Electron Push-Pull Effects in 3,9-Bis(p-(R)-diphenylamino)perylene and Constraint on Emission Color Tuning

Article abstract of DOI:10.1021/acs.joc.9b01849

A series of perylene-based donor-acceptor-donor (D-A-D) compounds, 3,9-bis(p-(R)-diphenylamino)perylene (R: CN (2a), F (2b), H (2c), Me (2d), and OMe (2e)), was synthesized using 3,9-dibromoperylene with p-(R)-diphenylamine, and the intramolecular charge transfer (ICT) on the D-A-D system with regard to the electron push-pull substituent effect was investigated. By introducing various p-(R)-diphenylamine derivatives with electron-donating or electron-withdrawing R groups, the energy band gaps of the D-A-D compounds were systematically controlled and the emission colors were efficiently tuned from green to red. As expected, the steady state emission spectra of all D-A-D compounds were observed, as well as the emission color controlled, depending on the Hammett substituent constants (σ_p). In the Lippert-Mataga plots, a different charge-transfer character was observed depending on the electron push-pull substitution, which showed gradually increased ICT characters from the electron-withdrawing to donating substitution. However, exceptionally, the strong electron-withdrawing group of CN-substituted 2a did not correlate with the other R group compounds. From the experimental data and density functional theory calculations, we assume that there is a constraint on emission color tuning to generate higher energy of blue emission in the D-A-D molecular system, due to the reverse charge-transfer property caused by the strong electron-withdrawing group.

Full text of DOI:10.1021/acs.joc.9b01849

Subscriber access provided by Macquarie University
Article
Electron Push–Pull Effects in 3,9-Bis(p-(R)-
diphenylamino)perylene and Constraint on Emission Color Tuning
Mina Ahn, Min-Ji Kim, and Kyung-Ryang Wee
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01849 • Publication Date (Web): 28 Aug 2019
Downloaded from pubs.acs.org on August 30, 2019
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.

Page 1 of 27
The Journal of Organic Chemistry
1
2
3
4
5
Electron Push–Pull Effects in 3,9-Bis(p-(R)-diphenylamino)perylene and
6
7
Constraint on Emission Color Tuning
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Mina Ahn, Min-Ji Kim, and Kyung-Ryang Wee*
Department of Chemistry and Institute of Basic Science, Daegu University, Gyeongsan
38453, Republic of Korea.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 27
1
2
3
4
5
Abstract
6
7
8
9
A series of perylene-based donor–acceptor–donor (D–A–D) compounds, 3,9-Bis(p-(R)-
diphenylamino)perylene (R: CN (2a), F (2b), H (2c), Me (2d), and OMe (2e)), were
synthesized using 3,9-dibromoperylene with p-(R)-diphenylamine, and the intramolecular
charge transfer (ICT) on the D–A–D system with regards to the electron push–pull
substituents effect was investigated. By introducing various p-(R)-diphenylamine derivatives
with electron-donating or electron-withdrawing R groups, the energy band gaps of the D–A–
D compounds were systematically controlled, and the emission colors were efficiently tuned
from green to red. As expected, the steady state emission spectra of all D–A–D compounds
were observed, as well as the emission color being controlled, depending on the Hammett
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
substituent constants ( ). In the Lippert-Mataga plots, the different charge transfer character
휎푝
was observed depending on the electron push–pull substitution, which showed gradually
increased ICT characters from the electron-withdrawing to donating substitution. However,
exceptionally, the strong electron withdrawing group of CN substituted 2a did not correlate
with the other R group compounds. From the experimental data and DFT calculations, we
assume that there is a constraint on emission color tuning to make higher energy of blue
emission in the D–A–D molecular system, due to the reverse charge transfer property caused
by the strong electron withdrawing group.
Keywords: Perylene, Diphenylamine, Donor-Acceptor, Electron Push-Pull, Intramolecular
Charge Transfer, Band-gap Control, Emission Color Tuning
ACS Paragon Plus Environment

Page 3 of 27
The Journal of Organic Chemistry
1
2
3
4
5
Introduction
6
7
8
9
Polycyclic aromatic hydrocarbons (PAHs) based materials play an important role in
emerging technologies concerning molecular electronics, optoelectronics, energy conversion
devices, and diverse forms of nano-technology.1 For example, Anthracene and Tetracene
derivatives have been used as emitting materials to produce efficient and stable emission for
full color organic electroluminescence devices (OLEDs) or organic light-emitting field-effect
transistor (OLEFET), which demonstrated good chromaticity and luminescence efficiency
with high device stability.2-3 To achieve multi-functional optoelectronic properties, many
researchers are trying to develop various types of PAHs based materials. Among the various
PAHs, Perylene has been regarded as an appealing light-emitting dopant molecule in OLEDs
application, due to its good optical and electronic properties. Perylene in dilute solution
exhibits excellent fluorescence quantum yields as high as 0.94,4 and shows an intense blue
emission.5-6 In addition, the planar geometry enables molecular aggregation, which causes the
generation of self-quenching, broad emission band, and bathochromic shift.7 In particular,
perylene has mainly focused on the study of the perylene diimides (PDIs), which shows the
different electronic and optical properties by introducing various substituents for the bay-
positions at the (1, 6, 7, and 12)-positions of the conjugated perylene core.8-10 The PDIs have
been utilized in various applications, such as organic field-effect transistors (OFETs),11-15
light-harvesting arrays,16-17 and organic photovoltaic cells (OPVs).18-26
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Furthermore, PAHs containing the donor–acceptor (D–A) system have been intensively
investigated and applied to diverse research areas, due to their unique photophysical and
electrochemical properties. In particular, PAHs-based dipolar organic molecules containing
D–A units have been well known in many organic optoelectronic device applications.27-30 In
the PAHs-based dipolar organic molecules, the donor or acceptor units influence the
regulating molecular orbital partitioning, energy band gap, emission color, and charge
transfer efficiency.27 Basically, these properties can be modulated either by increasing the
donor and acceptor strength, or altering the π-conjugated linker between the donor and
acceptor unit.31 Also, PAHs containing D–A molecular systems show intramolecular charge
transfer (ICT) properties, and the ICT can be controlled by changing the donor or acceptor
units.32 For example, pyrene is of interest to regioselective functionalization considering the
substitution of symmetry or asymmetry about the main active site at the (1, 3, 6, and 8)-
positions and the K-regions at the (4, 5, 9, and 10)-positions with regards to the donor and
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 27
1
2
3
4
5
6
7
8
9
acceptor system.27,33 Specifically, Wang et al. reported the emission color of pyrene-based
chromophores is controlled by simple functional R group (R= F, H, Me, tBu, OMe)
modification at the para position of the diphenylamine (DPA) donor.34-35 Not only for the
pyrene based D-A molecule, various PAHs based D–A molecules that showed controllable
ICT properties have also been reported by many researchers.36-39 Likewise, donor or acceptor
substituted perylenes are particularly important in terms of the controllable ICT property,
which is enhanced by introducing electron-donating or electron-withdrawing groups on the
centrosymmetric perylene core.34,40 The amount of charge transferred from the donor to
acceptor depends on the substitution of the donor, and can be roughly described by the
electron-donating or -withdrawing ability of the substituent.41 The ICT effects on perylene
based D–A systems through donor modulation have been reported in the previous literature.
Zagranyarski et al. reported that the optical and electronic properties of the (1, 6, 7, 12)-
tetrachloroperylene compounds are tuned depending on substitution of the electron-donating
or -withdrawing groups at the four peri-positions, which are the (3, 4, 9, 10)-positions of the
perylene core.42 Although various Perylene-based D–A materials were reported, systematic
and fine control by electron push–pulled substitutions on the Perylene based D–A molecule is
still to be reported. In addition, the ICT properties with emission color tuning range in the
Perylene based D–A molecule also lack substantial information.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
In this study, we designed and synthesized a series of perylene D–A–D molecules
consisting of two DPA donor units linked directly to perylene at the (3, 9)-positions as an
acceptor unit. This excluded the effect on the π-conjugated linker, and facilitated stronger
ICT effects between the donor and acceptor units. By introducing various DPA (p-(R)-
diphenylamine) derivatives with electron-donating or -withdrawing R groups, the energy
band gap of the D–A–D compound was systematically controlled, and the emission colors
were efficiently tuned from green to red. Different charge transfer character was observed
depending on the electron push–pull substitution, which showed gradually increased ICT
characters from the electron-withdrawing to donating substitution. In particular, the CN-
substituted compound emission was originated by reverse ICT character from arylamine to
CN unit. This result indicates that there is a constraint on emission color tuning to make
higher energy of blue emission in the D–A–D molecular system, due to the reverse charge
transfer property caused by the strong electron withdrawing group.
ACS Paragon Plus Environment

