Di(alkoxy)- and di(alkylthio)-substituted perylene-3,4;9,10-tetracarboxy diimides with tunable electrochemical and photophysical properties

Article abstract of DOI:10.1021/jo062150j

Nucleophilic substitution of N,N′-dicyclohexyl-1,7-dibromoperylene-3, 4:9,10-tetracarboxydiimide (PTCDI) with an excess of corresponding alkanol in the presence of sodium hydride or anhydrous potassium carbonate at 85-100 °C provided both di(alkoxy)- and

Full text of DOI:10.1021/jo062150j

Di(alkoxy)- and Di(alkylthio)-Substituted
Perylene-3,4;9,10-tetracarboxy Diimides with Tunable
Electrochemical and Photophysical Properties
Chuntao Zhao, Yuexing Zhang, Renjie Li, Xiyou Li,* and Jianzhuang Jiang*
Department of Chemistry, Shandong UniVersity, Jinan 250100, China
xiyouli@sdu.edu.cn; jzjiang@sdu.edu.cn
ReceiVed October 17, 2006
Nucleophilic substitution of N,N′-dicyclohexyl-1,7-dibromoperylene-3,4:9,10-tetracarboxydiimide (PTCDI)
with an excess of corresponding alkanol in the presence of sodium hydride or anhydrous potassium
carbonate at 85-100 °C provided both di(alkoxy)- and mono(alkoxy)-substituted PTCDI compounds,
namely, N,N′-dicyclohexyl-1,7-di(alkoxy)perylene-3,4:9,10-tetracarboxydiimide (3) and N,N′-dicyclohexyl-
1-bromo-7-alkoxyperylene-3,4:9,10-tetracarboxydiimide (2). Starting from mono(alkoxy)-substituted
PTCDI, nucleophilic substitution with thiol, thiophenol, or alkylamine led to the formation of
unsymmetrical 1,7-di(substituted) PTCDI compounds (7-10). For the purpose of comparative studies,
symmetrical di(substituted) N,N′-dicyclohexyl-1,7-di(alkylthio)perylene-3,4:9,10-tetracarboxydiimide (4),
N,N′-dicyclohexyl-1,7-di(thiophenyl)perylene-3,4:9,10-tetracarboxydiimide (5), and N,N′-dicyclohexyl-
1,7-di(alkylamine)perylene-3,4:9,10-tetracarboxydiimide (6) have also been prepared by a similar
nucleophilic substitution. These newly prepared PTCDI compounds have been characterized by a wide
range of spectroscopic methods in addition to elemental analysis. Electronic absorption and fluorescence
studies revealed that the absorption and emission bands as well as the fluorescence quantum yield can be
tuned continuously over a large range by incorporating substituents with different electron-donating abilities.
Introduction
crystal properties were recently demonstrated by PTCDI com-
pounds as well as nano- and mesoscopic supramolecular
structure.28-33 These dyes have generated great interest because
of their outstanding photochemical and thermal stability, ease
of synthetic modification, and desirable optical and redox
characteristics.
Perylene-3,4;9,10-tetracarboxydiimide (PTCDI) derivatives
have attracted increasing attention in the past decade due to
their potential applications in molecular electronics, such as field
effect transistors,1-8 solar cells,9-14 light-harvesting arrays,15-19
and light emitting diodes.20-24 These functional dyes were also
used in electrophotography25 and lasers.26,27 Furthermore, liquid
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10.1021/jo062150j CCC: $37.00 © 2007 American Chemical Society
Published on Web 03/07/2007
2402
J. Org. Chem. 2007, 72, 2402-2410

Di(alkoxy)- and Di(alkylthio)-Substituted PTCDI
Driven by their use in many different applications,34 the
structure of PTCDIs has been modified by introducing side
groups either to the imide nitrogen atoms or at the bay positions
(i.e., 1, 6, 7, 12 positions, Scheme 1). Incorporation of
substituents to the imide nitrogen atoms has been found to
increase the solubility of corresponding PTCDI derivatives in
organic solvents and affect the packing model of PTCDI
molecules in solid film.35-37 However, substitution at the imide
does not significantly affect the electronic structure and proper-
ties of PTCDI compounds because the nodes in both the HOMO
and LUMO of PTCDI along the long axis of the molecule limit
the electronic interactions between PTCDI and corresponding
substituents.2 In contrast, introduction of substituents at the bay
positions of PTCDI was demonstrated to significantly alter the
electronic properties, including electronic absorption spectra,
fluorescence spectra, and redox potentials.38-40 The substituents
that have previously been incorporated onto the bay positions
of PTCDIs are limited to phenoxy groups,41-51 aryls,38,43 cyclic
secondary amines,52-60 cyano groups,1 and halogens.61 To the
best of our knowledge, there appears to be no report on PTCDI
compounds with alkoxy and/or alkylthio substituents at their
bay positions.
In the present work, we describe the synthesis and photo-
physical properties of a series of novel substituted PTCDIs with
long alkoxy and/or alkylthio groups at the bay positions of the
PTCDI ring. As opposed to bulky phenoxy or cyclic secondary
amines, the long linear alkoxy and/or alkylthio groups cause
less of a perturbation to the planar conformation of PTCDI core
due to their smaller steric hindrance. This, in addition to the
hydrophobic interaction between long alkyl chains62-64 and
strong electron-donating nature of long alkoxy groups, induces
novel photophysical properties to PTCDIs.
Results and Discussion
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J. Org. Chem, Vol. 72, No. 7, 2007 2403

Zhao et al.
