Microwave-Assisted Method for the Synthesis of Perylene Ester Imides as a Gateway Toward Unsymmetrical Perylene Bisimides

Article abstract of DOI:10.1021/acs.joc.8b00161

A high yielding microwave-assisted synthetic method to obtain unsymmetrical perylene diester monoimide (PEI) by treating the perylene tetrester (PTE) with a requisite amine is reported. Perylene-based molecules are widely used in the construction of self-assembled supramolecular structures because of their propensity to aggregate under various conditions. In comparison to perylene bisimides (PBIs), PEIs are less studied in organic electronics/self-assembly due to the synthetic difficulty and low yields in their preparation. PEIs are less electron deficient and have an unsymmetric structure in comparison to PBIs. Further, the PEIs have a higher solubility than PBIs. The present method is applicable with a wide range of substrates like aliphatic, aromatic, benzyl amines, PTEs, and bay-annulated PTEs. This method provides a tuning handle for the optical/electronic properties of perylene derivatives and also provides an easy access to unsymmetrical PBIs from the PEIs.

Full text of DOI:10.1021/acs.joc.8b00161

Subscriber access provided by Kaohsiung Medical University
Article
Microwave Assisted-Method for the Synthesis of Perylene Ester
Imides as a Gateway towards Unsymmetrical Perylene Bisimides
Ravindra Kumar Gupta, and Ammathnadu Sudhakar Achalkumar
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00161 • Publication Date (Web): 18 May 2018
Downloaded from http://pubs.acs.org on May 18, 2018
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 24
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
Microwave Assisted-Method for the Synthesis of Perylene Ester Imides as a
Gateway Towards Unsymmetrical Perylene Bisimides
9
Ravindra Kumar Gupta and Ammathnadu S. Achalkumar*
10
11
12
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, 781039, Assam, India.
Corresponding Author: *E-mail: achalkumar@iitg.ernet.in
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
Supporting Information Placeholder
ABSTRACT: A high yielding microwaveꢀassisted synthetic method to obtain unsymmetrical perylene
diester monoimide (PEI), by treating the perylene tetrester (PTE) with requisite amine is reported.
Peryleneꢀbased molecules are widely used in the construction of selfꢀassembled supramolecular
structures because of their propensity to aggregate under various conditions. In comparison to perylene
bisimides (PBIs), PEIs are less studied in organic electronics/selfꢀassembly due to the synthetic
difficulty and low yields in their preparation. PEIs are less electron deficient and have an unsymmetric
structure in comparison to PBIs. Further, the PEIs got higher solubility than PBIs. The present method is
applicable with a wide range of substrates like aliphatic, aromatic, benzyl amines, PTEs and bayꢀ
annulated PTEs. This method provides a tuning handle for the optical/electronic properties of perylene
derivatives and also provides an easy access to unsymmetrical PBIs from the PEIs.
INTRODUCTION
Perylene bisimide (PBI) based molecules are known to exhibit interesting properties and found
applications as photo stable dyes, highly luminescent materials, as a component of photoreceptors of
photocopiers and laser printers.1e They are also utilized as electron acceptors in organic solar cells
(OSCs) or as active components in organic field effect transistors (OFETs), or as building block
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 24
materials for liquid crystalline and organogel selfꢀassembly.1 More recently, suitably functionalized PBIs
have been utilized for the functionalization of gold nanorods that exhibit unique selfꢀassembly and
photophysical behavior.1fꢀi Further, with the availability of several positions that can be substituted, the
photophysical and electronic properties can be modified. The bayꢀsubstitution of the PBIs had shown to
shift the emission towards the red region, with an increase in the Stokes shift and fluorescence lifeꢀ
time.2a The increased stability of such bayꢀsubstituted PBIs make them potential materials for lasing
applications.2b Tetraesters of perylene tetracarboxylic acids (PTEs), which are structurally related to
PBIs were also utilized as materials in the area of liquid crystals,3 fluorescent dyes,4 electron acceptors
in light harvesting antennae,5 and organic light emitting diodes (OLEDs).6 Similar to PBIs, PTEs have
significant electronꢀaccepting ability due to the four carboxylate groups. They are also capable of
forming aggregates with strong πꢀπ overlap in both solutions7 and the solid state.8 Recently, perylene
tetracarboxylic diester monoimides (PEIs), are attracting increasing interest due to their intermediate
electron deficient nature between PTEs and PBIs as well as higher solubility.9 As the name suggests,
here an imide and two ester groups are connected to the same perylene core. Nonetheless, in comparison
to PBIs, the applications of PTEs and PEIs are relatively limited. Most of the reported PTEs are the
symmetrically substituted ones, whereas PEIs that are explored are only limited to simple alkyl
derivatives. In comparison, the applications of PBIs have seen steady rise due to their tunability to alter
the properties by unsymmetric substitution with various amines. However, the balancing of the
electronic levels of organic semiconductors with respect to electrodes is vital for their application in
organic electronic devices. The synthesis of PEIs, which are inherently unsymmetric is a bit challenging.
An overview of the research done over the past years is presented in Scheme 1. A common approach to
obtain alkylꢀsubstituted PEI starts with diimidification of perylene tetracarboxylic acid bisanhydride
(PTCBA) with an alkylamine, which is followed by its monohydrolysis under mild conditions.10,11
Recently few reports on obtaining PEIs are described. Yang et al. recently reported perylene imidoꢀ
diesters with three nꢀalkyl substituents of same length.9a Their synthetic approach provided
unsubstituted perylene tetracarboxylic monoimidoꢀmonoanydride in lowꢀyield, which after isolation
subjected to phaseꢀtransfer trialkylation of its dipotassium salt. This required an excess amount of the
alkyl bromide. In spite of providing access to PEIs, it’s drawback is the inability to obtain
unsymmetrically substituted PEIs. Zhang et. al reported the preparation of PEIs by the reaction of alkyl
bromides with perylene tetracarboxylic monoanhydride monoimide.9b Here the perylene tetracarboxylic
bisanhydride (PTCBA) was treated with nꢀalkylamine, which results in the formation of two products,
i.e., the perylene tetracarboxylic monoanhydride monoimide and the other one is corresponding PBI.
After the isolation of monoanhydride monoimide, it is treated with required alkyl bromide to obtain the
PEI.9b The yield was varying from 30ꢀ77%. Xue et.al. prepared perylene tetracarboxylic monoanhydride
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
2
ACS Paragon Plus Environment

Page 3 of 24
The Journal of Organic Chemistry
diester from corresponding PTE. This on treatment with nꢀalkyl amine yielded the PEI.9c Although the
yields are good, it involves three steps. Earlier, PEIs were also obtained by the controlled hydrolysis of
PTCBA with a base to obtain monoanhydride, and its
1
2
3
4
5
6
7
8
Scheme 1. Various routes to prepare PEIs/the key intermediates to prepare them over the years.
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
treatment with alkylamine to get alkyl imidoanhydride which can be further converted to the PEI.10,11
Such alkylimidoanhydrides can then be esterified to get PEI, or may be condensed with another amine
to obtain PBI.12,13 These procedures require the isolation of monoimido monoanhydride (PEA).
However, when the monoimido monoanhydride is formed, it possesses an increased solubility in
comparison to that of PTCBA. Due to this, its reactivity is increased and often it gives the symmetric
PBI. Kelber et.al. recently approached this problem in a different way.14 They obtained perylene
teracarboxylic diester from PTCBA, after which they added alkyl amine to obtain imidoꢀesterꢀacid,
which on treatment with bromoalkane yielded imidoꢀdiester. However, this reaction depends on the
initial solubility of initial starting material in excess alcohol and alkyl bromides, thus it can be used only
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 24
for small chain alcohols. In addition, corresponding alkyl bromides are also required in addition to long
reaction duration. All these previous investigations made us to investigate the problem of obtaining PEI
in a simple, high yielding method. In this report we have presented a high yielding method for the
preparation of PEI in two steps, starting from PTCBA. PTCBA is converted to its PTE and later this is
treated with the required amine under microwave conditions to yield the requisite PEI (Scheme 2). The
PEI obtained can be converted to an unsymmetric PBI if required, thus providing an easy access to
unsymmetrical PBIs.
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
RESULTS AND DISCUSSION
Initially we thought of treating PTCBA directly with requisite amine to get corresponding imide
anhydride. But this suffers from the insolubility of the starting material in most of the solvents and the
increased reactivity of the imide anhydride formed due to its higher solubility than PTCBA, which
eventually ends up in the formation of symmetrical PBI. Microwaveꢀassisted synthesis has attracted the
material and synthetic chemists, as it provides a green alternative to obtain useful products in higher
yields under milder reaction conditions along with higher product purities. Microwaves greatly
accelerate the rate of the reactions in comparison to conventional heating.15 There are few reports on the
application of microwave assisted synthesis to obtain symmetrical perylene bisimides.16 However
utilization of microwave assisted synthesis to obtain unsymmetrical derivatives are not reported to the
best of our knowledge. The time for the reaction was optimized as 35 min to obtain the maximum yield.
Compared to earlier methods, which had several low yielding steps with a difficulty in isolation, this
method is straightforward and provides a good yield of 50ꢀ55%. The remaining amount of PTE is
converted to PBI, which is highly insoluble and remain trapped with the neutral alumina used for the
column chromatography. Further we studied the substrate scope of this procedure. The PTE 4 was
treated with different aliphatic and aromatic amines (Scheme 3, Table 1) to obtain corresponding PEIs.
Further we wanted to test the scope of this reaction in the preparation of perylene tetracarboxylic diester
monoimides from bayꢀannulated perylene tetraesters (7-9). Bayꢀannulated perylene tetraesters with
heteroatoms like nitrogen, sulfur and selenium have shown ordered columnar hexagonal (Colh) phase
over a wide thermal range along with a good luminescence.17aꢀc The bayꢀsubstitution and bayꢀextension
of perylene derivatives provided an access to modify the photophysical and electrochemical properties
of perylene derivatives.17 Recently we have reported hostꢀguest OLEDs based on bayꢀannulated
perylene tetraesters exhibiting room temperature Colh phase.19 Thus considering the importance of bayꢀ
annulated perylene derivatives, we thought of synthesizing the bayꢀannulated PEIs (BAPEIs), by
utilizing the corresponding perylene tetraesters (BAPTEs) with four nꢀbutyloxy chains.18 These
tetraesters were prepared similarly to the recently published report.18 These BAPTEs were treated with
4
ACS Paragon Plus Environment