Page 5 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
Results and discussion
Synthesis
8
9
Scheme 1. Synthesis of 3,9-bis(N,N-bis(4′-(R)-phenyl)amino)perylene.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
R
R
Br
N
H
Br
I
N
CuI
N
LiNH2
Buchwald-Hartwig
coupling
R
R
R
K3PO4
24h , 130 o
DMF
R
2
1
C
R
2a : R=CN (60%)
2b : R=F
2c : R=H
(78%)
(79%)
2d : R=Me (83%)
2e : R=OMe (81%)
Scheme 1 shows the synthetic procedures for a series of perylene-based D–A–D
compounds, 3,9-Bis(p-(R)-diphenylamino)perylene (R: CN (2a), F (2b), H (2c), Me (2d), and
OMe (2e)). For the first step, the donor units of the various electron-donating or withdrawing
group substituted diphenylamines at the para-positions, p-(R)-diphenylamine (R: CN (1a), F
(1b), H (1c), Me (1d), and OMe (1e)), were prepared according to the previously reported
procedures. Then, the Perylene based D–A–D compounds were successfully synthesized by
modified Buchwald-Hartwig cross-coupling reaction using 3,9-dibromoperylene with 2 molar
ratios of p-(R)-diphenylamines (1). Specifically, 3,9-bis(p-(R)-diphenylamino)perylene (2)
was prepared in the presence of 5 mol.% Pd2(dba)3 with Xantphos as a catalyst and excess
amounts of NaOtBu base as an orange or red solid in toluene solvent with a yield of 60–81 %.
All of the compounds were purified by silica gel column chromatograph using
hexane/dichloromethane mixture eluents, and further purified by recrystallizations for high
purity. The molecular structure of all compounds was characterized by H- and 13C{1H}-
1
NMR, elemental analysis, and mass spectrometry. The experimental section and the
Supporting Information (SI) provide the detailed synthetic procedures and characterization
data.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 27
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 1. UV-vis absorption (top) and emission (bottom) spectra of compounds 2 in CH2Cl2 solution.
ACS Paragon Plus Environment

Page 7 of 27
The Journal of Organic Chemistry
1
2
3
4
5
Table 1. Photophysical properties of 2a-2e
푑
푑
푘rad × 107 푘nr × 107푠푘rad/푘
6
7
8
9
휆
푚푎푥abs
휆
푚푎푥PL
Stokes
Φ푓푐
τF
Shift
(nm)
(nm)
(cm-1)
sol푎 film푏
sol푎 film푏
sol푎 film푏
(ns)
Compd
/
/
/
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2a
2b
2c
2d
2e
451/463
491/499
491/508
503/513
514/541
525/629
558/578
561/608
582/605
624/566
3,125
2,445
2,541
2,698
0.91/0.57
0.64/0.31
0.65/0.32
0.61/0.30
0.37/0.27
3.538
4.265
4.715
6.246
7.800
25.7
15.0
13.8
9.77
4.74
2.54
8.44
7.42
6.24
8.08
10.1
1.78
1.86
1.57
0.59
3,430
a
b
c
Measured in CH2Cl2 at room temperature (RT). Measured in thin neat films. Relative to 9,10-diphenylantracene or
rhodamine B as standards in CH2Cl2 at RT. d Values of
푘rad
푘nr
푘rad = Φ푓
were calculated according to the equations,
and
/휏F
푘nr = (1/휏 ― 푘
)
F rad
and
.
Photophysical Properties
As shown in Fig. 1 and Fig S4-S6, the steady state UV-visible absorption and fluorescence
spectra were measured both in solution and film state, and Table 1 summarizes the spectral
parameters. Fig. 1 (top), and Fig. S4 of the SI show that the absorption spectra of 2a–2e were
different from pure perylene unit, but the 2a showed similar absorption spectrum to perylene
in the range (400–525) nm, which is red-shifted within 15 nm for the
band of
푆0→푆1
perylene with less vibrational structures. In the nonpolar solvent, these properties were
clearly explained, showing the broader structured absorption peak than perylene at around
(400–500) nm, as shown in Fig. S5 of the SI. In addition, the 2a showed distinctive
structureless single peaks in the range (250–350) nm, which were not observed in the other
compounds, and the peak shape was similar to that of the pure perylene compound. The 2b–
2e compounds showed structured and relatively intense absorption bands in the range
(240−310) nm, which can be attributed to the π−π* transitions of each substituent and
perylene core, and showed broad, relatively weak absorption bands in the range (450−600)
nm, which can be attributed to the charge transfer absorption in the ground state. From the
steady state absorption spectral comparison between 2a and 2b–2e, the 2a showed a unique
origin, due to the remaining perylene character. We also carefully compared the molar
absorption coefficient for the 2a–2e compounds with each substituent and perylene core, to
understand the substituent effects in the D–A–D compounds. It was found that the low-
energy band is relatively more affected than the high-energy band by the para substituents of
the N,N-diphenylamine according to the molar absorption coefficient. In particular, the
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 27
1
2
3
4
5
6
7
8
9
compounds 2a−2e have a high-energy band that corresponds to a molar absorption coefficient
at around (32,047–57,135) cm−1 M−1, and a low-energy band that corresponds to a molar
absorption coefficient ranging (23,791 to 44,422) cm−1 M−1. Exceptionally, the CN-
substituted 2a has the stronger molar absorption coefficient in both the high- and low-energy
bands than those of the other compounds. To understand the inter-molecular interactions in
the steady state absorption properties, the absorption spectra in the thin film were also
recorded (Fig. S6), and all the compounds were found to exhibit a broader red shift trend in
comparison to their corresponding absorption spectra in solution, which implies that the
perylene based D–A–D molecules may aggregate in a head to-tail arrangement to form a J-
aggregate.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
푘
푟
Figure 2. Plots of the absorption maximum and radiative decay rate constants ( ) versus Hammett
휎
substituent constants ( ).
푝
As shown in Fig. 1 (bottom), the emission maxima of the 2a–2e ranged from (525 to 624)
nm in CH2Cl2 solutions, and the emission profiles covered from green to red. In addition, we
measured the solvent-dependent emission spectra for each D–A–D compound to determine
the origin of emission. Fig. S10 of the SI show that all compounds are red-shifted with
increasing solvent polarity from cyclohexane to CH3CN, which indicates the presence of
charge transfer state in the excited state. The compounds 2b–2e show a strong ICT property
in accordance with increasing the electron-donating power of the substituents, while the
compound 2a diverges from this tendency. This result implies that partial charge transfer is
finely controlled in this perylene based D–A–D system with substituent effects, but the trend
ACS Paragon Plus Environment