SCHEME 1. Synthesis of Compounds 3-10
PTCDI derivatives prepared by this methodology, probably due
to the weaker nucleophilicity of alkanols compared to that of
phenols. Trials of the reaction between halogenated PTCDIs,
for example, 1, and alkanol in polar organic solvents such as
DMF, NMP, and DMSO, which was used to prepare the
phenoxy-substituted PTCDIs, failed to provide the target long
alkoxy-substituted PTCDI compounds. Both the target mono-
and di(alkoxy)-substituted PTCDI compounds were, however,
obtained from the reaction between halogenated PTCDIs and
excess alkanol with sodium hydride or anhydrous potassium
carbonate as a promoter at 85-100 °C (Scheme 1). Reaction
temperature in this range proved to be crucial for the good
reaction yields, as a lower or higher reaction temperature led
to lower production yield of the corresponding long alkoxy-
substituted PTCDI compounds. It is worth pointing out that the
yield of disubstituted product 3 is always lower than that of
monosubstituted 2, no matter what kind of reaction conditions
were adopted. It is also noteworthy that we carried out a two-
phase reaction procedure with toluene or xylene and water as
solvents, potassium hydroxide or anhydrous potassium carbonate
as the base, and cetyltrimethylammonium bromide (CTAB) or
18-crown-6 as phase transfer catalyst, which, however, led to
the isolation of alkoxy-substituted PTCDI compounds in very
low yield.
As expected, the mono(alkoxy)-substituted 2 with one
remaining halogen atom in the PTCDI ring can react further
with a phenol or secondary cyclic amine, such as 4-tert-
butylphenol and morpholine, respectively, under reported reac-
tion conditions to form unsymmetrical 1-(alkoxy)-7-(phenoxy)-
or 1-(alkoxy)-7-(morpholinyl)-substituted PTCDI compounds,
9 and 10, with good reaction yield. These appear to represent
the first example of PTCDI compounds with two different
electron-donating groups at bay positions of the PTCDI ring.
Alkylthio-substituted PTCDI compounds can also be provided
with the newly developed reaction route starting from haloge-
nated PTCDI compound 1 and excess of alkylthiols. Due to
2404 J. Org. Chem., Vol. 72, No. 7, 2007

Di(alkoxy)- and Di(alkylthio)-Substituted PTCDI
TABLE 1. Photophysical Properties of Molecules 3-12
λabs
(nm)
λem
(nm)
Φf
(%)
τ
(ns)
compound
ꢀ (mol-1‚L‚cm-1
)
3
4
5
6
7
8
9
10
11
12
570
574
556
703
558
568
606
640
546
526
5.41 × 104
3.16 × 104
3.51 × 104
3.17 × 104
5.14 × 104
4.12 × 104
3.49 × 104
3.26 × 104
4.13 × 104
597
655
651
761
588
640
697
722
578
534
72.4
15.5
18.6
0.8
82.7
39.0
6.7
1.0
96.2
100
5.4
8.5
7.8
1.4
5.0
7.8
3.4
0.8
4.5
3.8
the stronger nucleophilicity of alkylthio groups than that of
alkoxy groups, reaction between 1 and alkylthiols occurs much
more easily and gives di(alkylthio)-substituted PTCDI com-
pound 4 instead of the mono(alkylthio)-substituted PTCDI
compound as the main product. As also displayed in
Scheme 1, this reaction happened in a phase transfer system
with xylene as organic solvent, potassium carbonate as the base,
CTAB as a PT catalyst, and even without utilization of any
aqueous phase. With the mono(alkoxy)-substituted 2 as starting
material, similar reaction with alkylthiol led to the isolation of
unsymmetrical substituted PTCDI compound 8 in high yield.
FIGURE 1. UV-vis absorption spectra of compounds 3-12 in
chloroform.
For the substitution with thiophenol, reaction with halogenated
PTCDI 1 was found to take place under more milder reaction
conditions, without utilization of any phase transfer reagent and
providing di(phenylthio)-substituted PTCDI compound 5 in high
yield, because of the extremely increased nucleophilicity of the
thiophenyl group.
UV-Vis Absorption. The electronic absorption spectra of
compounds 3-10 were recorded in CHCl3, and the data are
summarized in Table 1. Figure 1 displays the UV-vis absorp-
tion spectra for compounds 3-10 together with that of two
model compounds, namely, N,N′-dicyclohexyl-1,7-bi(4-tert-
butyl)phenoxy)perylene-3,4:9,10-tetracarboxy diimide (11) and
N,N′-dicyclohexyl)perylene-3,4:9,10-tetracarboxydiimide (12).
All of these compounds show intense absorption in the
UV-vis region with a large extinction coefficient. Compared
with the parent PTCDI 12, the main absorption bands of 3-11
become broadened and gradually shift to the red side de-
pending on the identity of substitution groups on the PTCDI
ring.
The maximum absorption peak of parent PTCDI 12 is at 525
nm, while that of compound 11 is shifted to 546 nm due to the
introduction of two electron-donating phenoxy groups onto the
PTCDI ring.66,67 Incorporation of two alkoxy groups as opposed
to phenoxy groups in compound 3 further red shifts the main
absorption band to 570 nm. Just as expected, the asymmetrical
disubstituted PTCDI compound 7 with one phenoxy group and
one alkoxy group at the bay positions of the PTCDI ring shows
a red-shifted absorption band at 558 nm, just between those of
compound 11 with two phenoxy groups and compound 3 with
two alkoxy groups.