Page 5 of 24
The Journal of Organic Chemistry
1ꢀaminooctadecane (14) under microwave conditions, which yielded the corresponding BAPEIs in good
1
2
3
yield (Scheme 2, Table 1).
4
5
Scheme 2. Synthesis of PEI and bayꢀannulated PEIs.
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
o
Reagents and conditions. i) KOH, H2O, 70 C, 0.5 h, 1M HCl, Aliquat 336, KI,1ꢀBromoꢀbutane,
o
o
reflux, 12 h (76%); (ii) NaNO2, HNO3, 0 C, 1h (90%); (iii) Triethyl phosphite, 160 C, reflux, 4 h, N2
(60%); (iv) Sulfur powder, anhyd.NMP, N2, 70 C, 0.5 h, 180 C, 17 h (55%); (v) Selenium powder,
anhyd. NMP, N2, 70 C, 0.5 h, 180 C, 17 h (55%); (vi) NaH, 1ꢀIodoethane, Dry THF, reflux, 17h
(75%); (vii) 1ꢀAminooctadecane, imidazole, 165 oC, microwave, 35 min. (50ꢀ55%).
o
o
o
o
The compound 14 was prepared by Gabriel’s phthalimide synthesis (See Scheme 1 in SI).20 An
unsymmetrical PBI 12 was also prepared in good yield using the PEI as starting material to show the
utility of this method (Scheme 3, Table 1). The synthesized compounds were completely characterized
1
13
1
with the help of H, C NMR, IR spectroscopy and MALDIꢀTOF mass spectrometry. The H NMR
spectra of the BAPEIs were interesting and the effect of the inclusion of the heteroatom in the molecular
5
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 24
structure was evident with the change of the chemical shifts of the aromatic protons. The protons near to
the imide group appear in the downfield region, while the protons near the esters resonate in the upfield
region in the case of PEI. The bay protons (Hc and Hd) appear in between the two sets of protons.
Presence of the heteroatoms gives rise to a complex pattern by breaking the symmetry. In the case of
compound 1, Hc and Hd resonate at same position, while protons in ortho positions splits to form
doublets. In the case of Sꢀ and Seꢀannulated BAPEIs, Hc and Hd also appear as doublets in addition to
the doublets of He and Hf. The aromatic signals obtained for compound 3 is similar to that of compound
2 but they appear at upfield (Fig.S31).
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
Scheme 3. Synthesis of different perylene ester imdides (10,11) and an unsymmetrical perylene
bisimide 12.a
o
Reagents and Conditions: (i) Aniline, imidazole, 165 C, 35 min. (55%); (ii) Benzylamine, imidazole,
o
o
165 C, 35 min. (58%); (iii) 1ꢀAminooctadecane, imidazole, 165 C, 35 min. (55%); (iv) 3,4,5ꢀtriꢀnꢀ
decyloxy aniline, imidazole, zinc acetate, 165 oC, 35 min. (75%). a all these reactions were done using a
microwave reactor.
Table 1. Substrate scope of the present reaction for the synthesis of various PEIs and PBI (12).
Yield (%)
Starting
material
PTE (4)a
PTE (4) a
PTE (4) a
Reactant
nꢀOctyldecylamine
Aniline
PEI (55)
10 (55)
11 (58)
1 (55)
2 (55)
3 (55)
Benzylamine
BPTE (7) a nꢀOctyldecylamine
BPTE (8) a nꢀOctyldecylamine
BPTE (9) a nꢀOctyldecylamine
PEI b
3,4,5ꢀtriꢀnꢀdecyloxyaniline PBI (12) (75)
aImidazole, 165 C, microwave, 35 min.; Imidazole, Zinc
o
b
acetate, 165 oC, microwave, 35 min.
6
ACS Paragon Plus Environment

Page 7 of 24
1
The Journal of Organic Chemistry
Photophysical properties of these compounds were explored by obtaining their absorption and
emission spectra in micromolar chloroform solutions (Table 2 and Fig.1a, b). The absorption spectra of
these PEI and BAPEIs were wellꢀstructured and showed the characteristic vibronic bands. There was
not much change observed in the case of PEI and Nꢀannulated derivative 1 as both of them exhibited an
absorption maximum centered at 506 nm. However, the absorption spectra of Sꢀ and Seꢀannulated
derivatives were blue shifted with the absorption maxima centered at 480 and 486 nm respectively. All
the PEIs exhibited high molar extinction coefficients at their absorption maxima (ε: 11,500 to 15,500
Lmolꢀ1cmꢀ1). The optical band gap calculated from the absorption onset showed that the optical band
gap of PEI and Nꢀannulated derivative 1 were almost similar (2.28ꢀ2.33 eV), while that of the Sꢀ and
Seꢀannulated derivatives shown an increase (2.42ꢀ2.44 eV). Emission spectra of these compounds
showed two main bands, with the high intensity band was in the range of 499ꢀ543 nm. The Stokes shift
was found to be more for PEI (1347 cmꢀ1) and for other PEIs the value was in the range of 774ꢀ793 cmꢀ
1. Introduction of hetero atoms led to a blue shifted emission spectra for the bayꢀannulated derivatives.
Relative fluorescence quantum yields measured with respect to fluorescein (0.1 M NaOH solution, Qf =
0.79), showed a higher quantum yield for PEI, 1 and 2, but a lower quantum yield for compound 3
(Table 2). Both the solution and thin films showed visually perceivable emission under the UV light of
long wavelength. A weak emission was noticed for Seꢀderiative 3, due to the ‘heavy atom effect’.17c, 19
The absorption and emission spectra obtained in thin film state were found to be broad and blue
shifted, while the emission spectra have shown a redꢀshift (Fig.1d, e), which confirmed the formation of
Hꢀtype aggregates,21a though it may not be a classic Hꢀaggregate with an exact overlap of the molecules
one above the other. In the case of perylene based molecules with out any bayꢀsubstitution, it is quite
common to see that such molecules aggregate one above the other, with their major absorption band
getting blue shifted indicating the predominant Hꢀtype excitonic coupling.21b Here, as a consequence of
a rotational displacement of neighboring molecules, the optical transition into the lower energy exciton
state becomes allowed,22 as evidenced by the second absorption band at longer wavelength (Fig.1a and
d, Table 2). The particular arrangement and the concomitant photophysical properties of the aggregates
are strongly dependent on the substituents at periꢀposition.
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
In literature, for PBIs bearing electronically active rather innocent trialkylꢀphenyl substituents, a
relatively longꢀlived excited state with an appreciably high fluorescence quantum yield of 47% has been
reported,21b which was attributed to the relaxation of the exciton into an excimer.21cAs these PEIs are
unsymmetrically substituted, they are slightly rotated from the exact overlap, to accommodate the steric
bulk of ester functional groups. Because of this slight rotation there will not be a perfect overlap as
observed in the case of the classical Hꢀaggregates leading to the complete luminescence quenching. This
is clearly visible in the overlay of the emission spectra of thin films with that of the solutions. A huge
7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 24
reduction in the emission intensity was observed because of the aggregation caused quenching (Fig.
S40).
1
2
3
4
5
6
7
(b)
(a)
(c)
1
2
3
PEI
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
(e)
(f)
1
2
PEI
3
(d)
Figure 1. (a) Normalized absorption and (b) emission spectra in micromolar chloroform solution of 1, 2,
3 and PEI obtained on exciting at their absorption maxima; (c) Images of the same solutions under the
UV light of long wavelength (λ = 365 nm); (d) Normalized absorption and (e) emission spectra of the
spin coated films of 1, 2, 3 and PEI obtained on exciting at their absorption maxima; (f) Images of the
same thin films under the UV light of long wavelength (λ = 365 nm).
Table 2. Photophysical and electrochemical properties of PEI and BAPEIs (1, 2, 3).
Solutiona
Thin filmd
Cyclic Voltammetrye,f
E1red
c
g
h
Entry
Absorption Emissionb ꢁEg,opt
Stokes
shift
ɸg
Absorption Emissioni
EHOMO
(eV)
ELUMO
(eV)
(nm)
(nm)
(eV)
(nm)
(nm)
(V)
(cmꢀ1)
1347
506, 475, 446
543, 571,
622
527, 557,
615
499, 529,
579
2.33
2.28
2.42
2.44
0.93
0.89
0.70
0.06
439, 516
447, 544
434, 514
451, 533
631
626
616
615
ꢀ0.81
ꢀ0.96
ꢀ0.92
ꢀ0.92
ꢀ5.86
ꢀ5.66
ꢀ5.84
ꢀ5.86
ꢀ3.53
ꢀ3.38
ꢀ3.42
ꢀ3.42
PEI
1
506, 475,
448, 417
480, 450,
423, 399
486, 456,
434, 408
788
793
774
2
505, 531,
577
3
amicromolar solution in chloroform, excited at 506 nm for PEI and 1, 480 nm, 486 nm for 2 and 3 respectively, ccalculated from the red
b
edge of the longest wavelength in the absorption spectrum dprepared from the millimolar solution in chlorobenzene, micromolar solution
e
f
in dichloromethane, Experimental conditions: Ag/AgNO3 as reference electrode, Glassy carbon working electrode, Platinum wire counter
g
electrode, TBAP (0.1 M) as a supporting electrolyte, room temperature, Estimated from the formula EHOgMO = ELUMO – ꢁEg(UV)eV ;
hEstimated from the formula by using ELUMO = – (4.8 –E1/2, Fc/Fc+ + Ered
,
onset) eV; E1/2
,
= 0.462 eV, relative quantum yields are
calculated with respect to Fluorescein in 0.1M NaOH solution as the standard, Qf = 0.79.iFec/xFcc+ited at 439 nm for PEI, 447 nm for 1, 434
nm, 486 nm for 2 and 3 respectively.
8
ACS Paragon Plus Environment