Page 9 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
is not completely consistent with the substituent effects. Table 1 shows that going from
compound 2a to 2e, the fluorescence quantum yields, in general, decrease while the lifetimes
increase with increasing the electron-donating power of the substituents, showing the energy
gap law behavior. Both the above-mentioned values were mainly explained by the radiative
and nonradiative decay rate constants. All the emission decay profiles were well fitted by the
single exponential functions, suggesting the radiative decay from a single specific excited
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
state.43 Using the relationship between the
and
values, the radiative and nonradiative
τF
Φ푓
decay rate constants were calculated. Following the energy gap law, the
value gradually
푘푟
decreases, while the
value rapidly increases with increasing the electron-donating
푘푛푟
power. However, as shown in Table 1, and Fig. S8 of the SI, there was a general trend in the
value, but not in the value, showing that the value changes according to the
푘푟
푘푛푟
푘푟
휎푝
value is controlled by the electron
value with good linear correlation. This means that the
푘푟
value plays a key role in controlling the
effect of the substituents, and as a result, the
푘푟
emission color. In particular, among the perylene series, the CN substituted 2a compound
was well fitted to the correlation between the value and the value, as well as the
푘푟
휎푝
absorption maximum and the
value, as shown in Fig. 2. Based on these results, the CN
휎푝
compound seems to show the same trend as the other compounds, but the distinctive effect of
the CN compound was identified, which will be further discussed in a later section.
Figure 3. Relative slope comparison of the Lippert–Mataga plots for the 2a–2e.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 27
1
2
3
4
5
6
7
8
9
The intramolecular charge transfer (ICT) process was further evaluated by the relationship
between the Stokes shifts in various solvents, and the Lippert-Mataga equation. Therefore,
the sensitivity of the solvent polarity can be analyzed in terms of the difference between the
dipole moments in the ground and excited states. The Stokes shift between the maximum
absorption and emission wavelengths, in wavenumbers (Δν), is expressed using Eq. (1):
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2
ℎ푐푎30
휀 ― 1
푛 ― 1
2
( )
× 휇푒 ― 휇푔
푣푎 ― 푣푓 =
×
―
(
)
(
)
2휀 + 1 2푛 + 1
2
ℎ푐푎30
=
(
× (∆휇)2∆푓
(1)
)
where, μe − μg (Δμ) is the difference between the dipole moments of the excited and ground
states, c is the speed of light, h is Planck’s constant, and a0 is the radius of the Onsager cavity
around the fluorophore. The dielectric constant (ε) (ε: 2.02; cyclohexane, 2.38; toluene, 7.6;
THF, 9.1; CH2Cl2, 37.5; CH3CN) and the refractive index (n) of the solvents are included in
the term Δf, known as orientation polarizability. The Onsager radii, which were obtained by
DFT calculations, were considered to be half of the average size of (19.8, 19.1, 18.6, 20.7,
and 20.0) Å for 2a–2e, respectively. Fig. 3 shows the Stokes shift for the ICT process in
various solvents changed linearly with Δf. Using the slope values in Eq. (1), the values of
dipole moment change (Δμ) for 2a–2e were estimated to be (19.8, 15.2, 14.3, 20.3, and 21.7)
D, respectively. Table S3 of the SI shows the values of the ground state dipole moment
(휇푔)
for energy minimized structures obtained by the DFT method close to zero due to the
symmetry of compounds. Using the values of the ground state dipole moment and
(휇푔)
were calculated to be
dipole moment change (Δμ), the excited state dipole moments
(휇푒)
(20.6, 15.2, 14.3, 20.3, and 22.0) D for 2a–2e. This result explains that the excited state
dipole moments for 2a–2e are considerably larger than the ground state dipole moments,
qualitatively showing the small charge transfer gap in the ground state and the large charge
transfer gap in the excited state, as measured in the UV–Vis and emission spectroscopy. As
anticipated, the trend in the excited state dipole moments was consistent with the trend in the
slope of the Lippert-Mataga plots in the order 2c < 2b < 2d < 2a < 2e, which is consistent
with the red-shifting interval on increasing the solvent polarity from cyclohexane to CH3CN.
In short, except for 2a, according to increasing the electron-donating power of the
substituents, the excited state dipole moments increase. From these results, we assumed that
ACS Paragon Plus Environment