The reaction of halogenated PTCDIs with alkylamines has
been the focus of several literature reports. As mentioned above,
secondary cyclic amines, such as piperidine, morpholine, and
pyrrolidine, have been introduced onto the PTCDI rings to form
di(amino)-PTCDI compounds by the reaction of halogenated
PTCDIs with an excess of corresponding cyclic secondary
amines according to Wasielewski and co-workers.52 However,
to the best of our knowledge, introduction of two primary
alkylamino groups onto the PTCDI ring seems limited to an
octylamino group.65 Reactions of halogenated PTCDI compound
1 with a primary alkylamine, such as cyclohexylamine, led to
the formation of corresponding di(cyclohexylamino)-PTCDI
compound 6 in low reaction yield in addition to the mono-
(cyclohexylamino)-PTCDI compound as the main product. In
line with previous findings,65 the debrominated product was
isolated as the side product of this reaction.
In addition, efforts to connect the secondary alkoxy or
secondary noncyclic alkylamino groups onto the PTCDI rings
have also been conducted. However, the reaction of cholesterol,
cyclohexanol, 2-ethylhexane-2-ol, or diethylamine with halo-
genated PTCDI compound 1 failed to give any nucleophilic
mono- or disubstituted product, indicating that the steric
hindrance might dominate this reaction process.
Similar to the introduction of alkoxy and phenoxy groups
onto the PTCDI ring, incorporation of two alkylthio and
thiophenyl groups, also with electron-donating properties, leads
to the red shift of the main absorption band to 574 and 556 nm
for compounds 4 and 5, respectively (Table 1).
As revealed in Table 1, the largest red shift in the main
absorption band was observed for the alkylamino-substituted
PTCDI compounds including 6, 9, and 10. This effect is
probably associated with increased electron-donating properties
Satisfactory elemental analysis results were obtained for all
the newly prepared PTCDI compounds 3-10. The compounds
were further characterized by MALDI-TOF and 1H NMR. The
asymmetrical substitution pattern of compounds 7-10 was
supported by the splitting signals of the aromatic PTCDI protons
1
in their H NMR spectra.
(66) Thalacker, C.; Miura, A.; De Feyter, S.; DeSchryver, F. C.;
Wu¨rthner, F. Org. Biomol. Chem. 2005, 3, 414-422.
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J. Org. Chem, Vol. 72, No. 7, 2007 2405

Zhao et al.
TABLE 2. Calculated HOMO and LUMO Energy of Compounds
1-10 by AM1
HOMO
(eV)
LUMO
(eV)
twisting
angle (°)
compound
3
4
5
6
7
8
9
10
11
12
-8.465
-8.472
-8.351
-7.947
-8.551
-8.527
-8.406
-8.112
-8.810
-8.826
-2.227
-2.482
-2.526
-2.050
-2.297
-2.402
-2.209
-2.122
-2.436
-2.454
9.0
21.5
21.7
27.8
18.0, 18.3a
18.2, 21.4a
18.6, 24.4a
18.4, 25.1a
18.5
0
a Two twisting angles for one molecule because of the different
substitutions at the 1,7 position.
of alkylamino groups. Introduction of one cyclohexylamino
group onto the PTCDI ring red shifts the main absorption band
of compound 10 to 640 nm, whereas introduction of the second
cyclohexylamino group shifts it further to 703 nm in compound
6. Nevertheless, comparison of the main absorption band
between the two mono(alkylamino)-substituted PTCDI com-
pounds, 640 nm for 10 with one primary alkylamino group on
the PTCDI ring, 606 nm for 9 with one secondary alkylamino
group, clearly indicates different tuning ability to the main
absorption band of PTCDI derivatives between the primary and
secondary alkylamino groups.
FIGURE 2. The normalized fluorescence spectra of compound 3, 4,
5, 6, 7, 8, 9, and 11 in chloroform with excitation at 410 nm.
to the red, following the same order observed for corresponding
main absorption bands, due to the incorporation of various kinds
of electron-donating substituents at the bay position(s) of the
PTCDI ring (Figure 2). Additionally, the alkylthio- and thiophe-
nyl-substituted PTCDI compounds 4, 5, and 8 were found to
display larger Stokes shift in comparison with that of alkoxy-
and phenoxy-substituted analogues 3 and 11, indicating larger
structure relaxation during the photoexcitation process.
Due to the very strong electron-withdrawing nature of the
PTCDI core, introducing electron-donating side groups onto the
bay positions of the PTCDI core leads to charge transfer
character in the excited state of the PTCDI molecules, which
in turn results in a significant decrease in the fluorescence
quantum yield (Table 1). This corresponds well with the result
found for other PTCDI compound systems.38,65
The fluorescence lifetimes measured by the phase modulation
method for all of these PTCDI compounds are summarized in
Table 1, which also shows dependence on the number and, in
particular, identity of substituents on the bay positions of the
PTCDI core. For example, the fluorescence lifetime recorded
for di(alkoxy)-substituted PTCDI 3, 5.4 ns, is longer than that
for di(phenoxy)-substituted PTCDI 11, 4.5 ns, because of the
more stable excited state of the former.69 However, the longest
fluorescence lifetime was actually observed for the alkylthio-
and thiophenyl-substituted PTCDI compounds 4, 5, and 8,
indicating the most stable excited state of these compounds. In
contrast, the alkylamino-substituted compounds of 6, 9, and 10
showed the shortest fluorescence lifetime among the PTCDI
derivatives of 3-12 due to the electron transfer between the
PTCDI core and alkylamino side groups. These experimental
results will be rationalized on the basis of AM1 calculations
and orbital analysis below.