Page 9 of 24
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Figure 2. (a) Cyclic voltammograms of PEI and bayꢀannulated PEIs (1, 2 and 3); (b) Energy band level
diagram showing HOMOꢀ and LUMOꢀ energy levels of PEI and BAPEIs.
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
Cyclic voltammetry (CV) studies are carried out to understand the electronic energy levels that
decide the energy and electron transfer process and reversibility of a redox process. CV studies were
carried out in anhydrous dichloromethane solutions (Table 2). PBIs are known to be electron deficient
nꢀtype semiconductors and known to have high electron affinity.1 We expected the PEIs to be less
electron deficient in comparison to PBIs. All the PEIs exhibited two quasiꢀreversible reduction peaks,
which are due to the reduction of the neutral molecule to a radical anion in the first step and to a dianion
in the second step (Fig.2a). The addition of the first electron in the first reduction increases the electron
density on the carbonyl of imide. The addition of the second electron in the second reduction is
supported by the ability of the core to delocalize this extra electron density to reduce the Coulombic
repulsion of the similar charges.23 It was difficult to obtain the oxidation potentials of these electron
deficient compounds even with a CV measurement window up to +1 V vs Ag/AgNO3. Thus we have
estimated the HOMO levels, by subtracting the LUMO energy values from the optical band gap that
was obtained from the absorption onset of the respective compounds in solutions. From the CV studies
it was found that the bayꢀannulated PEIs showed increased LUMO levels in comparison to PEI
(Fig.2b). A small increase of 0.15 eV in the LUMO level was noted in the case of 1, while 2 and 3
displayed a lowering of LUMO levels by 0.11 eV respectively, with respect to the LUMO of PEI
(Fig.2b). Thus in the case of compound 1, an increase in the HOMO level was observed, while that of
compound 2 and 3 remained fairly unaltered.
9
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 24
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 3. Optimized geometry of compounds PEI, 1, 2 and 3 (a); HOMO (b) and LUMO (c) frontier
molecular orbitals of compounds of the same at the B3LYP/6ꢀ31G(dp) level. EH and EL denote
energies of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular
orbital (LUMO), respectively.
We further probed the energy levels and their separations with the help of DFT calculations. The
energy minimized structures for PEI, 1, 2 and 3 are showed in Fig.3a. Images of frontier molecular
orbitals (FMOs) and the differences in their energies offer information about the length of conjugation
and the separation of energy levels, which helps in comparing the PEI with its bayꢀannulated
derivatives. In the energyꢀminimized structures, we can notice the planarity of the perylene ring remains
unchanged after bayꢀannulation. The contours of the HOMO and LUMO of PBIs are shown in Fig. 3b
and c. The HOMOꢀLUMO energy levels of PEIs are distributed on the entire aromatic ring. Imide
groups are known to be closed chromophoric (electronically decoupled) systems. This is due to the
presence of nodes of the HOMO and LUMO orbitals on imide nitrogen atoms, while some electron
density is found to be distributed on the ester group or oxygen atoms. Thus the substitution at imide
nitrogen does not alter the optical properties significantly, but the bayꢀannulation is supposed to affect
10
ACS Paragon Plus Environment

Page 11 of 24
The Journal of Organic Chemistry
the HOMOꢀLUMO levels. In the case of bayꢀannulated derivatives, HOMO and LUMOs were found to
be spreading over heteroatoms (for compounds 2 and 3). In the case of compound 1, only the LUMO
was distributed on the N atom, which serves as a node for HOMO. In fact, the HOMO and LUMO
levels of bayꢀannulated PEIs have increased in comparison to the simple PEI. The HOMOꢀLUMO
separations for PEI, 1, 2 and 3 were found to be 2.65, 2.82, 2.85 and 2.83 eV respectively.
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
CONCLUSIONS
We have presented an easy microwave assisted method for the synthesis of unsymmetric PEIs by
treating PTEs with requisite amines, in good yield. This microwave assisted synthetic method has a
wide substrate scope including various PTEs, bayꢀannulated PTEs, aliphatic amines, aromatic amines
and benzyl amines. Especially, application of this method to bayꢀannulated tetraesters, provide bayꢀ
annulated PEIs, which provide new avenues in organic semiconductors. Photophysical and
electrochemical properties of the bayꢀannulated PEIs were studied in comparison with the simple PEI
along with the DFT calculations to visualize the electronic energy levels. Moreover, this synthetic
method provides an easy access to synthesize unsymmetrical perylene bisimides, which are very
important materials from the viewpoint of organic electronics as well as supramolecular selfꢀassembly.
EXPERIMENTAL SECTION
Commercially available chemicals were used without any purification; solvents were dried following
the standard procedures. Chromatography was performed using either neutral aluminum oxide. For thin
layer chromatography, aluminum sheets preꢀcoated with silica gel were employed. IR spectra were
recorded on a Perkin Elmer IR spectrometer at normal temperature by using KBr pellet. The spectral
positions are given in wave number (cmꢀ1) unit. NMR spectra were recorded using Varian Mercury 400
1
MHz (at 298K) or Bruker 600 MHz NMR spectrometer. For H NMR spectra, the chemical shifts are
reported in ppm relative to TMS as an internal standard. Coupling constants are given in Hz. Mass
spectra were determined from MALDIꢀTOF mass spectrometer using αꢀCyanoꢀ4ꢀhydroxycinnamic acid
as a matrix or High Resolution Mass Spectrometer (AgilantꢀQTOFꢀ450). Elemental analysis was carried
out with Perkin Elmerꢀ2400, Series II, CHNSO Analyser. UVꢀVis spectra were obtained by using
PerkinꢀElmer Lambda 750, UV/VIS/NIR spectrometer. Fluorescence emission spectra in solution state
as well as thin film state were recorded with Horiba Fluoromaxꢀ4 fluorescence spectrophotometer or
Perkin Elmer LS 50B spectrometer. Cyclic Voltammetry studies were performed using a Versa Stat 3
(Princeton Applied Research) Electrochemical workstation. Microwave reactions were performed in
CEM discover instrument. All microwave reactions were performed in sealed tube reaction condition
11
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 24
and the reaction temperatures were monitored by internal probe and the temperature is reached or
maintained in each experiment. Other reactions were performed in oil bath condition and reaction
temperature was monitored by external probe. The quantum mechanical calculations of molecular
properties were performed using DFT by employing the combination of Becke3–Lee–Yang–Parr
(B3LYP) hybrid functional and 6ꢀ31G(d,p) basis set using the Gaussian09 package24, to obtain the
information related to molecular conformation and frontier molecular orbitals (HOMO–LUMO) of all
the compounds. Full geometry optimizations were carried out by using the Hatree–Fock method with
the 321ꢀG basic set followed by DFT calculations using the B3LYP hybrid functional and the 6ꢀ
31G(d,p) standard basis set because of the successful application of such methods for larger organic
molecules. The absence of imaginary frequency ensured the stable structure of compound.
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
Tetrakis(butyl) perylene-3,4,9,10-tetracarboxylate (4)18 Perylene tetracarboxylic dianhydride (2g, 5
mmol, 1 equiv.) was dissolved in 30 mL aqueous KOH (1.5g, 27 mmol, 5.4 equiv.) solution and stirred
o
at 70 C for 0.5 h. The solution was filtered and pH value of filterate was adjusted to 8ꢀ9 using 10%
HCl. Then Aliquat 336 (0.72g, 1.8 mmol, 0.4 equiv.) and KI (0.17g, 1 mmol, 0.2 equiv.) were charged
into the solution and then stirred vigorously for 10 min. 1ꢀBromobutane (4g, 31 mmol, 6 equiv.) was
added to this reaction mixture. After the addition the reaction mixture was refluxed for 12 h until a red
oil floats on the top and the rest of the solution becomes clear. Subsequently, chloroform (10 mL) was
poured into the mixture and filtered through the celite bed to remove unreacted part and the celite bed
was washed with chloroform. This chloroform layer was separated and washed twice with 15% sodium
chloride solution, dried over sodium sulfate and concentrated in vacuo to get a viscous concentrate.
Methanol was added to precipitate the compound from this concentrate. The solid was precipitated,
filtered and dried in vacuum. Yield of this compound was 76%.
4: Rf = 0.6 (20% EtoAcꢀHexane); orange solid, yield: 2.48g, 76%; IR (KBr pellet) vmax in cmꢀ1 2960
1
(CꢀH), 2930 (CꢀH), 2872 (CꢀH), 1725 (C=O), 1627 (C=C), 1590 (C=C); H NMR (600 MHz, CDCl3,
299 K): 8.04 (d, J = 7.8Hz, 4H, HAr), 7.90 (d, J = 7.8Hz, 4H, HAr), 4.36ꢀ4.34 (m, 8H, 4 × ꢀOCH2),
13
1.82ꢀ1.78 (m, 8H, 4 × ꢀOCH2ꢀCH2), 1.62ꢀ1.49 (m, 8H, 4 ×CH2), 1.02ꢀ1.0 (m, 12H, 4 × ꢀCH3) ; C
NMR (150 MHz, CDCl3, 298.1K): 168.8, 132.9, 130.5, 129, 128.8, 121.5, 65.5, 30.9, 19.5, 14 ;
MALDIꢀTOF : exact mass calculated for C40H44O8 (M+): 652.3, found: 652.5; HRMS (APCI mode)
exact mass calculated for C40H44O8 (Mꢀ): 652.3042, found: 652.3297.
Tetrakis(butyl) 1-nitroperylene-3,4,9,10-tetracarboxylate (5)18 To a solution of 4 (0.9g, 1.4 mmol, 1
equiv.) in dichloromethane (15 mL), added NaNO2 (0.1g, 0.7 mmol, 1 equiv.) at 0 oC and stirred. To this
well stirred suspension, 69% HNO3 (3.42 mmol, 5 equiv., 10% solution in dichloromethane) was added
12
ACS Paragon Plus Environment