Page 11 of 27
The Journal of Organic Chemistry
1
2
3
4
5
the emission of the CN substituted 2a, which has similar molecular structure to the other
6
7
compounds, results from the different chromophore region.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 4. CV curves of 2a–2e in CH2Cl2 solution containing 0.1 M TBAP as electrolyte, at a scan rate
of 0.1 Vs−1.
Electrochemical Properties
As shown in Fig 4, the electrochemical properties of 2a–2e were also investigated by
cyclic voltammetry (CV), which was performed by using a three-electrode cell system; a
glassy carbon electrode was used as the working electrode, while a platinum wire and SCE
were used as the counter and reference electrodes, respectively. All compounds showed
reversible oxidation peaks, and the first oxidation onset potential is located at (0.62, 0.64,
0.61, 0.52, and 0.44) V for 2a–2e, respectively. These peaks can be ascribed to the
diphenylamine perylene unit in its oxidized form. Once a unit electron is taken out from the
triarylamine to generate the oxidized form, the molecules are stabilized by the π-conjugation
effect. This means that the stronger the electron-donating group of the substituents, the better
the π-conjugation effect, which affects the values of the first oxidation onset potential.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 27
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 5. Comparison of the experimental and calculated energy levels of HOMO–LUMO.
As shown in Fig. 5, the experimental and the calculated HOMO-LUMO energy levels for
the D–A–D perylene series were compared. The experimental HOMO energy levels were
estimated from the first oxidation onset potential, indicating approximately (−5.44 ± 0.2) eV.
Because no cathodic reduction processes were measured, using the optical band gaps
calculated from the edge of the absorption spectra, the experimental LUMO energy levels
were estimated from the optical band gaps and the HOMO energy levels. In common with the
HOMO energy levels, most of the LUMO energy levels show similar values, indicating
approximately (-3.12 ± 0.13) eV. The calculated HOMO energy levels were in the range (-
5.63 ± 1.24) eV, and were higher than the experimental ones, except for 2a. The calculated
LUMO energy levels were in the range (-2.84 ± 1.01) eV, and all compounds were higher
than the experimental ones. The experimental and calculated values of the HOMO–LUMO
energy level indicated that the OMe substitution is the most efficient electron donor group in
this D–A–D perylene series. However, the most efficient electron acceptor group was not
exactly matched with the experimental and calculated values in this system. The experimental
value showed that the F (2b) is the best electron acceptor, while the calculated value showed
the CN (2a) is the best electron acceptor. The calculated HOMO and LUMO energy levels
increased with increasing electron-donating power in the order 2e > 2d > 2c > 2b > 2a,
ACS Paragon Plus Environment

Page 13 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
whereas the experimental ones were less sensitive to electronic variations of the substituents.
The effect of the HOMO and LUMO levels on the substituent is also explained as a function
of the Hammett substituent constants ( ), both experimentally and computationally. Fig. S8
8
9
σp
of the SI shows that except for 2a, the experimental HOMO and LUMO energy levels of 2b–
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2e show good linear correlation with the
values, showing the HOMO slope is larger than
σp
that of the LUMO. However, compound 2a deviates from the tendency of the HOMO and
LUMO energy levels of the 2b–2e. In the case of the calculated HOMO and LUMO energy
levels of all compounds, the same as mentioned above applies to the experimental results of
compounds 2b–2e. On the basis of the correlation of the HOMO/LUMO energy level and the
Hammett substituent constants ( ), it can be seen that except for the 2a, the substituent
σp
effect impacts on the HOMO level control with the tuning of the band gap. Table 2 also
summarizes the optical and calculated energy band gaps ( 푔) for 2a–2e. As the electron-
퐸
withdrawing power of the para-substituent of the diphenylamino moiety increases, both of
the energy band gaps are gradually expanded, showing that the calculated energy gaps are
larger than the optical gaps. These results demonstrate that the band gap of the donor and
acceptor substituted molecules can be significantly reduced, when compared to the pure
perylene molecule. Therefore, whatever powerful electron-withdrawing group and electron-
donating group are appended, the emission color is capable of the region from green to red
only, and it is difficult to tune higher energy of the blue emission region. We suggest that
only with the effect of the substituents, the emission color of the similar molecular structures
is finely controlled by tuning the band gap.
Table 2. Energy band gap properties of 2a-2e
HOMO푎
LUMO푏
퐸푔opt
(eV)
2.43
2.32
2.31
2.25
2.18
HOMO푐
(eV)
LUMO푐
(eV)
퐸푔
Compounds
(eV)
(eV)
(eV)
2.79
2.67
2.68
2.63
2.56
2a
2b
2c
2d
-5.42
-5.44
-5.41
-5.32
-2.99
-3.12
-3.10
-3.07
-3.06
-5.63
-4.84
-4.68
-4.55
-4.39
-2.84
-2.17
-2.00
-1.92
-1.83
2e
-5.24
ox
LUMO (eV) = ―푒(퐸HOMO + 퐸gopt
a
b
c
(
)
.
퐸
HOMO (eV) = ― 푒 퐸onset + 4.8
퐸 )
. Obtained by DFT calculation.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 27
1
2
3
4
5
DFT Calculations
6
7
8
9
Fig. 6 shows the HOMO and LUMO orbitals of perylene based D–A–D compounds (2a–
2e), which were obtained by the Gaussian 16 and visualized Chem3D and GaussView
program. The geometries were optimized by the DFT method using the B3LYP correlation
function, employing the 6-31G (d,p) level in the vacuum state. The HOMOs for 2a–2e are
distributed on the entire molecule, delocalized in the most perylene moiety with N atom and a
little phenyl moiety. Given the HOMO orbital distribution of phenyl moiety, except for 2a,
2b–2e compounds were affected by the substituent effect, and it was demonstrated by the
tendency of the calculated HOMO energy level, as shown in Fig. 5. The H-1 orbitals of 2a–
2e were largely populated on the diphenylamino moiety containing the para substituents. In
contrast, the LUMO for 2a–2e was mainly distributed on the perylene core. Similarly, the
L+1 orbitals of 2b–2e were distributed on the perylene cores with slight contribution to the
phenyl moieties as the substituent’s electron-withdrawing power is increased. In contrast, the
L+1 orbital of 2a was populated on the diphenylamino moiety containing the para
substituents but not N atom, as well as perylene core. Due to the strong electron-withdrawing
power of CN unit, the L+1 orbital distribution of 2a compound was completely transferred to
the diphenylamino moiety from the perylene core. However, as shown in Table S4 of the SI,
the relatively small energy level difference of the L+1 and LUMO of 2a allows both acceptor
properties to be considered.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2a
2b
2c
2d
2e
L+1
LUMO
HOMO
H-1
Figure 6. Frontier orbital distributions (HOMO-1, HOMO, LUMO, LUMO+1) of 2a–2e calculated
by DFT with B3LYP function and 6-31G (d,p) basis.
ACS Paragon Plus Environment