On the basis of previous reports,2,38,46,57,68 the broadening and
loss of detailed vibronic structure for the absorption bands of
PTCDI compounds 4, 5, 6, 8, 9, and 10 were attributed to both
the participation of the side groups in the conjugation of the
PTCDI core and the twisting in molecular conformation of the
PTCDI ring because of the 1,7 disubstitution. According to our
calculation results using the AM1 method (Table 2), the bigger
twisting angle obtained for compound 4 in comparison with 3
is in line with the experimentally observed more significant
broadening in the main absorption bands of compound 4 than
that in 3. A similar degree of broadening was observed for the
main absorption bands of compounds 6, 9, and 10 to that of 4,
corresponding well with the similar twisting angle obtained by
calculations for all of these compounds. Furthermore, signifi-
cantly different broadening of the main absorption bands
observed for compounds 5 and 11 with similar twisting angle,
21.7 and 18.5° for 5 and 11, respectively, is attributed to
different participation extent in the conjugation of the PTCDI
core between the thiophenyl and phenyloxy side groups. This
argument is also supported by the orbital analysis described
below.
As summarized in Figure 1, successful tuning of the electronic
absorption spectra over a large range (400-800 nm) has been
realized by introducing different electron-donating substituents,
including alkoxy, alkythio, phenoxy, thiophenyl, and alkylamino
groups to the bay positions of the PTCDI ring.
Fluorescence. The fluorescence spectra of compounds 3-11
are recorded in chloroform with excitation at 410 nm. Fluores-
cence quantum yields (Φf) are calculated with parent compound
PTCDI 12 as the standard.38 Figure 2 displays the fluorescence
spectra of these compounds, and Table 1 summarizes the
experiment data.
Electrochemical Properties. The electrochemical behavior
of all the disubstituted PTCDI compounds was investigated by
cyclic voltammetry (CV) and differential pulse voltammetry
(DPV) in CH2Cl2. The half-wave redox potential values versus
SCE for all the disubstituted compounds (3-10) together with
two model compounds, 11 and 12, are summarized in Table 3.
Figure 3 shows the cyclic voltammograms and differential pulse
voltammograms of unsymmetrical disubstituted PTCDI 8 as a
In line with the red-shifted electronic absorption bands, the
emission band of all substituted PTCDI compounds also shifts
(69) Sinks, L. E.; Rybtchinski, B.; Iimura, M.; Jones, B. A.; Goshe, A.
J.; Zuo, X.; Tiede, D. M.; Li, X.; Wasielewski, M. R. Chem. Mater. 2005,
17, 6295-6303.
(68) Kohl, C.; Weil, T.; Qu, J.; Mu¨llen, K. Chem.sEur. J. 2004, 10,
5297-5310.
(70) Langhals, H.; Jona, W. Eur. J. Org. Chem. 1998, 847-851.
2406 J. Org. Chem., Vol. 72, No. 7, 2007

Di(alkoxy)- and Di(alkylthio)-Substituted PTCDI
TABLE 3. Half-Wave Redox Potentialsa (vs SCE) of 3-12 in
by the experimental results of compounds 4 and 5 organized in
Table 3. Incorporating two alkylthio groups at the bay positions
of PTCDI in compound 4 induces a great shift to the negatiVe
direction of the first oxidation potential and slight shift to the
negatiVe direction of the first reduction potential, relative to
parent PTCDI 12, again reflecting the same electron-donating
nature of the alkythio group. However, the relatively slight shift
for both the first oxidation and first reduction potential in
compound 4 induced by two alkylthio groups as opposed to
that in 3 by two alkoxy groups suggests relatively weaker
electron-donating properties of the alkylthio group than that of
the alkoxy group. As can be expected, the shift to the negatiVe
direction of both the first oxidation and first reduction potentials
of unsymmetrical PTCDI compound 8 locates the potentials
between those of the symmetrical disubstituted counterparts 3
and 4 (Table 3). Examination of electrochemical data in Table
3 also reveals that introducing two thiophenyl groups onto the
bay positions of the PTCDI ring leads to a significant shift to
the negatiVe direction of the first oxidation potential but a slight
shift to the positiVe direction of the first reduction potential,
therefore reducing the potential difference between these two
redox processes.
CH2Cl2
b
compound
Oxd2
Oxd1
Red1
Red2
Eo
1/2
3
4
5
6
7
8
9
10
11
12
1.79
1.79
1.45
0.84
1.59
1.83
1.24
1.39
1.31
1.37
1.45
0.72
1.38
1.33
1.03
0.91
1.44
1.62
-0.76
-0.62
-0.55
-0.82
-0.70
-0.68
-0.71
-0.78
-0.85
-0.58
-0.92
-0.83
-0.76
-1.01
-0.89
-0.87
-0.90
-0.96
-0.67
-0.81
2.07
1.99
2.00
1.54
2.08
2.01
1.74
1.69
2.29
2.20
a Values obtained by DPV in dry CH2Cl2 with 0.1 M TBAP as the
supporting electrolyte and Fc/Fc+ as internal standard. b Eo ) Oxd1
-
1/2
Red1.
At the end of this section, it is worth pointing out that the
stronger electron-donating property of the alkylamino groups
in comparison with that of either alkoxy, phenoxy, or alkylthio
substituents is clearly revealed by the larger shift to the negatiVe
direction of the first oxidation and first reduction potentials for
the mono- and di(alkylamino)-substituted PTCDI compounds
6, 9, and 10 than that for di(alkoxy)-, di(phenoxy)-, and di-
(alkylthio)-substituted analogues 3, 4, 7, and 8 (Table 3).
AM1 Calculation. To enhance our understanding of the effect
of substituents on the electronic spectra and electrochemistry
of PTCDI compounds, we carried out molecular orbital (MO)
calculations on compounds 3-12 at the AM1 level. The
calculated molecular orbital (HOMO and LUMO) energies are
summarized in Table 2. Most of the trends found by experi-
mental measurements in the potentials of the first oxidation and
first reduction processes and, in particular, the decrease in the
HOMO-LUMO gap, according to different types of the
substituents on the PTCDI ring, are reproduced by calculation.