Page 13 of 24
The Journal of Organic Chemistry
o
dropwise. This mixture was stirred at 0 C for 1 h. The reaction mixture was poured into water and
extracted with dichloromethane (25 mL). Finally, organic layer was dried over anhyd Na2SO4 and
concentrated. The crude product was purified by column chromatography on neutral alumina. Elution
with 50% dichloromethaneꢀhexane yielded the desired product. Yield of this nitro compound was 90%.
1
2
3
4
5
6
7
8
9
5: Rf = 0.6 (20% EtoAcꢀHexane); red viscous liquid, yield: 0.88g, 90%; IR (KBr pellet) vmax in cmꢀ1
2958 (CꢀH), 2928 (CꢀH), 2872 (CꢀH), 1725 (C=O), 1660 (C=C), 1591 (C=C), 1533 (NꢀO), 1356 (NꢀO);
1H NMR (600 MHz, CDCl3, 299 K): 8.34ꢀ8.29 (m, 2H, HAr), 8.24 (s, 1H, HAr), 8.18 (d, J = 6Hz, 1H,
HAr), 8.10 (d, J = 6Hz, 1H, HAr), 7.95ꢀ7.93 (m, 1H, HAr), 7.86ꢀ7.84 (m, 1H, HAr), 4.37ꢀ4.33 (m, 8H, 4 ×
ꢀOCH2), 1.81ꢀ1.77 (m, 8H, 4 × ꢀOCH2ꢀCH2), 1.51ꢀ1.46 (m, 8H, 4 ×CH2), 1.01ꢀ0.98 (m, 12H, 4 × ꢀCH3),
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
;
13C NMR (150 MHz, CDCl3, 298.1K): 168.2, 168, 167.9, 166.8, 146.2, 133.6, 132.3, 132.1, 131.4,
131.3, 130.8, 130.4, 129.9, 129.6, 129.1, 128.5, 128.4, 127.5, 126.6, 125.7, 123.2, 122.7, 66.2, 65.9,
65.8, 65.7, 30.7, 30.7, 29.8, 19.4, 14; MALDIꢀTOF : exact mass calculated for C40H43NO10 (Mꢀ): 697.3,
found: 697.8; Elemental analysis calcd. (%) for C40H43NO10: C 68.85, H 6.21, N 2.01; found: C 69.19,
H 6.26, N 2.11.
Tetrakis(butyl) 1H-phenanthro[1,10,9,8-cdefg]carbazole-3,4,9,10-tetracarboxylate18(6) A mixture
of compound 5 (0.84g, 0.6 mmol) and triethyl phosphite (7 mL) were refluxed for 4 h under argon
atmosphere. Reaction mixture was cooled to room temperature and methanol was added to this solution
to precipitate the compound. This precipitated product was filtered off and washed with water, dried in
vacuum. Further purification was done by repeated recrystallization from dichloromethaneꢀmethanol
system. Yield of this carbazole was 60%.
6: Rf = 0.6 (20% EtoAcꢀHexane); yellow solid, yield: 0.48 g, 60%; IR (KBr pellet) vmax in cmꢀ1 3458
1
(NꢀH), 2959 (CꢀH), 2927 (CꢀH), 2853 (CꢀH), 1722 (C=O), 1637 (C=C), 1593 (C=C); H NMR (600
MHz, CDCl3, 299 K): 9.42 (s, 1H, NH), 8.01 (d, J = 7.8 Hz, 2H, HAr), 7.94ꢀ7.92 (m, 4H, HAr), 4.54ꢀ4.5
(m, 8H, 4 × ꢀOCH2), 1.97ꢀ1.92 (m, 8H, 4 × ꢀOCH2ꢀCH2), 1.66ꢀ1.61 (m, 8H, ꢀCH2), 1.10 (t, J = 7.2Hz,
12H, 4 × ꢀCH3); 13C NMR (150 MHz, CDCl3, 298.1K): 169.9, 130.9, 130.1, 128.4, 127.4, 127.1, 122.6,
121.5, 119.2, 117.6, 65.7, 65.6, 31.1, 31.1, 19.6, 19.6, 14.1 ; MALDIꢀTOF : exact mass calculated for
C40H43NO8 (M+): 665.3, found:665.7; Elemental analysis calcd. (%) for C40H43NO8: C 72.16, H 6.51, N
2.1; found: C 72.06, H 6.45, N 2.08.
Tetrabutyl 1-ethyl-1H-phenanthro [1,10,9,8- cdefg]carbazole-3,4,9,10-tetracarboxylate (7)18A
mixture of compound (6, 0.16g, 0.24 mmol, 1 equiv.), sodium hydride (0.03 g, 60% in wax, 0.36 mmol,
3 equiv.) and ethyl iodide (0.06g, 0.18 mmol, 1.53 equiv.) in a dry THF was refluxed for overnight
under argon atmosphere. After cooling to room temperature, water (2 mL) was added to the mixture and
13
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 24
stirred for 10 min at 0 oC. The resulting mixture was extracted with dichloromethane and the extract was
washed with water and brine. Finally, organic layer was dried over anhyd. Na2SO4 and concentrated.
The crude residue obtained was purified by column chromatography on neutral alumina. Elution with
hexane, 50% dichloromethaneꢀhexane solution followed by dichloromethane yielded the desired
product with 75% yield.
1
2
3
4
5
6
7
8
9
7: Rf = 0.6 (15% EtoAcꢀHexane); Yellowish solid, yield: 0.126 g, 75%; IR (KBr pellet) vmax in cmꢀ1
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
1
2959 (CꢀH), 2929 (CꢀH), 2873 (CꢀH), 1720 (C=O), 1586 (C=C); H NMR (600 MHz, CDCl3, 299 K):
8.49 (d, J = 7.8Hz, 2H, HAr), 8.22 (s, 2H, HAr), 8.18 (d, J = 7.8Hz, 2H, HAr), 4.74ꢀ4.7 (m, 2H, ꢀNꢀCH2),
4.45ꢀ4.42 (m, 8H, 4 × ꢀOCH2), 1.87ꢀ1.82 (m, 8H, 4 × ꢀOCH2ꢀCH2), 1.56ꢀ1.5 (m, 8H, 4 × ꢀCH2 ), 1.25
13
(bs, 3H, ꢀNꢀCH2ꢀCH3), 1.04ꢀ1.01 (m, 12H, 4 × ꢀCH3); C NMR (150 MHz, CDCl3, 298.1K): 169.7,
169.3, 131.9, 131.4, 129.2, 128.2, 127.8, 124.4, 123.3, 121.9, 118.1, 117.9, 65.7, 65.6, 40.8, 31, 30.9,
29.9, 19.5, 16.7, 14.1, 14.09; MALDIꢀTOF: exact mass calculated for C42H47NO8 (M+): 693.3, found:
693.7; HRMS (APCI mode) exact mass calculated for C42H48NO8 (MH+): 694.3374, found: 694.3371.
Dibutyl 6-ethyl-9-octadecyl-8,10-dioxo-6,8,9,10-tetrahydroindolo [2',3',4',5':4,10,5] anthra[2,1,9-
def] isoquinoline-3,4-dicarboxylate (1) A mixture of compound (5, 0.17g, 0.25 mmol, 1 equiv.), 1ꢀ
aminoꢀoctadecane (0.073 g, 0.27 mmol, 1.1 equiv.) and imidazole (1 g) were taken in microwave vessel,
flushed with nitrogen and put in microwave reactor. The mixture was heated to 165 oC for 35 minutes at
35 W. After cooling, reaction mixture was poured in 2N HCl and extracted with chloroform. Organic
mixture was washed with water and saturated sodium chloride solution. The crude compound was
purified by neutral alumina column chromatography using 50% chloroformꢀhexane system yields the
desired product.
1: Rf = 0.4 (20% EtoAcꢀHexane); Red waxy solid, yield: 0.11g, 55%; IR (KBr pellet) vmax in cmꢀ1 2958
1
(CꢀH), 2924 (CꢀH), 2854 (CꢀH), 1712 (C=Oester), 1695 (C=Oimide), 1679 (C=Oimide), 1597 (C=C); H
NMR (600 MHz, CDCl3, 299 K): 8.88 (s, 1H, HAr), 8.81 (d, J = 7.8 Hz, 1H, HAr), 8.75 (s, 2H, HAr),
8.44 (s, 1H, HAr),8.37 (d, J = 7.8 Hz, 1H, HAr), 4.85ꢀ4.81 (m, 2H, ꢀNCH2), 4.47ꢀ4.44 (m, 4H, 2 × ꢀ
OCH2), 4.33 (m, 2H, NꢀCH2), 1.86ꢀ1.83 (m, 6H, CH2), 1.74 (t, 3H, ꢀNCH2CH3), 1.55ꢀ1.24 (m, 34H,
alkyl chain), 1.03ꢀ1.00 (m, 6H, 2 × ꢀCH3 ), 0.88ꢀ0.86 (m, 3H, ꢀCH3); 13C NMR (150 MHz, CDCl3,
298.1K): 169.3, 168.8, 165, 163.8, 132.7, 132.3, 131.6, 130.5, 130.4, 130.4, 127.8, 126.8, 124, 123.5,
123, 122.8, 121.4, 120, 119.9, 119.7, 118.8, 117.8, 117.3, 116.8, 66, 65.9, 41.1, 40.9, 32.1, 31, 30.9,
29.9, 29.9, 29.9, 29.9, 29.6, 22.9, 19.6, 19.6, 16.7, 14.3, 14.1; MALDIꢀTOF exact mass calculated for
C52H66N2O6 (Mꢀ): 814.5, found: 814.9; HRMS (APCI mode) exact mass calculated for C52H67N2O6
(MH+): 815.4994, found: 815.4993.
14
ACS Paragon Plus Environment