Page 15 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Fig. S12 and Table S6 of the SI show the time-dependent DFT (TD-DFT) with the same
functional and basis set confirms the origin of the π–π* transitions and the ICT transitions of
2a–2e with the spectral shift showing. The TD-DFT calculations exhibited three distinct
absorption bands that are not perfectively matched with the experimental data, due to the
strong spectral shift in the ICT transition. In particular, it can be seen that among the perylene
series, the compound 2a has strong spectral shift in both π–π* and ICT transitions, and the
most similar absorption spectrum shape to the TD-DFT calculation. Considering the
transition assignment of the spectra band, the ICT bands consist of the major transition from
the HOMO to the LUMO, and the minor transition from the H-1 to the LUMO. The former
corresponded to transition from the perylene moiety with nitrogen atom as an electron donor
to the perylene core as an electron acceptor, while the latter corresponded to transition from
the diphenylamino moiety including substituents as an electron donor to the perylene core as
an electron acceptor. Compound 2a has the structured absorption peak at about 380 nm,
which shows the larger contribution to the transition from HOMO to L+1 than from H-2 to
LUMO, and its transition corresponded to the perylene moiety with nitrogen atom as an
electron donor to diphenylamino moiety, without N atom as an electron acceptor. However,
compound 2b–2e compounds showed a greater contribution in the transition from H-2 to
LUMO than from HOMO to L+1. It can be suggested that compound 2a has a unique
transition origin distinct from the 2b–2e; the sole nitrogen atom acts like an electron donor
due to the strong electronegativity and lone pair, and as a result, the transition of the 2a can
occur within the diphenylamine region. As a result, unlike the other compounds, the ICT of
2a occurs not only in the opposite direction, but also in the same direction, as shown in the
other compounds. Therefore, we assume that the 2a shows the additional reverse ICT
property, as well as the ICT property that generally appears in the 2b–2e, and there is a limit
to the emission control, due to the inversion of the region to allow ICT to occur.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 27
1
2
3
4
5
Conclusion
6
7
8
9
A series of perylene-based donor-acceptor-donor (D–A–D) compounds, 3,9-Bis(p-(R)-
diphenylamino)perylene (2a–2e), were designed and synthesized using a Buchwald-Hartwig
coupling reaction, and their photophysical and electrochemical properties were investigated
both experimentally and computationally. Based on the UV-Vis spectroscopy and theoretical
calculation, donor-acceptor substituted molecules showed the ICT character accompanied by
a significant decrease of the optical energy gap, compared with the pure donor and acceptor
unit. Moreover, the ICT process was controlled from the simple substituent effect, and the
emission color was adjusted from green to red. A good linear correlation between the
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
photophysical properties and the Hammett substituent constants
indicates that all
(σp)
compounds follow the general trend. However, exceptionally, the CN (2a) compound has
proven to have unique properties that are different from the other compounds on the basis of
the UV–Vis absorption spectrum measured in the Lippert-Mataga plot and the DFT/TD-DFT
calculation. In particular, the DFT calculation showed that with regards to the emission
control, the CN compound reached breaking point, due to the reverse ICT. As a result, we
assumed that there is constraint on emission color tuning to make the higher energy of blue
emission in the D–A–D molecular system, due to the reverse charge transfer property caused
by the strong electron withdrawing group.
ACS Paragon Plus Environment

Page 17 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
Experimental Section
General
8
9
Based on standard Schlenk techniques, all of the synthesis experimental procedures were
performed under a dry argon condition. All of the reagents and solvents were obtained from
Sigma-Aldrich, Duksan and Chemical Oriental Chemical Industries, and used without
purification. Deuterated solvent for NMR experiments was obtained from Merck or
Cambridge Isotope Lab. Inc. All reactions were monitored with thin layer chromatography
(TLC) using commercial TLC plates (Merck Co.). Silica gel column chromatography was
performed on silica gel 60 G (230–400 mesh ASTM, Merck Co.). The synthesized
compounds were characterized by 1H-NMR or 13C-NMR, and elemental analysis. The 1H and
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
13
proton-decoupled C spectra were recorded on a Bruker500 spectrometer operating at 500
and 125 MHz, respectively, and all proton and carbon chemical shifts were measured relative
to internal residual chloroform (99.5 % CDCl3) from the lock solvent. The elemental analyses
(C, H, N, O) were performed using Thermo Fisher Scientific Flash 2000 series analyzer. The
3,9-dibromoperylene44,
N,N-bis(4′-cyanophenyl)amino45
(1a)
and
N,N-bis(4′-
fluorophenyl)amino46 (1b), diphenylamine46 (1c), N,N-bis(4′-methylphenyl)amino46 (1d), and
N,N-bis(4′-methoxyphenyl)amino46 (1e) were prepared based on the previously published
method. The UV/Vis absorption spectra were recorded with photodiode array
spectrophotometry by Agilent (HP8453), and the fluorescence emission measurements were
carried out using Jasco spectrofluorometry (FP-6300) with a wavelength resolution of ~1 nm.
Fluorescence lifetimes were measured by PicoQuant FluoTime 200 that takes advantage of
the time-correlated single photon counting method. A pulsed diode laser operated at 20 MHz
repetition rate was used as the excitation source. The FWHM of a laser pulse was typically 45
ps, and the instrument response function was ~190 ps when the Hamamatzu photomultiplier
tube (H5783-01) was used. The emission quantum yields (ΦPL) were calculated using
William’s comparative method for samples of five different concentrations of (1 – 10) μM,
using 9,10-diphenylanthracene (ФPL = 0.95) as a reference standard. A CH Instruments 701D
potentiostat was used for electrochemical measurements, and cyclic voltammetry (CV) was
performed in an electrolytic solution prepared using 1 mM of electroactive compounds and
0.1 M tetrabutyl ammonium hexafluorophosphate (NBu4PF6) at RT under argon atmosphere.
A three-electrode configuration, glassy carbon, platinum wire, and SCE, were used as
working, counter, and reference electrodes, respectively. Thermal properties were determined
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 27
1
2
3
4
5
by thermogravimetric analysis (TGA) in the temperature range of 0−600 °C under a N2
6
7
atmosphere by heating at a rate of 10 °C/min.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Synthesis of 3,9-Bis(p-(R)-diphenylamino)perylene (2)
A mixture of 3,9-dibromoperylene (0.6 g, 1.47 mmol), p-(R)-diphenylamine (3.82 mmol,
R: CN (1a), F (1b), H (1c), Me (1d), and OMe (1e)), sodium tert-butoxide (1.02 g, 10.6
mmol), Xantphos (0.04 g, 5 mol.%), Pd2(dba)3 (0.07 g, 5 mol.%) in toluene/1,2-
dimethoxyethane (2:1, 40 mL) was refluxed under argon at 110 °C for overnight. After
cooling to RT, deionized water (50 mL) was poured, and organic layer was separated using a
separating funnel. The water layer was washed using methylene chloride (×3) for the
extracted remained organic residue. After combined all of the organic solvents, the organic
layer was dried over anhydrous MgSO4, and then filtered off. The solvent was removed under
reduced pressure, and the residue was purified by silica gel column chromatography using
CH2Cl2/hexane mixture eluent. Finally, 3,9-Bis(p-(R)-diphenylamino)perylene compounds
were further purified by using hexane hot filter washing.
3,9-bis(N,N-bis(4′-cyanophenyl)amino)perylene (2a): Rf 0.15 (CH2Cl2/hexane = 1:1). Red
powder (0.6 g, Yield: 60 %). mp 274 °C. IR νmax (ZnSe) 2211, 1602, 1577, 1523, 1509, 1382,
1322, 1170, 819, 806, 798, 754 cm-1. 1H-NMR (500 MHz, CDCl3, ppm) δ 8.19–8.16 (m, 2H),
8.15–8.13 (m, 2H), 7.69–7.67 (m, 2H), 7.45 (d, J = 7.5 Hz, 8H), 7.36 (t, J = 8.0 Hz, 2H), 7.26
13
(d, J = 8.0 Hz, 2H), 7.09 (d, J = 9.0 Hz, 8H). C{1H} (125 MHz, CDCl3, ppm) δ 150.0,
133.7, 130.6, 128.8, 128.6, 128.5, 128.1, 126.8, 126.7, 122.4, 121.5, 121.0, 120.6, 118.9,
105.6. Anal. Calcd for C48H26N6: C, 83.95; H, 3.82; N, 12.24. Found: C, 83.74; H, 3.81; N,
12.45.
3,9-bis(N,N-bis(4′-fluorophenyl)amino)perylene (2b): Rf 0.40 (CH2Cl2/hexane = 1:3). Red
powder (0.75 g, Yield: 78 %). mp 150 °C. IR νmax (ZnSe) 1496, 1388, 1267, 1213, 1153, 823,
1
809, 792, 761 cm-1. H-NMR (500 MHz, CDCl3, ppm) δ 8.10–8.08 (m, 2H), 8.05–8.01 (m,
2H), 7.70–7.68 (m, 2H), 7.29 (td, J = 8.5, 3.5 Hz, 2H), 7.15 (dd, J = 8.0, 2.0 Hz, 2H), 6.93–
13
6.89 (m, 8H), 6.86–6.81 (m, 8H). C{1H} (125 MHz, CDCl3, ppm) δ 159.2, 157.3, 144.7,
143.3, 131.8, 131.6, 130.1, 129.2, 129.0, 127.1, 124.1, 123.5, 120.9, 116.1. Anal. Calcd for
C44H26F4N2: C, 80.23; H, 3.98; N, 4.25. Found: C, 80.14; H, 3.81; N, 4.36.
3,9-bis(N,N-diphenylamino)perylene (2c): Rf 0.38 (CH2Cl2/hexane = 1:3). Orange powder
(0.68 g, Yield: 79 %). mp 329 °C. IR νmax (ZnSe) 1583, 1488, 1388, 1324, 1290, 1267, 808,
ACS Paragon Plus Environment