FIGURE 3. CV (A) and DPV (B) plot of compound 8 in dichlo-
romethane containing 0.1 M TBAP.
representative of the series of compounds. Within the electro-
chemical window of CH2Cl2, all the disubstituted PTCDI
compounds undergo two quasi-reversible one-electron oxidations
and two quasi-reversible one-electron reductions as the separa-
tion of the reduction and oxidation peak potentials for each
process is 60-95 mV. All these processes are attributed to
successive removal from or addition of electron to the PTCDI
orbitals. The oxidations and reductions are labeled as Oxdn and
Redn, respectively.
The effect of substituent species and substitution number is
clearly reflected by the shift in the half-wave potentials of the
first oxidation and first reduction of compounds 3-10. As can
be seen in Table 3, substitution of two alkoxy groups at the
bay positions of compound 3 induces significant shift to the
negatiVe direction for both the first oxidation and first reduction,
relative to parent PTCDI 12, reflecting the electron-donating
nature of alkoxy groups attached onto the bay positions of the
PTCDI ring. Replacement of one alkoxy group in compound 3
with one phenoxy group in 7 results in shift to the positiVe
direction of the first oxidation as well as the first reduction
processes, suggesting the larger electron-donating ability of the
alkoxy group in comparison with that of phenoxy group.
According to the calculation results, incorporation of alkoxy
and phenoxy groups onto the bay positions of the PTCDI core
increases the energy level of both HOMO and LUMO and
slightly reduces the energy gap between the HOMO and LUMO
(Table 2). This not only corresponds well with the electrochemi-
cal measurement results but also is in line with the red shift of
the main absorption band observed in the UV-vis spectrum of
compounds 3, 7, and 11 in comparison with that of the parent
PTCDI 12.
Calculation on the molecular orbital energies for alkythio-
and thiophenyl-substituted compounds 4, 5, and 8 reveals that
incorporating two alkylthio or thiophenyl groups onto the bay
positions of the PTCDI ring induces a significant positive shift
in the energy level of the HOMO while the energy level of
LUMO remained almost unchanged, leading to a decrease in
the HOMO-LUMO gap, compared with those of parent PTCDI
compound 12. As clearly shown in Figure 4, the HOMO of
compound 4 locates on the sulfur atoms and the carbon atoms
which close to the sulfur on the PTCDI core, while the LUMO
is only PTCDI core centered. This dichotomy explains how
introduction of alkylthio groups onto the PTCDI ring signifi-
cantly affects the energy level of HOMO but has no effect on
The effect of alkylthio and thiophenyl groups at bay positions
of the PTCDI core on their electrochemistry is clearly revealed
J. Org. Chem, Vol. 72, No. 7, 2007 2407

Zhao et al.
FIGURE 4. Calculated molecular orbitals of 4 and 6: (A) HOMO of 4; (B) LUMO of 4; (C) HOMO of 6; (D) LUMO of 6.
that of LUMO. These results also agree well with the experi-
mental findings as described above.
compound 6 are centered on the PTCDI core, with the HOMO
extended to the amino side groups (Figure 4). The contribution
from the amino side groups to the HOMO results in partial
charge separation for the ground state and excited state and is
responsible for both the low fluorescence quantum yield and
the short fluorescence lifetime of compound 6. This is also true
for the analogues 9 and 10.38
With excitation of compound 4 from ground state to the first
excited state, electron transfer takes place from the HOMO (on
the alkylthio groups) to the LUMO (on the PTCDI core),
resulting in the charge transfer nature for the excited state of
this compound. This induces significant change on the distribu-
tion of electronic density over the whole molecule and thus a
large structure relaxation, which is then responsible for the
observation of the broadened absorption band in the UV-vis
spectrum and a big Stokes shift for compound 4 as well as
analogous 5 and 8. The decay of the excited state of this
compound (charge recombination) is also accompanied by the
redistribution of the electron density and a large structure
relaxation and therefore needs a large amount of activation
energy. As a consequence, the decay rate of the excited sate
for this compound is decreased and the fluorescence lifetime
prolonged.
Conclusion
A series of novel symmetrical and unsymmetrical disubsti-
tuted PTCDI compounds with alkoxy, alkylthio, and/or thiophe-
nyl groups at the bay positions of the PTCDI ring have been
prepared by nucleophilic substitution. Successful tuning of the
electronic absorption spectra and fluorescence spectra over a
large range has been realized by introducing a different number
of substituents with varying electron-donating ability onto the
bay positions of the PTCDI ring.
As tabulated in Table 2, more significant increase in the
energy level of both HOMO and LUMO and decrease in the
HOMO-LUMO gap have been revealed for the PTCDI
compounds 6, 9, and 10 with the introduction of mono- or di-
(alkylamino) substituents onto the PTCDI ring, according to
the calculations. These accurately produce the experimental
results that introduction of the alkylamino groups onto the bay
positions of the PTCDI ring induces the largest shift to the
negatiVe direction of the first oxidation and first reduction
potentials and the largest red shift in the main absorption band
for these compounds in comparison with those substituted by
alkoxy, alkylthio, phenyloxy, and thiophenyl groups. Calcula-
tions also indicate that both the HOMO and LUMO of
Experimental Section
(N,N′-Dicyclohexyl-1,7-dibromo)perylene-3,4:9,10-tetracarboxy-
diimide (1),65 11,47 and 1270 were prepared following the literature
methods. All other chemicals were purchased from commercial
source. Solvents were of analytical grades and were purified by
the standard method.