Page 15 of 24
The Journal of Organic Chemistry
Tetrakis(butyl) peryleno[1,12-bcd]thiophene-3,4,9,10-tetracarboxylate(8)18A mixture of compound
(5, 0.17 g, 0.26 mmol) and Sulfur powder (0.083 g, 2.602 mmol) was heated to dissolve in Nꢀ
methylpyrrolidone (10 mL) at 70 oC for 30 min. and then refluxed at 180 oC under Argon atmosphere for
overnight by TLC monitoring. After cooling to room temperature, 2 M HCl was added, the precipitate
was filtered, washed with water and dried. The crude product was purified by column chromatography
on neutral alumina. Elution with 20ꢀ30% DCMꢀHexanes system followed by 50% DCMꢀHexane system
yields the desired product. Further purification was done by the addition of concentrated solution of
compound in cold methanol.
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
8: Rf = 0.6 (20% EtoAcꢀHexane); orange solid, yield: 0.1g, 55%; IR (KBr pellet) vmax in cmꢀ1 2955 (Cꢀ
H), 2927 (CꢀH), 2869 (CꢀH), 1720 (C=O), 1583 (C=C); 1H NMR (600 MHz, CDCl3, 299 K): 8.59ꢀ8.57
(m, 4H, HAr), 8.27 (d, J = 7.8Hz, 2H, HAr), 4.44ꢀ4.41 (m, 8H, 4 × ꢀOCH2), 1.87ꢀ1.81 (m, 8H, 4 × OCH2ꢀ
CH2), 1.56ꢀ1.51 (m, 8H, 4 × CH2), 1.04ꢀ1.01 (m, 12H, 4 × ꢀCH3); 13C NMR (150 MHz, CDCl3,
298.1K): 168.9, 168.7, 135.2, 132.1, 130.6, 130, 129.4, 126.3, 125.6, 125.4, 121.9, 65.8, 65.7, 30.9,
30.92, 19.6, 19.5, 14.1; MALDIꢀTOF : exact mass calculated for C40H42O8S (M+): 682.3, found:682.4;
HRMS (APCI mode) exact mass calculated for C40H42O8S (M+): 682.2595, found: 682.2578.
Dibutyl 9-octadecyl-8,10-dioxo-9,10-dihydro-8H-thieno[2',3',4',5':12,1] peryleno[3,4-cd]pyridine-
3,4-dicarboxylate (2) A mixture of compound (6, 0.15g, 0.22 mmol, 1 equiv.), 1ꢀaminoꢀoctadecane
(0.065 g, 0.24 mmol, 1.1 equiv.) and imidazole (1 g) were taken in microwave vessel, flushed with
nitrogen and put in microwave reactor. The mixture was heated to 165 oC for 35 minutes at 35 W. After
cooling, reaction mixture was poured in 2N HCl and extracted with chloroform. Organic mixture was
washed with water and saturated sodium chloride solution. The crude compound was purified by neutral
alumina column chromatography using 50% chloroformꢀhexane to get the desired product.
2: Rf = 0.4 (20% EtoAcꢀHexane); Orange red waxy solid, yield: 0.097g, 55%; IR (KBr pellet) vmax in
cmꢀ1 2959 (CꢀH), 2924 (CꢀH), 2853 (CꢀH), 1727 (C=Oester), 1697 (C=Oimide), 1655 (C=Oimide), 1629
(C=C), 1590 (C=C); 1H NMR (600 MHz, CDCl3, 299 K): 8.94 (s, 1H, HAr), 8.58 (s, 1H, HAr), 8.57 (d, J
= 8.4 Hz, 1H, HAr), 8.51 (d, J = 7.8 Hz, 1H, HAr), 8.4 (d, J = 7.8 Hz, 1H, HAr), 8.29 (d, J = 7.8 Hz, 1H,
HAr), 4.48ꢀ4.44 (m, 4H, 2 × ꢀOCH2), 4.28ꢀ4.25 (m, 2H, NꢀCH2), 1.9ꢀ1.82 (m, 6H, CH2), 1.59ꢀ1.24 (m,
13
34H, alkyl chain), 1.07ꢀ1.03 (m, 6H, 2 × ꢀCH3), 0.87 (t, J = 7.2 Hz 3H, ꢀCH3); C NMR (150 MHz,
CDCl3, 298.1K): 168.3, 168.2, 163.4, 163.1, 137.1, 135, 132.4, 131.1, 130.8, 130.5, 130.3, 129.2, 128.7,
128.5, 126, 125.7, 125.4, 124.8, 124.4, 122.4, 121.1, 120.9, 120.7, 120.5, 66.1, 65.9, 41.1, 32.1, 29.9,
29.9, 29.9, 29.9, 29.6, 22.9, 19.6, 19.6, 14.3, 14.1, 14.12; MALDIꢀTOF exact mass calculated for
C50H61NO6S (Mꢀ): 803.4, found: 803.6; HRMS (APCI mode) exact mass calculated for C50H62NO6S
(M+): 804.4292, found: 804.4295.
15
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 24
Tetrakis(butyl) peryleno[1,12-bcd] selenophene-3,4,9,10-tetracarboxylate (9)18 A mixture of
compound (5, 0.18g, 0.26 mmol) and Selenium powder (0.21g, 2.602 mmol) was heated to dissolve in
Nꢀmethylpyrrolidone (10 mL) at 70 oC for 30 min. and then refluxed at 180 oC under Ar atmosphere for
overnight until the starting material could not be detected by TLC. After cooling to room temperature, 2
M HCl was added, then the precipitate was filtered, washed with water and dried. The crude product
was purified by column chromatography on neutral alumina. Elution with 20ꢀ30% DCMꢀHexanes
system followed by 50% DCMꢀHexane system yields the desired product. Further purification was done
by addition of concentrate solution of compound in cold methanol gives the product.
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
9: Rf = 0.6 (20% EtoAcꢀHexane); orange solid, yield: 0.103g, 55%; IR (KBr pellet) vmax in cmꢀ1 2955
(CꢀH), 2927 (CꢀH), 2869 (CꢀH), 1719 (C=O), 1582 (C=C); 1H NMR (400 MHz, CDCl3, 299 K): 8.57ꢀ
8.53 (m, 4H, HAr), 8.24ꢀ8.23 (m, 2H, HAr), 4.41 (bs, 8H, 4 × ꢀOCH2), 1.86ꢀ1.82 (m, 8H, 4 × OCH2ꢀ
CH2), 1.55ꢀ1.51 (m, 8H, 4 × ꢀCH2), 1.04ꢀ1.01 (m, 12H, 4 × ꢀCH3); 13C NMR (100 MHz, CDCl3,
298.1K): 168.9, 168.7, 137.6, 133.3, 132.2, 129.9, 129.3, 128.7, 128.7, 127, 125.7, 121.6, 65.8, 65.6,
30.9, 30.9, 19.5, 19.5, 14.1, 14.08; MALDIꢀTOF : exact mass calculated for C40
H42
O
Se(M+):730.2,
8
found: 730.8; Elemental analysis calcd. (%) for C40H42O8Se: C 65.84, H 5.80; found: C 65.74, H 5.80.
Dibutyl
9-octadecyl-8,10-dioxo-9,10-dihydro-8H-selenopheno[2',3',4',5':12,1]
peryleno[3,4-
cd]pyridine-3,4-dicarboxylate (3) A mixture of compound (7, 0.15g, 0.21 mmol, 1 equiv.), 1ꢀaminoꢀ
octadecane (0.061g, 0.23 mmol, 1.1 equiv.) and imidazole (1g) were taken in microwave vessel, flushed
o
with nitrogen and placed in microwave reactor. The mixture was heated to 165 C for 35 minutes at 35
W. After cooling, reaction mixture was poured into 2N HCl and extracted with chloroform. Organic
mixture was washed with water and saturated sodium chloride solution. The crude compound was
purified by neutral alumina column chromatography using 50% chloroformꢀhexane system to yield the
desired product.
3: Rf = 0.4 (20% EtoAcꢀHexane); Dark red waxy solid, yield: 0.096 g, 55%; IR (KBr pellet) vmax in cmꢀ
1
2959 (CꢀH), 2924 (CꢀH), 2853 (CꢀH), 1724 (C=Oester), 1701 (C=Oimide), 1651 (C=Oimide), 1597 (C=C);
1H NMR (600 MHz, CDCl3, 299 K): 8.91 (s, 1H, HAr), 8.57 (s, 1H, HAr), 8.52 (d, J = 7.8 Hz, 1H, HAr),
8.42 (d, J = 7.8 Hz, 1H, HAr), 8.31 (d, J = 8.4 Hz, 1H, HAr), 8.25 (d, J = 7.8 Hz, 1H, HAr), 4.47ꢀ4.44 (m,
4H, 2 × ꢀOCH2), 4.26ꢀ4.23 (m, 2H, NꢀCH2), 1.9ꢀ1.81 (m, 6H, CH2), 1.57ꢀ1.24 (m, 34H, alkyl chain),
13
1.07ꢀ1.03 (q, 6H, 2 × ꢀCH3 ), 0.87 (t, J = 7.2 Hz, 3H, ꢀCH3); C NMR (150 MHz, CDCl3, 298.1K):
168.4, 168.2, 163.3, 163.1, 139.8, 137.4, 133.3, 132.6, 131.4, 131.1, 130.5, 130, 129.1, 128.4, 128.2,
126.1, 125.7, 124.6, 122.3, 122, 120.8, 120.5, 119.9, 66, 65.9, 41, 32.1, 30.9, 29.9, 29.7, 29.6, 27.6,
22.9, 19.6, 14.3, 14.1; MALDIꢀTOF exact mass calculated for C50H61NO6Se (Mꢀ): 851.4, found: 851.6;
16
ACS Paragon Plus Environment