Page 19 of 27
The Journal of Organic Chemistry
1
2
3
4
5
1
744, 692 cm-1. H-NMR (500 MHz, CDCl3, ppm) δ 8.10–8.08 (m, 2H), 8.07–8.04 (m, 2H),
6
7
8
7.74–7.71 (m, 2H), 7.28 (td, J = 8.5, 1.5 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.15 (t, J = 7.5 Hz,
13
8H), 7.01 (d, J = 7.5 Hz, 8H), 6.89 (td, J = 7.5, 1.0 Hz, 4H). C{1H} (125 MHz, CDCl3,
9
ppm) δ 148.2, 143.2, 132.2, 130.1, 129.2, 127.8, 127.0, 124.3, 124.0, 122.0, 121.9, 121.0,
120.8, 117.8. Anal. Calcd for C44H30N2: C, 90.07; H, 5.15; N, 4.77. Found: C, 90.01; H, 5.00;
N, 4.99.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3,9-bis(N,N-bis(4′-methylphenyl)amino)perylene (2d): Rf 0.33 (CH2Cl2/hexane = 1:4).
Red powder (0.78 g, Yield: 83 %). mp 257 °C. IR νmax (ZnSe) 2917, 2854, 1606, 1583, 1504,
1454, 1388, 1315, 1290, 1265, 806, 759, 711 cm-1. 1H-NMR (500 MHz, CDCl3, ppm) δ 8.05–
8.04 (m, 2H), 8.02–8.01 (m, 2H), 7.72 (s, 2H), 7.26 (td, J = 8.0, 3.5 Hz, 2H), 7.18–7.17 (m,
13
2H), 6.94 (d, J = 8.5 Hz, 8H), 6.88 (d, J = 8.5 Hz, 8H), 2.21 (s, 12H). C{1H} (125 MHz,
CDCl3, ppm) δ 146.2, 131.7, 131.2, 130.1, 129.8, 128.9, 128.8, 127.2, 126.8, 124.4, 124.1,
122.1, 120.9, 120.3, 20.7. Anal. Calcd for C48H38N2: C, 89.68; H, 5.96; N, 4.36. Found: C,
89.41; H, 5.88; N, 4.71.
3,9-bis(N,N-bis(4′-methoxyphenyl)amino)perylene (2e): Rf 0.15 (CH2Cl2/hexane = 1:1).
Red powder (0.84 g, Yield: 81 %). mp 130 °C. IR νmax (ZnSe) 2927, 2852, 1583, 1502, 1454,
1
1390, 1238, 1178, 1033, 825, 808 cm-1. H-NMR (500 MHz, CDCl3, ppm) δ 8.05–8.00 (m,
2H), 7.99–7.94 (m, 2H), 7.74–7.70 (m, 2H), 7.26–7.21 (m, 2H), 7.10 (dd, J = 8.0, 3.0 Hz,
13
2H), 6.88 (d, J = 9.0 Hz, 8H), 6.68 (d, J = 8.5 Hz, 8H), 3.68 (s, 12H). C{1H} (125 MHz,
CDCl3, ppm) δ 154.8, 144.4, 142.6, 131.8, 131.6, 130.1, 128.3, 126.6, 126.5, 126.4, 124.5,
123.6, 120.5, 114.6, 55.5. Anal. Calcd for C48H38N2O4: C, 81.56; H, 5.42; N, 3.96; O, 9.05.
Found: C, 82.00; H, 5.39; N, 3.77; O, 8.84.
Density functional theory calculations
Density functional theory (DFT) calculations were performed by using Gaussian’16
software package. Full geometry optimizations in their ground state were performed using the
B3LYP functional and the 6-31G (d,p) basis set for all atoms. The excitation energies and
oscillator strengths for the lowest 100 singlet–singlet transitions at the optimized geometry in
the ground state were obtained in time-dependent DFT (TD-DFT) calculations using the same
basis set and functional as for the ground state. All Isodensity plots of the frontier orbitals
were visualized by Chem3D Ultra and GaussView software. More detail DFT/TD-DFT
calculation results for 9-bis(p-(R)-diphenylamino)perylenes were described in SI.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 27
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment

Page 21 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
ASSOCIATED CONTENT
Supporting Information
8
9
1H and 13C{1H} NMR spectra of all of the D–A–D perylene compounds, TGA data,
Emission lifetime profile, Absorption and emission spectra in various solvents and solid state,
Hammett plots, Lippert-Mataga plots, DFT/TD-DFT calculation results. This material is
available free of charge via the Internet at http://pubs.acs.org.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
AUTHOR INFORMATION
Corresponding Author
* krwee@daegu.ac.kr
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This research was supported by the Basic Science Research Program through the National
Research Foundation of Korea (NRF), funded by the Ministry of Education (NRF-
2017R1C1B1010736).
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 22 of 27
1
2
3
4
5
Reference
6
7
8
9
1. Watson, M. D.; Fechtenkötter, A.; Müllen, K., Big is beautiful−“aromaticity” revisited
from the viewpoint of macromolecular and supramolecular benzene chemistry. Chem.
Rev. 2001, 101 (5), 1267-1300.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2. Shi, J.; Tang, C. W., Anthracene derivatives for stable blue-emitting organic
electroluminescence devices. Appl. Phys. Lett. 2002, 80 (17), 3201-3203.
3. Hepp, A.; Heil, H.; Weise, W.; Ahles, M.; Schmechel, R.; von Seggern, H., Light-
emitting field-effect transistor based on a tetracene thin film. Phys. Rev. Lett. 2003, 91
(15), 157406.
4. Dawson, W. R.; Windsor, M. W., Fluorescence yields of aromatic compounds. J. Phys.
Chem. 1968, 72 (9), 3251-3260.
5. Li, J.; Takaishi, S.; Fujinuma, N.; Endo, K.; Yamashita, M.; Matsuzaki, H.; Okamoto,
H.; Sawabe, K.; Takenobu, T.; Iwasa, Y., Enhancement of luminescence intensity in
TMPY/perylene co-single crystals. J. Mater. Chem. 2011, 21 (44), 17662-17666.
6. Mi, B.; Gao, Z.; Lee, C.; Lee, S.; Kwong, H.; Wong, N., Reduction of molecular
aggregation and its application to the high-performance blue perylene-doped organic
electroluminescent device. Appl. Phys. Lett. 1999, 75 (26), 4055-4057.
7. Chen, C.; Shi, J.; Tang, C. In Recent developments in molecular organic
electroluminescent materials, Macromol., Wiley Online Library: 1998; pp 1-48.
8. Huang, C.; Barlow, S.; Marder, S. R., Perylene-3, 4, 9, 10-tetracarboxylic acid diimides:
synthesis, physical properties, and use in organic electronics. J. Org. Chem. 2011, 76 (8),
2386-2407.
9. Tsai, H.-Y.; Chen, K.-Y., 1,7-Diaminoperylene bisimides: Synthesis, optical and
electrochemical properties. Dyes Pigm. 2013, 96 (2), 319-327.
10. Chen, K.-Y.; Chang, C.-W., 1,7-Bis-(N,N-dialkylamino)perylene bisimides: Facile
synthesis and characterization as near-infrared fluorescent dyes. Materials 2014, 7 (11),
7548-7565.
11. Ahrens, M. J.; Fuller, M. J.; Wasielewski, M. R., Cyanated perylene-3, 4-dicarboximides
and perylene-3,4:9,10-bis(dicarboximide): Facile chromophoric oxidants for organic
photonics and electronics. Chem. Mater. 2003, 15 (14), 2684-2686.
12. Zhan, X.; Tan, Z. a.; Domercq, B.; An, Z.; Zhang, X.; Barlow, S.; Li, Y.; Zhu, D.;
Kippelen, B.; Marder, S. R., A high-mobility electron-transport polymer with broad
absorption and its use in field-effect transistors and all-polymer solar cells. J. Am. Chem.
ACS Paragon Plus Environment

Page 23 of 27
The Journal of Organic Chemistry
1
2
3
4
5
Soc. 2007, 129 (23), 7246-7247.
6
7
8
9
13. Lindner, S. M.; Kaufmann, N.; Thelakkat, M., Nanostructured semiconductor block
copolymers: π–π Stacking, optical and electrochemical properties. Org. Electron. 2007, 8
(1), 69-75.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
14. Jones, B. A.; Ahrens, M. J.; Yoon, M. H.; Facchetti, A.; Marks, T. J.; Wasielewski, M.
R., High‐mobility air‐stable n‐type semiconductors with processing versatility:
dicyanoperylene‐3,4:9,10‐bis(dicarboximides). Angew. Chem. Int. Ed. 2004, 43 (46),
6363-6366.
15. Jiménez, Á. J.; Spänig, F.; Rodriguez-Morgade, M. S.; Ohkubo, K.; Fukuzumi, S.;
Guldi, D. M.; Torres, T., A tightly coupled bis (zinc(II)phthalocyanine)−
perylenediimide ensemble to yield long-lived radical ion pair states. Org. Lett. 2007, 9
(13), 2481-2484.
16. Li, X.; Sinks, L. E.; Rybtchinski, B.; Wasielewski, M. R., Ultrafast aggregate-to-
aggregate energy transfer within self-assembled light-harvesting columns of zinc
phthalocyanine tetrakis(perylenediimide). J. Am. Chem. Soc. 2004, 126 (35), 10810-
10811.
17. Rybtchinski, B.; Sinks, L. E.; Wasielewski, M. R., Combining light-harvesting and
charge separation in a self-assembled artificial photosynthetic system based on
perylenediimide chromophores. J. Am. Chem. Soc. 2004, 126 (39), 12268-12269.
18. Kozma, E.; Kotowski, D.; Catellani, M.; Luzzati, S.; Famulari, A.; Bertini, F., Synthesis
and characterization of new electron acceptor perylene diimide molecules for
photovoltaic applications. Dyes Pigm. 2013, 99 (2), 329-338.
19. Li, J.; Dierschke, F.; Wu, J.; Grimsdale, A. C.; Müllen, K., Poly (2, 7-carbazole) and
perylene tetracarboxydiimide: a promising donor/acceptor pair for polymer solar cells. J.
Mater. Chem. 2006, 16 (1), 96-100.
20. Dinçalp, H.; Aşkar, Z.; Zafer, C.; İçli, S., Effect of side chain substituents on the electron
injection abilities of unsymmetrical perylene diimide dyes. Dyes Pigm. 2011, 91 (2),
182-191.
21. Ramanan, C.; Smeigh, A. L.; Anthony, J. E.; Marks, T. J.; Wasielewski, M. R.,
Competition between singlet fission and charge separation in solution-processed blend
films of 6,13-bis(triisopropylsilylethynyl)pentacene with sterically-encumbered
perylene-3,4:9,10-bis(dicarboximide)s. J. Am. Chem. Soc. 2011, 134 (1), 386-397.
22. Shibano, Y.; Umeyama, T.; Matano, Y.; Imahori, H., Electron-donating perylene
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 24 of 27
1
2
3
4
5
6
7
tetracarboxylic acids for dye-sensitized solar cells. Org. Lett. 2007, 9 (10), 1971-1974.
23. Kozma, E.; Catellani, M., Perylene diimides based materials for organic solar cells. Dyes
Pigm. 2013, 98 (1), 160-179.
8
9
24. Tian, H.; Liu, P.-H.; Zhu, W.; Gao, E.; Wu, D.-J.; Cai, S., Synthesis of novel multi-
chromophoric soluble perylene derivatives and their photosensitizing properties with
wide spectral response for SnO2 nanoporous electrode. J. Mater. Chem. 2000, 10 (12),
2708-2715.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
25. Choi, H.; Paek, S.; Song, J.; Kim, C.; Cho, N.; Ko, J., Synthesis of annulated thiophene
perylene bisimide analogues: Their applications to bulk heterojunction organic solar
cells. Chem. Comm. 2011, 47 (19), 5509-5511.
26. Hongyu, W.; Bo, P.; Wei, W., Solar cells based on perylene bisimide derivatives. Prog.
Chem. 2008, 20 (11), 1751-1760.
27. Feng, X.; Tomiyasu, H.; Hu, J.-Y.; Wei, X.; Redshaw, C.; Elsegood, M. R.; Horsburgh,
L.; Teat, S. J.; Yamato, T., Regioselective substitution at the 1,3-and 6,8-positions of
pyrene for the construction of small dipolar molecules. J. Org. Chem. 2015, 80 (21),
10973-10978.
28. Duan, L.; Qiao, J.; Sun, Y.; Qiu, Y., Strategies to Design Bipolar Small Molecules for
OLEDs: Donor‐Acceptor Structure and Non‐Donor‐Acceptor Structure. Adv. Mater.
2011, 23 (9), 1137-1144.
29. Kulkarni, A. P.; Kong, X.; Jenekhe, S. A., High‐Performance Organic Light‐Emitting
Diodes Based on Intramolecular Charge‐Transfer Emission from Donor–Acceptor
Molecules: Significance of Electron‐Donor Strength and Molecular Geometry. Adv.
Funct. Mater. 2006, 16 (8), 1057-1066.
30. Tanaka, H.; Shizu, K.; Nakanotani, H.; Adachi, C., Twisted intramolecular charge
transfer state for long-wavelength thermally activated delayed fluorescence. Chem.
Mater. 2013, 25 (18), 3766-3771.
31. Misra, R.; Gautam, P.; Mobin, S. M., Aryl-substituted unsymmetrical benzothiadiazoles:
synthesis, structure, and properties. J. Org. Chem. 2013, 78 (24), 12440-12452.
32. Panja, S. K.; Dwivedi, N.; Saha, S., Tuning the intramolecular charge transfer (ICT)
process in push–pull systems: effect of nitro groups. RSC Adv. 2016, 6 (107), 105786-
105794.
33. Zöphel, L.; Beckmann, D.; Enkelmann, V.; Chercka, D.; Rieger, R.; Müllen, K.,
Asymmetric pyrene derivatives for organic field-effect transistors. Chem. Comm. 2011,
ACS Paragon Plus Environment