(N,N′-Dicyclohexyl-1,7-didodecyloxy)perylene-3,4;9,10-tetra-
carboxydiimide (3) and (N,N′-Dicyclohexyl-1-bromo-7-dodecyl)-
perylene-3,4;9,10-tetracarboxydiimide (2). A mixture of dode-
canol (15 mL) and sodium hydride (60 mg, 2.5 mmol) was stirred
at room temperature for 15 min. Then 1 (320 mg, 0.45 mmol) was
added to the reaction mixture. The mixture was heated to 90 °C
2408 J. Org. Chem., Vol. 72, No. 7, 2007

Di(alkoxy)- and Di(alkylthio)-Substituted PTCDI
and kept at this temperature for 24 h. Methanol (60 mL) was added
to the reaction mixture after it was cooled to room temperature.
The purple precipitate was isolated from the reaction mixture by
filtration and was washed with methanol thoroughly three times.
The crude product was chromatographed on silica gel with
chloroform as eluent. The first fraction contains 3 (72 mg, yield
2H), 7.83 (s, 2H), 5.81 (d, 2H), 5.04 (m, 2H), 3.45 (br, 2H), 2.58
(m, 4H), 2.05 (m, 4H), 1.92 (m, 4H), 1.56-1.26 (m, 24H); 13C
NMR (75 Hz, CDCl3) δ 163.7, 163.1, 144.0, 133.4, 129.7, 126.2,
122.3, 121.6, 120.2, 119.7, 115.9, 112.7, 53.5, 51.7, 32.6, 28.6,
26.1, 25.1, 25.0, 24.3; MALDI-TOF MS (m/z) 748.4, calcd for
C48H52N4O4 (m/z), 748.9. Anal. Calcd for C48H52N4O4(CHCl3)0.25
:
1
17%): mp >280 °C; H NMR (300 MHz, CDCl3) δ 9.14 (d, J )
C, 74.33; H, 6.68; N, 7.19. Found: C, 74.38; H, 6.98; N, 7.01.
8.4 Hz, 2H), 8.28 (d, J ) 8.4 Hz, 2H), 7.92 (s, 2H), 4.98 (m, 2H),
4.22 (m, 4H), 2.59 (m, 4H), 1.99 (m, 8H), 1.91 (m, 4H), 1.49-
1.25 (br, 44H), 0.89 (t, 6H); 13C NMR (75 Hz, CDCl3) δ 163.2,
162.8, 155.9, 132.5, 127.7, 127.6. 127.4, 122.6, 122.3, 120.8, 119.2,
115.6, 69.8, 69.7, 53.7, 53.5, 53.3, 31.4, 29.2, 29.1, 29.0, 28.9, 28.6,
26.2, 26.0, 25.1, 22.2, 13.6; MALDI-TOF MS (m/z) 923.7, calcd
for C60H78N2O6 (m/z), 923.3. Anal. Calcd for C60H78N2O6: C, 78.05;
H, 8.52; N, 3.03. Found: C, 77.67; H, 8.55; N, 2.98.
From the second red fraction, (N,N′-dicyclohexyl-1-bromo-7-
dodecyloxy)perylene-3,4;9,10-tetracarboxydiimide (2) was collected
(161 mg, yield 44%): 1H NMR (300 MHz, CDCl3) δ 9.22 (d, J )
7.84 Hz, 1H), 9.08 (d, J ) 7.79 Hz, 1H), 8.56 (s, 1H), 8.35 (d, J
) 7.84 Hz, 1H), 8.29 (d, J ) 7.79 Hz, 1H), 8.18 (s, 1H), 5.00 (m,
2H), 4.32 (m, 2H), 2.56 (m, 2H), 1.95 (m, 8H), 1.93 (m, 8H), 1.49-
1.25 (br, 22H), 0.87 (t, 3H); 13C NMR (75 Hz, CDCl3) δ 163.0,
163.0, 162.9, 162.3, 156.8, 137.2, 132.8, 312.6, 131.7, 130.3, 128.5,
128.3, 127.8, 127.5, 126.9, 126.6, 124.0, 122.9, 112.5, 122.0, 121.2,
119.1, 118.7, 117.1, 70.1, 53.7, 53.6, 31.4, 29.2, 29.1, 29.1, 28.8,
28.8, 28.7, 28.6, 26.1, 25.8, 25.0, 22.2, 13.6; MALDI-TOF MS
(m/z) 817.3, calcd for C48H53BrN2O5, m/z 817.9. Anal. Calcd for
C48H53BrN2O5: C, 70.49; H, 6.53; N, 3.43. Found: C, 70.63; H,
6.37; N, 3.31.
(N,N′-Dicyclohexyl-1-dodecyloxy-7-(4-tert-butylphenoxy))per-
ylene-3,4;9,10-tetracarboxydiimide (7). 2 (81 mg, 0.1 mmol) was
mixed with potassium carbonate anhydrous (60 mg), 4-tert-
butylphenol (25 mg, 0.16 mmol), and dried DMF (10 mL). The
mixture was heated to 70 °C under the protection of nitrogen and
was stirred at this temperature for about 2 h. The reaction mixture
was cooled to room temperature and acidified with HCl (15 mL, 2
M L-1). The red solid was separated by filtration and washed with
water and methanol. The crude material was purified via flash
column chromatography on silica gel using chloroform as eluent
to give 7 as red solid (57 mg, yield 64%): mp >232 °C; 1H NMR
(300 MHz, CDCl3) δ 9.28 (d, J ) 8.8 Hz, 1H), 9.18 (d, J ) 8.8
Hz, 1H), 8.40 (d, J ) 8.8 Hz, 1H), 8.29 (d, J ) 8.8 Hz, 1H), 8.07
(s, 1H), 8.02 (s, 1H), 7.45 (d, J ) 8.9 Hz, 2H), 7.01 (d, J ) 8.9
Hz, 2H), 5.01 (m, 2H), 4.49 (m, 2H), 2.55 (m, 4H), 2.08 (m, 2H),
1.92 (m, 4H), 1.77 (m, 4H), 1.55-1.27 (m, 32H), 0.88 (t, 3H); 13
C
NMR (75 Hz, CDCl3) δ 163.1, 163.0, 162.9, 162.6, 156.1, 154.3,
151.9, 147.5, 133.1, 131.9, 128.8, 128.2, 127.8, 127.7, 126.9, 123.2,
123.1, 122.4, 121.7, 121.2, 118.6, 116.4, 70.0, 53.6, 53.5, 53.3,
34.0, 31.4, 31.0, 29.2, 29.1, 29.0, 28.9, 28.6, 26.1, 25.9, 25.1, 22.2,
13.6; MALDI-TOF MS (m/z) 887.0, calcd for C58H66N2O6 (m/z),
887.2. Anal. Calcd for C58H66N2O6: C, 78.52; H, 7.50; N, 3.16.
Found: C, 78.32; H, 7.37; N, 3.14.
(N,N′-Dicyclohexyl-1,7-di(dodecylthio))perylene-3,4;9,10-tet-
racarboxydiimide (4). A mixture of 1 (80 mg, 0.11 mmol), xylene
(10 mL), potassium carbonate anhydrous (162 mg), water (2.0 mL),
CTAB (10 mg), and 1-dodecylthiol (60 mg, 0.3 mmol) was heated
to 85 °C under nitrogen. The reaction mixture was kept at this
temperature for about 2 h, and then the solvents were evaporated
under reduced pressure. The residue was column chromatographed
on silica gel with chloroform as eluent. The second red fraction
was collected. After recrystallization from chloroform and methanol,
(N,N′-Di(cyclohexyl)-1-dodecyloxy-7-dodecylthio)perylene-
3,4;9,10-tetracarboxydiimide (8). 2 (120 mg, 0.15 mmol) was
mixed with CTAB (6 mg, 0.01 mmol), potassium carbonate
anhydrous (0.16 g), o-xylene (8 mL), and dodecylthiol (40 mg,
0.2 mmol) and heated to 80 °C. The mixture was stirred at this
temperature for 5 h, and then the solvents were evaporated under
reduced pressure. The residue was purified by flash column
chromatography on silica gel with chloroform as eluent to get the
1
4 was collected as red solid (140 mg, yield 61%): mp 93 °C; H
1
product 8 as a red solid (110 mg, yield 80%): mp 168 °C; H
NMR (300 MHz, CDCl3) δ 8.70 (d, J ) 10.4 Hz, 2H), 8.66 (s,
2H), 8.58 (d, J ) 10.4 Hz, 2H), 5.00 (m, 2H), 3.15 (t, 4H), 2.57
(q, 4H), 1.95 (m, 4H), 1.80 (m, 4H), 1.55 (m, 4H), 1.50-1.21 (br,
44H), 0.86 (t, 6H); 13C NMR (75 Hz, CDCl3) δ 163.3, 163.2, 137.9,
131.8, 131.6, 130.1, 128.2, 128.2, 127.7, 124.8, 121.9, 121.4, 53.6,
35.4, 31.4, 29.2, 29.0, 29.0, 28.9, 28.8, 28.7, 28.6, 28.4, 27.9, 26.1,
25.0, 22.2, 13.6; MALDI-TOF MS (m/z) 955.3, calcd for
C60H78N2O4S2 (m/z), 955.4. Anal. Calcd for C60H78N2O4S2: C,
75.43; H, 8.23; N, 2.93. Found: C, 75.56; H, 8.31; N, 2.87.
(N,N′-Dicyclohexyl-1,7-di(thiophenyl))perylene-3,4;9,10-tet-
racarboxydiimide (5). Following the similar procedures of 4 except
using thiophenol instead of dodecylthiol, we got 5 as red solid (yield
94%): mp >280 °C; 1H NMR (300 MHz, CDCl3) δ 8.58 (d, 2H),
8.50 (d, 2H), 8.48 (s, 2H), 7.43 (m, 10H), 4.97 (t, 2H), 2.54 (q,
4H), 1.90 (d, 4H), 1.72 (d, 6H), 1.44-1.28 (br, 6H); 13C NMR (75
Hz, CDCl3) δ 163.1, 162.8, 137.9, 133.6, 132.7, 132.5, 131.7, 131.3,
129.9, 129.2, 128.5, 128.4, 127.5, 125.2, 122.2, 121.7, 53.5, 28.6,
26.1, 24.9; MALDI-TOF MS (m/z) 769.0, calcd for C48H38N2O4S2
(m/z), 770.0. Anal. Calcd for C48H38N2O4S2: C, 74.78; H, 4.97; N,
3.61. Found: C, 74.53; H, 4.82; N, 3.68.
NMR (300 MHz, CDCl3) δ 9.29 (m, 1H), 8.56 (m, 2H), 8.49 (s+d,
2H), 8.30 (s, 1H), 5.06 (m, 2H), 4.47 (m, 2H), 3.14 (m, 2H), 2.59
(m, 4H), 2.06(m, 2H), 1.96 (m, 4H), 1.82 (m, 4H), 1.63-1.20 (m,
46H), 0.87 (m, 6H); 13C NMR (75 Hz, CDCl3) δ 163.3, 163.3,
163.3, 163.3, 156.5, 137.1, 132.4, 130.3, 129.0, 128.8, 128.3, 127.5,
127.2, 125.0, 123.4, 122.5, 122.0, 121.2, 121.1, 119.7, 116.6, 70.0,
53.6, 53.5, 35.9, 31.4, 31.4, 29.2, 29.2, 29.1, 29.1, 29.0, 29.0, 28.9,
28.8, 28.7, 28.6, 26.1, 25.0, 22.2, 22.2, 13.6; MALDI-TOF MS
(m/z) 938.2, calcd for C60H78N2O5S (m/z), 939.4. Anal. Calcd for
C60H78N2O5S: C, 76.72; H, 8.37; N, 2.98. Found: C, 76.99; H,
8.53; N, 2.84.
(N,N′-Dicyclohexyl-1-dodecyloxy-7-morpholinyl)perylene-
3,4;9,10-tetracarboxydiimide (9). The mixture of 2 (128 mg, 0.16
mmol) and morpholine (12 mL) was heated to 85 °C and stirred at
this temperature for 24 h. Then the solvents were evaporated to
dryness under reduced pressure. The residue was purified by column
chromatography on silica gel with dichloromethane as eluent to
get product 9 as a deep green solid (121 mg, yield 93%): mp 154
°C; 1H NMR (300 MHz, CDCl3) δ 9.92 (d, J ) 8.2 Hz, 1H), 9.32
(d, J ) 8.1 Hz, 1H), 8.45 (d+d, 2H), 8.40 (s, 1H), 8.32 (s, 1H),
5.06 (m, 2H), 4.41 (t, 2H), 3.92 (m, 4H), 3.29 (d, 2H), 3.03 (m,
2H), 2.60 (q, 4H), 2.06-1.28 (m, 36H), 0.90 (t, 3H); 13C NMR
(75 Hz, CDCl3) δ 163.5, 163.4, 163.2, 163.1, 156.1, 149.6, 133.9,
133.1, 129.1, 128.5, 128.4, 127.6, 124.1, 124.0, 123.0, 122.9, 122.3,
121.3, 121.2, 120.4, 117.1, 69.9, 66.0, 53.5, 50.9, 31.4, 30.4, 29.1,
29.1, 29.1, 28.8, 28.7, 26.1, 25.8, 25.0, 22.2, 13.6; MALDI-TOF
MS (m/z) 823.7, calcd for C52H61N3O6 (m/z), 824.08. Anal. Calcd
for C52H61N3O6(H2O)1.5: C, 73.32; H, 7.52; N, 4.94. Found: C,
73.28; H, 7.42; N, 4.78.
(N,N′-Dicyclohexyl-1,7-di(cyclohexylamino))perylene-3,4;9,-
10-tetracarboxydiimide (6). 1 (260 mg, 0.32 mmol) was added
to cyclohexylamine (15 mL). The reaction mixture was heated to
110 °C under nitrogen and then kept at this temperature for 12 h.
The reaction mixture was cooled to room temperature, and the
solvents were evaporated under reduced pressure. The deep green
residue was column chromatographed on silica gel with chloroform
as eluent. The second green band was collected, and 6 was collected
1
as deep green solid (18 mg, 5%): mp >280 °C; H NMR (300
MHz, CDCl3) δ 8.58 (d, J ) 10.8 Hz, 2H), 8.01 (d, J ) 10.8 Hz,
J. Org. Chem, Vol. 72, No. 7, 2007 2409

Zhao et al.
(N,N′-Dicyclohexyl-1-dodecyloxy-7-cyclohexylamino)perylene-
3,4;9,10-tetracarboxydiimide (10). 2 (88 mg) was added to
cyclohexylamine (7 mL). The reaction mixture was heated to 90
°C and kept at this temperature overnight. Then the reaction mixture
was cooled to room temperature, and the excess cyclohexylamine
was evaporated under reduced pressure. The deep green residue
was purified by column chromatography on silica gel with
chloroform as eluent. The first green fraction was collected, and
the solid was recrystallized from chloroform and methanol to give
product 10 as deep green solid (44 mg, yield 51%): mp >280 °C;
1H NMR (300 MHz, CDCl3) δ 8.85 (d, J ) 8.4 Hz, 1H), 8.61 (d,
J ) 8.3 Hz, 1H), 8.14 (d, J ) 8.4 Hz, 2H), 8.07 (d, J ) 8.3 Hz,
1H), 7.95 (s, 1H), 7.68 (s, 1H), 6.19 (d, 1H), 5.03 (m, 2H), 3.95 (t,
2H), 3.65 (br, 1H), 2.55 (m, 6H), 2.15 (m, 2H), 1.94 (m, 4H), 1.82-
1.25 (m, 48H), 0.89 (t, 3H); 13C NMR (75 Hz, CDCl3) δ 163.5,
163.4, 163.2, 162.7, 154.8, 145.0, 134.7, 131.2, 128.6, 128.4, 127.9,
125.8, 123.3, 123.2, 121.4, 121.2, 121.0, 120.7, 1201.1, 117.6,
114.7, 69.1, 53.4, 53.3, 51.9, 32.5, 31.4, 29.2, 29.1, 28.9, 28.9, 28.7,
28.5, 26.1, 25.7, 25.2, 25.1, 25.0, 24.4, 22.2, 13.6; MALDI-TOF
MS (m/z) 836.1, calcd for C54H65N3O5 (m/z), 836.14. Anal. Calcd
for C54H65N3O5: C, 77.57; H, 7.84; N, 5.03. Found: C, 77.62; H,
7.68; N, 5.15.
Acknowledgment. Financial support from the Natural Sci-
ence Foundation of China (Grant Nos. 20571049, 20325105,
20431010), National Ministry of Science and Technology of
China (Grant No. 2001CB6105-07), Ministry of Education of
China, Shandong University, is gratefully acknowledged.
Supporting Information Available: 1H and 13C NMR spectra
of compounds 2-10. General experimental section including
instruments and methods. Atom coordinates from the AM1 calcula-
tion for compounds 3-10. This material is available free of charge
via the Internet at http://pubs.acs.org.
JO062150J
2410 J. Org. Chem., Vol. 72, No. 7, 2007