Page 17 of 24
The Journal of Organic Chemistry
Elemental analysis calcd. (%) for C50H61NO6Se: C 70.57, H 7.23, N 1.65; found: C 70.29, H 7.44, N
1.57.
1
2
3
4
5
6
7
2-Octadecylisoindoline-1,3-dione (13)19 Potassium phthalimide (2.4g, 12.9 mmol) was added to the
o
solution of 1ꢀbromoꢀoctadecane (4g, 12.1 mmol) in DMF. The reaction mixture was stirred at 90 C for
8
9
18 h, cooled the reaction mixture to room temperature, poured the mixture in water and extracted with
methylene chloride several times. The combined organic layer was washed with 0.2 N KOH, water,
saturated NH4Cl, dried over anhyd Na2SO4 and concentrated under reduced pressure after filtration. The
resulting crude compound was purified by column chromatography using methylene chloride as eluent
to give white solid in 95% yield.
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: Rf = 0.4 (10% EtoAcꢀHexane); white solid, yield: 4.55g, 95%; IR (KBr pellet) vmax in cmꢀ1 2965 (Cꢀ
H), 2917 (CꢀH), 2849 (CꢀH), 1775 (C=O), 1701 (C=O); 1H NMR (600 MHz, CDCl3, 299 K): 7.83ꢀ7.82
(m, 2H, HAr), 7.70ꢀ7.69 (m, 2H, HAr), 3.67ꢀ3.65 (m, 2H, ꢀNCH2), 1.68ꢀ1.64 (m, 2H, ꢀNCH2ꢀCH2), 1.31ꢀ
1.23 (m, 30H, alkyl chain), 0.88ꢀ0.85 (m, 3H, ꢀCH3); 13C NMR (150 MHz, CDCl3, 298.1K): 168.7, 134,
132.4, 123.3, 38.3, 32.1, 29.9, 29.8, 29.7, 29.6, 29.4, 27.1, 22.9, 14.3; HRMS (ESI mode) exact mass
calculated for C26H42NO2 (MH+): 400.3210, found: 400.3217.
1-amino-octadecane (14)19 A mixture of compound (11) (4g, 10 mmol, 1 equiv.) and 80% hydrazine
o
hydrate (1.5g, 30.2 mmol, 3 equiv.) in methanol were stirred at 95 C for 1 h. after the disappearance of
starting imide, methanol was removed under reduced pressure and residue was diluted with
dichloromethane and washed with 10% KOH. The combined aqueous layer was extracted with
dichloromethane. The combined organic layer was washed with brine and dried over anhyd Na2SO4.
After removal of solvent the product was obtained as a white solid in 95% yield.
14: Rf = 0.3 (20% EtoAcꢀHexane); white solid, yield: 2.6g, 95%; IR (KBr pellet) vmax in cmꢀ1 3334 (Nꢀ
1
H), 2956 (CꢀH), 2918 (CꢀH), 2851 (CꢀH); H NMR (600 MHz, CDCl3, 299 K): 2.67ꢀ2.64 (m, 2H, ꢀ
NCH2), 1.41ꢀ1.40 (m, 2H, ꢀNCH2ꢀCH2), 1.34 (s, 2H, NH2), 1.24ꢀ1.23 (m, 30H, alkyl chain), 0.87ꢀ0.84
(m, 3H, ꢀCH3); 13C NMR (150 MHz, CDCl3, 298.1K): 42.5, 34.1, 32.1, 29.9, 29.7, 29.6, 27.1, 22.9,
14.3; HRMS (ESI mode) exact mass calculated for C18H40N (MH+): 270.3155, found: 270.3152.
Dibutyl 2-octadecyl-1,3-dioxo-2,3-dihydro-1H-benzo [10,5] anthra[2,1,9-def] isoquinoline-8,9-
dicarboxylate (PEI) A mixture of compound (4, 0.3g, 0.46 mmol, 1 equiv.), 1ꢀaminoꢀoctadecane
(0.138g, 51 mmol, 1.1 equiv.) and imidazole (1.1g) were taken in microwave vessel, flushed with
nitrogen and put in microwave reactor. The mixture was heated to 165 oC for 35 minutes at 35 W. After
cooling, the reaction mixture was poured in 2N HCl and extracted with chloroform. Organic mixture
was washed with water and brine solution. The crude compound was purified by neutral alumina
17
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 24
column chromatography using 50% chloroformꢀhexane system yields the desired product. This was
further purified by recrystallization from DCMꢀmethanol system.
1
2
3
4
5
6
7
8
9
PEI: Rf = 0.4 (20% EtoAcꢀHexane); Bright orange solid, yield: 0.195g, 55%; IR (KBr pellet) vmax in
cmꢀ1 2958 (CꢀH), 2923 (CꢀH), 2852 (CꢀH), 1714 (C=Oester), 1693 (C=Oimide), 1649 (C=Oimide), 1618
(C=C), 1597 (C=C); 1H NMR (600 MHz, CDCl3, 299 K): δ 8.53 (d, J = 8.4 Hz, 2H, HAr), 8.34 (d, J =
7.8 Hz, 4H, HAr), 8.05 (d, J = 7.8 Hz, 2H, HAr), 4.37ꢀ4.34 (m, 4H, 2 × ꢀOCH2), 4.19ꢀ4.17 (m, 2H, Nꢀ
CH2), 1.83ꢀ1.73 (m, 6H, CH2), 1.54ꢀ1.24 (m, 34H, alkyl chain), 1.01 (t, J = 7.2 Hz, 6H, 2 × ꢀCH3 ),
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
0.88ꢀ0.86 (m, 3H, ꢀCH3); C NMR (150 MHz, CDCl3, 298.1K): δ 168.5, 163.7, 135.6, 132.3, 132.1,
131.5, 130.5, 129.4, 129.3, 129.2, 126.1, 122.7, 122.3, 122, 65.8, 40.8, 32.1, 30.8, 29.9, 29.9, 29.86,
29.8, 29.6, 29.58, 28.4, 27.4, 22.9, 19.5, 14.3, 14; MALDIꢀTOF exact mass calculated for C50H64NO6
(MH+): 774.5, found: 774.6; HRMS (APCI mode) exact mass calculated for C50H64NO6 (MH+):
774.4728, found: 774.4730.
Dibutyl
1,3-dioxo-2-phenyl-2,3-dihydro-1H-benzo[10,5]anthra[2,1,9-def]isoquinoline-8,9-
dicarboxylate (10) A mixture of compound (4, 0.1g, 0.15 mmol, 1 equiv.), aniline (0.016g, 0.17 mmol,
1.1 equiv.) and imidazole (0.7 g) were taken in microwave vessel, flushed with nitrogen and put in
o
microwave reactor. The mixture was heated to 165 C for 35 minutes at 35 W. After cooling, reaction
mixture was poured into 2N HCl and extracted with chloroform. Organic mixture was washed with
water and saturated sodium chloride solution. The crude compound was purified by neutral alumina
column chromatography using 50% DCMꢀhexane system followed by DCM yields the desired product.
This was further purified by recrystallization from DCMꢀmethanol system.
10: Rf = 0.4 (20% EtoAcꢀHexane); Bright red solid, yield: 0.05g, 55%; IR (KBr pellet) vmax in cmꢀ1
1
2959 (CꢀH), 2931 (CꢀH), 2872 (CꢀH), 1707 (C=Oester), 1660 (C=Oimide), 1593 (C=C); H NMR (600
MHz, CDCl3, 299 K): δ 8.63 (d, J = 7.8 Hz, 2H, HAr), 8.44ꢀ8.40 (m, 4H, HAr), 8.10 (d, J = 8.4 Hz, 2H,
HAr), 7.60ꢀ7.57 (m, 2H, HArꢀphenyl), 7.52ꢀ7.49 (m, 1H, HArꢀphenyl), 7.38ꢀ7.37 (m, 2H, HArꢀphenyl), 4.38ꢀ4.35
(m, 4H, 2 × ꢀOCH2), 1.83ꢀ1.78 (m, 4H, CH2), 1.54ꢀ1.48 (m, 4H, CH2 CH3), 1.01 (t, J = 7.2 Hz, 6H, 2 × ꢀ
13
CH3 ); C NMR (150 MHz, CDCl3, 298.1K): δ 168.4, 164, 136.1, 135.5, 132.3, 132.28, 132, 130.6,
129.8, 129.7, 129.4, 129.3, 129, 128.8, 126.4, 123, 122.4, 122.1, 65.8, 30.8, 19.5, 14; MALDIꢀTOF
exact mass calculated for C38H32NO6 (MH+): 598.2, found: 598.3; HRMS (APCI mode) exact mass
calculated for C38H32NO6 (MH+): 598.2224, found: 598.2224.
Dibutyl
2-benzyl-1,3-dioxo-2,3-dihydro-1H-benzo[10,5]anthra[2,1,9-def]isoquinoline-8,9-
dicarboxylate (11) A mixture of compound (4, 0.1g, 0.15 mmol, 1 equiv.), benzyl amine (0.018g, 0.17
mmol, 1.1 equiv.) and imidazole (0.7 g) were taken in microwave vessel, flushed with nitrogen and put
18
ACS Paragon Plus Environment