Page 25 of 27
The Journal of Organic Chemistry
1
2
3
4
5
47 (24), 6960-6962.
6
7
8
9
34. Wang, C.-Z.; Ichiyanagi, H.; Sakaguchi, K.; Feng, X.; Elsegood, M. R.; Redshaw, C.;
Yamato, T., Pyrene-based approach to tune emission color from blue to yellow. J. Org.
Chem. 2017, 82 (14), 7176-7182.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
35. Wee, K.-R.; Ahn, H.-C.; Son, H.-J.; Han, W.-S.; Kim, J.-E.; Cho, D. W.; Kang, S. O.,
Emission color tuning and deep blue dopant materials based on 1,6-bis(N-phenyl-p-(R)-
phenylamino)pyrene. J. Org. Chem. 2009, 74 (21), 8472-8475.
36. Chen, J.; Liu, W.; Ma, J.; Xu, H.; Wu, J.; Tang, X.; Fan, Z.; Wang, P., Synthesis and
properties of fluorescence dyes: tetracyclic pyrazolo [3,4-b] pyridine-based coumarin
chromophores with intramolecular charge transfer character. J. Org. Chem. 2012, 77 (7),
3475-3482.
37. Dell’Acqua, M.; Ronda, L.; Piano, R.; Pellegrino, S.; Clerici, F.; Rossi, E.; Mozzarelli,
A.; Gelmi, M. L.; Abbiati, G., MediaChrom: Discovering a Class of Pyrimidoindolone-
Based Polarity-Sensitive Dyes. J. Org. Chem. 2015, 80 (21), 10939-10954.
38. Iwanaga, T.; Ogawa, M.; Yamauchi, T.; Toyota, S., Intramolecular charge-transfer
interaction of donor–acceptor–donor arrays based on anthracene bisimide. J. Org. Chem.
2016, 81 (10), 4076-4080.
39. Wei, X.; Bu, L.; Li, X.; Ågren, H.; Xie, Y., Full color emissions based on intramolecular
charge transfer effect modulated by formyl and boron-dipyrromethene moieties. Dyes
Pigm. 2017, 136, 480-487.
40. Vasilev, A. A.; De Mey, K.; Asselberghs, I.; Clays, K.; Champagne, B.; Angelova, S. E.;
Spassova, M. I.; Li, C.; Müllen, K., Enhanced intramolecular charge transfer in new
type donor–acceptor substituted perylenes. J. Phys. Chem. C. 2012, 116 (43), 22711-
22719.
41. Winget, P.; Brédas, J.-L., Ground-state electronic structure in charge-transfer complexes
based on carbazole and diarylamine donors. J. Phys. Chem. C. 2011, 115 (21), 10823-
10835.
42. Zagranyarski, Y.; Chen, L.; Jänsch, D.; Gessner, T.; Li, C.; Müllen, K., Toward perylene
dyes by the hundsdiecker reaction. Org. Lett. 2014, 16 (11), 2814-2817.
43. Kurata, R.; Ito, A.; Gon, M.; Tanaka, K.; Chujo, Y., Diarylamino-and Diarylboryl-
Substituted Donor–Acceptor Pyrene Derivatives: Influence of Substitution Pattern on
Their Photophysical Properties. J. Org. Chem. 2017, 82 (10), 5111-5121.
44. Torres, É.; Berberan-Santos, M. N.; Brites, M. J., Synthesis, photophysical and
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 26 of 27
1
2
3
4
5
6
7
8
9
electrochemical properties of perylene dyes. Dyes Pigm. 2015, 112, 298-304.
45. Gorvin, J. H., The synthesis of di-and tri-arylamines through halogen displacement by
base-activated arylamines: comparison with the Ullmann condensation. J. Chem. Soc.,
Perkin Trans. 1 1988, (6), 1331-1335.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
46. Tlili, A.; Monnier, F.; Taillefer, M., Selective one-pot synthesis of symmetrical and
unsymmetrical di-and triarylamines with a ligandless copper catalytic system. Chem.
Comm. 2012, 48 (51), 6408-6410.
ACS Paragon Plus Environment

Page 27 of 27
The Journal of Organic Chemistry
1
2
3
4
5
TOC:
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment