21 V. The results
clearly show that the removal of one electron from 1
(1,6-) is more difficult in comparison to 2 (1,7-); these
findings are in good agreement with previous reports.31
Figure 6. Calculated frontier orbitals for 1 and 2. The
upper structures show the LUMOs and the lower ones show
the HOMOs. Methyl groups replace the cyclohexyl and hexyl
groups for clarity.
4. Conclusions
1,6−diaminoperylene bisimide (1) was synthesized and
characterized by single crystal X-ray diffraction. Com-
compounds is delocalized mainly on the amino group pound 1 crystallizes in the triclinic space group P-1
and the perylene core, while the LUMO is extended and possesses two intramolecular C–H· · · N hydrogen
from the central perylene core to the bisimide groups. bonds with two S(6) graph-set motifs. The core twist
Furthermore, the absorption spectra of 1 and 2 were cal- angles of 1 are much larger than those of unsubsti-
culated by time-dependent DFT (TD-DFT) calculations tuted and mono-substituted PBIs. DFT calculations also
(Franck–Condon principle). The calculated excitation showed that the core twist angles of 1,6-disubstituted
wavelengths for 1 and 2 are 624 (oscillator strength: PBI are slightly larger than those of 1,7-disubstituted
f = 0.3530) and 643 (f = 0.3758) nm, respectively, PBI, which may account for the fact that the 1,7-
which are in good agreement with the experimental regioisomer has a smaller band gap than the 1,6-
results.
regioisomer. This twist configuration induces the axial
The cyclic voltammograms of 1,6- and 1,7-diamino- chirality in this family of PBI chromophores; the two
perylene bisimides (1 and 2) are shown in Figure 7. enantiomers are only observed in the crystalline state
Both compounds exhibit two irreversible one-electron due to the low barrier of rotation in solution. More-
oxidations and two quasi-reversible one-electron reduc- over, the crystal structure is stabilized by intermolecular
tions in dichloromethane. The one-electron oxidation of C–H· · · π hydrogen bonds rather than π−π interac-
2 occurs at 0.62 V, whereas for 1, the first oxidation is tions, which indicates that the bulky n-hexyl groups not

1,6-Diaminoperylene bisimide
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Supplementary Information (SI)
Supplementary Information (1H and 13C NMR spectra) is
available at www.ias.ac.in/chemsci.
Acknowledgements
The project was supported by the Ministry of Science and
Technology (MOST 105-2113-M-035-001).
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