Page 19 of 24
The Journal of Organic Chemistry
in microwave reactor. The mixture was heated to 165 oC for 35 minutes at 35 W. After cooling, reaction
mixture was poured in 2N HCl and extracted with chloroform. Organic mixture was washed with water
and saturated sodium chloride solution. The crude compound was purified by neutral alumina column
chromatography using 50% DCMꢀhexane system followed by DCM yields the desired product. This
was further purified by recrystallization from DCMꢀmethanol system.
1
2
3
4
5
6
7
8
9
11: Rf = 0.4 (20% EtoAcꢀHexane); Bright orange solid, yield: 0.054g, 58%; IR (KBr pellet) vmax in cmꢀ1
2960 (CꢀH), 2933 (CꢀH), 2873 (CꢀH), 1720 (C=Oester), 1697 (C=Oimide), 1657 (C=Oimide), 1594 (C=C);
1H NMR (600 MHz, CDCl3, 299 K): δ 8.41 (d, J = 7.8 Hz, 2H, HAr), 8.22 (d, J = 7.8 Hz, 2H, HAr), 8.17
(d, J = 6 Hz, 2H, HAr), 8.01 (d, J = 7.8 Hz, 2H, HAr), 7.61 (d, J = 7.8 Hz, 2H, HArꢀphenyl), 7.37ꢀ7.35 (m,
2H, HArꢀphenyl), 7.29ꢀ7.27 (m, 1H, HArꢀphenyl), 5.38 (s, 2H, benzylꢀCH2), 4.36 (t, J = 6.6 Hz, 4H, 2 × ꢀ
OCH2), 1.83ꢀ1.79 (m, 4H, CH2), 1.54ꢀ1.48 (m, 4H, CH2 CH3), 1.03ꢀ1.00 (m, 6H, 2 × ꢀCH3 ); 13C NMR
(150 MHz, CDCl3, 298.1K): δ 168.4, 163.7, 137.5, 135.6, 132.1, 132.1, 131.6, 130.5, 129.4, 129.3,
129.2, 129.1, 128.7, 127.8, 125.9, 122.8, 122.1, 121.8, 65.8, 43.8, 30.8, 19.5, 14; MALDIꢀTOF exact
mass calculated for C39H34NO6 (MH+): 612.2, found: 612.4; HRMS (APCI mode) exact mass calculated
for C39H34NO6 (MH+): 612.2381, found: 612.2385.
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-Octadecyl-9-(3,4,5-tris(decyloxy)phenyl)anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10
(2H,9H)-tetraone (12) A mixture of compound (PEI, 0.042g, 0.05 mmol, 1 equiv.), 3,4,5ꢀ
tris(decyloxy)aniline (0.034g, 0.06 mmol, 1.1 equiv.), zinc acetate (0.01 g, 0.05 mmol, 1 equiv.) and
imidazole (0.5 g) were taken in microwave vessel, flushed with nitrogen and put in microwave reactor.
o
The mixture was heated to 165 C for 35 minutes at 35 W. After cooling, reaction mixture was poured
in 2N HCl and extracted with chloroform. Organic mixture was washed with water and saturated
sodium chloride solution. The crude compound was purified by neutral alumina column
chromatography using 50% DCMꢀhexane system, followed by DCM to obtain the desired product.
12: Rf = 0.4 (20% EtoAcꢀHexane); Dark red waxy solid, yield: 0.048g, 75%; IR (KBr pellet) vmax in cmꢀ
1
1
2958 (CꢀH), 2924 (CꢀH), 2854 (CꢀH), 1699 (C=Oimide), 1662 (C=Oimide), 1594 (C=C); H NMR (600
MHz, CDCl3, 299 K): δ 8.52ꢀ8.50 (m, 2H, HAr), 8.37ꢀ8.35 (m, 2H, HAr), 8.20ꢀ8.19 (m, 2H, HAr), 8.13ꢀ
8.12 (m, 2H, HAr), 4.17ꢀ4.15 (m, 2H, NꢀCH2), 4.06ꢀ4.04 (m, 2H, ꢀOCH2), 3.98ꢀ3.96 (m, 4H, 2 × ꢀ
OCH2), 1.83ꢀ1.73 (m, 8H, CH2), 1.54ꢀ1.24 (m, 74H, alkyl chain), 0.91ꢀ0.89 (m, 3H, ꢀCH3 ), 0.88ꢀ0.85
13
(m, 9H, ꢀCH3); C NMR (150 MHz, CDCl3, 298.1K): δ 163.4, 163, 153.9, 138.4, 134.2, 133.8, 131.3,
130.8, 130.1, 129.3, 128.7, 125.9, 125.8, 123.4, 123.3, 123.1, 122.9, 107, 73.7, 69.3, 41.1, 32.2, 32.1,
30.7, 30.1, 30, 29.9, 29.92, 29.8, 29.86, 29.72, 29.7, 29.68, 29.65, 29.6, 29.58, 28.3, 27.5, 26.4, 26.4, 23,
22.9, 14.4, 14.3, 14.3; MALDIꢀTOF exact mass calculated for C78H111N2O7 (MH+): 1187.8386, found:
19
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 24
1187.823; Elemental analysis calcd. (%) for C78H110N2O7: C 78.88, H 9.34, N 2.36; found: C 78.82, H
9.39, N 2.46.
1
2
3
4
5
6
7
8
9
ASSOCIATED CONTENT
Supporting 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
1
13
The Supporting Information is available free of charge on the ACS Publications website. H and C
NMR spectra of all new compounds, MALDIꢀTOF spectra of all new compounds, Experimental details
of photophysical and computational studies (PDF)
ACKNOWLEDGMENT
ASA acknowledge DSTꢀSERB and BRNSꢀDAE for funding this work through project No. SB/S1/PCꢀ
37/2012, DIA/2018/000030 and No. 2012/34/31/ BRNS/1039 respectively. CIF IIT Guwahati is
acknowledged for the analytical facilities. Ministry of Human Resource Development is acknowledged
for Centre of Excellence in FAST (F. No. 5ꢀ7/2014ꢀTSꢀVII). We acknowledge Dr. Chandan Mukherjee
for providing electrochemical workstation.
REFERENCES
1. (a)Würthner, F., Perylene Bisimide Dyes as Versatile Building Blocks for Functional
Supramolecular Architectures. Chem. Commun. 2004, 1564ꢀ1579; (b) Huang, C.; Barlow, S.;
Marder, S. R., Peryleneꢀ3, 4, 9, 10ꢀTetracarboxylic Acid Diimides: Synthesis, Physical
Properties, and Use in Organic Electronics. J. Org. Chem. 2011, 76, 2386ꢀ2407; (c) Chen, S.;
Slattum, P.; Wang, C.; Zang, L., SelfꢀAssembly of Perylene Imide Molecules into 1D
Nanostructures: Methods, Morphologies, and Applications. Chem. Rev. 2015, 115, 11967ꢀ
11998; (d) Würthner, F.; SahaꢀMöller, C. R.; Fimmel, B.; Ogi, S.; Leowanawat, P.; Schmidt, D.,
Perylene Bisimide Dye Assemblies as Archetype Functional Supramolecular Materials. Chem.
Rev. 2015, 116, 962ꢀ1052; (e) Law, K. Y., Organic Photoconductive Materials: Recent Trends
and Developments. Chem. Rev. 1993, 93, 449ꢀ486; (f) Xue, C.; Birel, O.; Gao, M.; Zhang, S.;
Dai, L.; Urbas, A.; Li, Q., Perylene Monolayer Protected Gold Nanorods: Unique Optical,
Electronic Properties and SelfꢀAssemblies, J. Phys. Chem. C 2012, 116, 10396−10404; (g) Xue,
C.; Xue, Y.; Dai, L; Urbas, A.; Li, Q., Sizeꢀ and ShapeꢀDependent Fluorescence Quenching of
Gold Nanoparticles on Perylene Dye, Adv. Optical Mater. 2013, 1, 581–587; (h) Xue, C.;
GutierrezꢀCuevas, K.; Gao, M.; Urbas, A.; Li, Q., Photomodulated SelfꢀAssembly of
20
ACS Paragon Plus Environment

Page 21 of 24
The Journal of Organic Chemistry
Hydrophobic Thiol Monolayerꢀ Protected Gold Nanorods and Their Alignment in Thermotropic
Liquid Crystal, J. Phys. Chem. C 2013, 117, 21603−21608; (i) Xue, C.; Birel, O.; Xue, Y.; Dai,
L.; Urbas, A.; (j) Li, Q., pH and Temperature Modulated Aggregation of Hydrophilic Gold
Nanorods with Perylene Dyes and Carbon Nanotubes, J. Phys. Chem. C 2013, 117, 6752−6758.
2. (a) Sivamurugan, V.; Kazlauskas, K.; Jursenas, S.; Gruodis, A.; Simokaitiene, J.; Grazulevicius,
J.; Valiyaveettil, S., Synthesis and Photophysical Properties of GlassꢀForming BayꢀSubstituted
Perylenediimide Derivatives. J. Phys. Chem. B 2010, 114, 1782ꢀ1789; (b) Miasojedovas, A.;
Kazlauskas, K.; Armonaite, G.; Sivamurugan, V.; Valiyaveettil, S.; Grazulevicius, J.; Jursenas,
S., Concentration Effects on Emission of BayꢀSubstituted Perylene Diimide Derivatives in a
Polymer Matrix. Dyes and Pigments 2012, 92, 1285ꢀ1291.
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
3. Benning, S.; Kitzerow, H.ꢀS.; Bock, H.; Achard, M.ꢀF., Fluorescent Columnar Liquid
Crystalline 3, 4, 9, 10ꢀTetraꢀ(Nꢀalkoxycarbonyl)ꢀPerylenes. Liquid Crystals 2000, 27, 901ꢀ906.
4. Langhals, H.; Karolin, J.; Johansson, L. B.ꢀÅ., Spectroscopic Properties of New and Convenient
Standards For Measuring Fluorescence Quantum Yields. J. Chem. Soc., Faraday Trans. 1998,
94, 2919ꢀ2922.
5. (a) Yang, M.; Lu, S.; Li, Y., Novel Electron Acceptors Based on Perylenetetracarboxylates for
Plastic Solar Cells. J. Mater. Sci. Lett. 2003, 22, 813ꢀ815; (b) Hassheider, T.; Benning, S.;
Lauhof, M.; Kitzerow, H.ꢀS.; Bock, H.; Watson, M. D.; Müllen, K., Organic Heterojunction
Photovoltaic Cells Made of Discotic, Mesogenic Materials. Mol. Cryst. Liq. Cryst. 2004, 413,
461ꢀ472.
6. Hassheider, T.; Benning, S. A.; Kitzerow, H. S.; Achard, M. F.; Bock, H., Color‐Tuned
Electroluminescence from Columnar Liquid Crystalline Alkyl Arenecarboxylates. Angew.
Chem. Int. Ed. 2001, 40, 2060ꢀ2063.
7. Arnaud, A.; Belleney, J.; Boué, F.; Bouteiller, L.; Carrot, G.; Wintgens, V., Aqueous
Supramolecular Polymer Formed from an Amphiphilic Perylene Derivative. Angew. Chem. Int.
Ed. 2004, 43, 1718ꢀ1721.
8. Seguy, I.; Jolinat, P.; Destruel, P.; Mamy, R.; Allouchi, H.; Courseille, C.; Cotrait, M.; Bock, H.,
Crystal and Electronic Structure of A Fluorescent Columnar Liquid Crystalline Electron
Transport Material. ChemPhysChem 2001, 2, 448ꢀ452.
9. (a) Yang, L.; Shi, M.; Wang, M.; Chen, H., Synthesis, Electrochemical, And Spectroscopic
Properties Of Soluble Perylene Monoimide Diesters. Tetrahedron 2008, 64, 5404ꢀ5409; (b)
Zhang, X.; Wu, Y.; Li, J.; Li, F.; Li, M., Synthesis and Characterization of Perylene
Tetracarboxylic Bisester Monoimide Derivatives. Dyes and Pigments 2008, 76, 810ꢀ816; (c)
Xue, C.; Sun, R.; Annab, R.; Abadi, D.; Jin, S., Perylene Monoanhydride Diester: A Versatile
21
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 22 of 24
Intermediate for the Synthesis of Unsymmetrically Substituted Perylene Tetracarboxylic
Derivatives. Tetrahedron Lett. 2009, 50, 853ꢀ856.
1
2
3
4
5
6
10. Langhals, H.; Sprenger, S.; Brandherm, M. T., Perylenamidine‐Imide Dyes. Liebigs Ann. 1995,
481ꢀ486.
7
8
9
11. (a) Kaiser, H.; Lindner, J.; Langhals, H., Synthesis of Nonsymmetrically Substituted Perylene
Fluorescent Dyes. Chem. Ber. 1991, 124, 529ꢀ535; (b) Nagao, Y.; Naito, T.; Abe, Y.; Misono,
T., Synthesis and Properties of Long and Branched Alkyl Chain Substituted
Perylenetetracarboxylic Monoanhydride Monoimides. Dyes and Pigments 1996, 32, 71ꢀ83.
12. (a) Gómez, R.; Segura, J. L.; Martín, N., Highly Efficient LightꢀHarvesting Organofullerenes.
Org. Lett. 2005, 7, 717ꢀ720; (b) Lindner, S. M.; Thelakkat, M., Nanostructures Of nꢀType
Organic Semiconductor in a pꢀType Matrix via SelfꢀAssembly of Block Copolymers.
Macromolecules 2004, 37, 8832ꢀ8835; (c) Langhals, H.; Rauscher, M.; Strübe, J.; Kuck, D.,
Three Orthogonal Chromophores Operating Independently Within the Same Molecule. J. Org.
Chem. 2008, 73, 1113ꢀ1116.
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. (a) Wescott, L. D.; Mattern, D. L., Donor− σ− Acceptor Molecules Incorporating a Nonadecylꢀ
Swallowtailed Perylenediimide Acceptor. J. Org. Chem. 2003, 68, 10058ꢀ10066; (b) Kota, R.;
Samudrala, R.; Mattern, D. L., Synthesis of DonorꢀΣꢀPerylenebisimideꢀAcceptor Molecules
Having PEG Swallowtails and Sulfur Anchors. J. Org. Chem. 2012, 77, 9641ꢀ9651.
14. Kelber, J.; Bock, H.; Thiebaut, O.; Grelet, E.; Langhals, H., Room‐Temperature Columnar
Liquid‐Crystalline Perylene Imido‐Diesters by a Homogeneous One‐Pot Imidification–
Esterification of Perylene‐3, 4, 9, 10‐tetracarboxylic Dianhydride. Eur. J. Org. Chem. 2011,
2011, 707ꢀ712.
15. (a) Kappe, C. O., Controlled Microwave Heating in Modern Organic Synthesis. Angew. Chem.
Int. Ed. 2004, 43, 6250ꢀ6284; (b) De la Hoz, A.; DiazꢀOrtiz, A.; Moreno, A., Microwaves in
Organic Synthesis. Thermal and NonꢀThermal Microwave Effects. Chem. Soc. Rev. 2005, 34,
164ꢀ178.
16. Rigodanza, F.; Tenori, E.; Bonasera, A.; Syrgiannis, Z.; Prato, M., Fast and Efficient
Microwave‐Assisted Synthesis of Perylenebisimides. Eur. J. Org. Chem. 2015, 2015, 5060ꢀ
5063.
17. (a) Gupta, R. K.; Pathak, S. K.; Pradhan, B.; Rao, D. S.; Prasad, S. K.; Achalkumar, A. S., Selfꢀ
Assembly of Luminescent NꢀAnnulated Perylene Tetraesters into Fluid Columnar Phases. Soft
matter 2015, 11, 3629ꢀ3636; (b) Gupta, R. K.; Pradhan, B.; Pathak, S. K.; Gupta, M.; Pal, S. K.;
Ammathnadu Sudhakar, A., Perylo [1, 12ꢀb, c, d] Thiophene Tetraesters: A New Class of
Luminescent Columnar Liquid Crystals. Langmuir 2015, 31, 8092ꢀ8100; (c) Gupta, R. K.;
22
ACS Paragon Plus Environment

Page 23 of 24
The Journal of Organic Chemistry
Pathak, S. K.; Pradhan, B.; Gupta, M.; Pal, S. K.; Sudhakar, A. A., Bay‐Annulated Perylene
Tetraesters: A New Class of Discotic Liquid Crystals. ChemPhysChem 2016, 17, 859ꢀ872; (d)
Schulze, M.; Philipp, M.; Waigel, W.; Schmidt, D.; Würthner, F., Library of AzabenzꢀAnnulated
CoreꢀExtended Perylene Derivatives with Diverse Substitution Patterns and Tunable Electronic
and Optical Properties. J. Org. Chem. 2016, 81, 8394ꢀ8405; (e) Sengupta, S.; Dubey, R. K.;
Hoek, R. W.; van Eeden, S. P.; Gunbaꢂ, D. D.; Grozema, F. C.; Sudhölter, E. J.; Jager, W. F.,
Synthesis of Regioisomerically Pure 1, 7ꢀDibromoperyleneꢀ3, 4, 9, 10ꢀTetracarboxylic Acid
Derivatives. J. Org. Chem. 2014, 79, 6655ꢀ6662; (f) Yang, T.; Pu, J.; Zhang, J.; Wang, W.,
SwallowꢀTailed Alkyl and Linear AlkoxyꢀSubstituted Dibenzocoronene Tetracarboxdiimide
Derivatives: Synthesis, Photophysical Properties, and Thermotropic Behaviors. J. Org. Chem.
2013, 78, 4857ꢀ4866.
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
18. Gupta, R. K.; Shankar Rao, D. S.; Prasad, S. K.; Achalkumar, A. S., Columnar Self‐Assembly of
Electron‐Deficient Dendronized Bay‐Annulated Perylene Bisimides. Chem. Eur. J. 2018, 24,
3566ꢀ3575.
19. Gupta, R. K.; Das, D.; Gupta, M.; Pal, S. K.; Iyer, P. K.; Achalkumar, A. S., Electroluminescent
Room Temperature Columnar Liquid Crystals Based on BayꢀAnnulated Perylene Tetraesters. J.
Mater. Chem. C 2017, 5, 1767ꢀ1781.
20. Kong, X.; He, Z.; Zhang, Y.; Mu, L.; Liang, C.; Chen, B.; Jing, X.; Cammidge, A. N., A
Mesogenic Triphenylene− Perylene− Triphenylene Triad. Org. Lett. 2011, 13, 764ꢀ767.
21. (a) Würthner, F.; Kaiser, T. E.; Saha‐Möller, C. R., J‐Aggregates: From Serendipitous Discovery
to Supramolecular Engineering of Functional Dye Materials. Angew. Chem. Int. Ed. 2011, 50,
3376ꢀ3410; (b) Chen, Z.; Stepanenko, V.; Dehm, V.; Prins, P.; Siebbeles, L. D.; Seibt, J.;
Marquetand, P.; Engel, V.; Würthner, F., Photoluminescence and Conductivity of Self‐
Assembled π–π Stacks of Perylene Bisimide Dyes. Chem. Eur. J. 2007, 13, 436ꢀ449; (c) Fink, R.
F.; Seibt, J.; Engel, V.; Renz, M.; Kaupp, M.; Lochbrunner, S.; Zhao, H.ꢀM.; Pfister, J.;
Würthner, F.; Engels, B., Exciton Trapping in πꢀConjugated Materials: A QuantumꢀChemistryꢀ
Based Protocol Applied to Perylene Bisimide Dye Aggregates. J. Am. Chem. Soc. 2008, 130,
12858ꢀ12859.
22. (a) McRae, E. G.; Kasha, M., Enhancement of Phosphorescence Ability Upon Aggregation of
Dye Molecules. J. Chem. Phys 1958, 28, 721ꢀ722; (b) Kasha, M.; Rawls, H.; ElꢀBayoumi, M.
A., The Exciton Model in Molecular Spectroscopy. Pure Appl. Chem. 1965, 11, 371ꢀ392.
23. (a) Lee, S. K.; Zu, Y.; Herrmann, A.; Geerts, Y.; Müllen, K.; Bard, A. J., Electrochemistry,
Spectroscopy and Electrogenerated Chemiluminescence of Perylene, Terrylene, and
Quaterrylene Diimides in Aprotic Solution. J. Am. Chem. Soc. 1999, 121, 3513ꢀ3520; (b) Pron,
23
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 24 of 24
A.; Reghu, R. R.; Rybakiewicz, R.; Cybulski, H.; Djurado, D.; Grazulevicius, J. V.; Zagorska,
M.; KulszewiczꢀBajer, I.; Verilhac, J.ꢀM., Triarylamine Substituted Arylene Bisimides as
Solution Processable Organic Semiconductors for Field Effect Transistors. Effect of Substituent
Position on Their Spectroscopic, Electrochemical, Structural, and Electrical Transport
Properties. J. Phys. Chem. C 2011, 115, 15008ꢀ15017.
1
2
3
4
5
6
7
8
24. (a) Gaussian 09, Revision B.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.;
Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.;
Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.;
Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. J. A.; Peralta, J. E.;
Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi,
R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi,
M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.;
Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.;
Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.;
Cioslowski J.; Fox, D. J. Gaussian Inc., Wallingford, CT, 2009; (b) Lee, C.; Yang, W.; Parr, R.
G., Development of The ColleꢀSalvetti CorrelationꢀEnergy Formula into A Functional of The
Electron Density. Physical review B 1988, 37, 785ꢀ789; (c) Becke, A. D., A New Mixing of
Hartree–Fock and Local Density‐Functional Theories. J. Chem. Phys 1993, 98, 1372ꢀ1377.
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
24
ACS Paragon Plus Environment