Dyes and Pigments 147 (2017) 211e224

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Dyes and Pigments

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Synthesis of regioisomerically pure piperidine substituted

perylenebisimide NIR dyes: A comparative study of spectroscopic,
electrochemical and crystalline properties
Ejaz Hussain a, b, Huipeng Zhou a, Na Yang a, Sohail Anjum Shahzad a, c, *, Cong Yu a, b, **
a
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, PR
China
b
University of Chinese Academy of Sciences, Beijing, 100049, PR China
c
Department of Chemistry, COMSATS Institute of Information Technology, Abbottabad 22060, Pakistan

a r t i c l e i n f o a b s t r a c t

Article history: New regioisomerically pure green and blue dyes i.e. 1,7 and 1,6 piperidine substituted perylenebisimides
Received 12 May 2017 (1A, 1B, 2A, 2B) were synthesized. Photophysical properties were compared with unsubstituted and
Received in revised form brominated perylenebisimide analogues (1, 1PBr2, 2, 2PBr2). Piperidine was substituted on the bay re-
14 July 2017
gion after imidization of dibromoperylene-3,4,9,10-tetracaboxylic dianhydride which induces strong
Accepted 2 August 2017
Available online 3 August 2017
bathochromic shifts. Large bathochromic shifts lower the optical band gaps which is the key feature of
NIR absorbing fluorescent dyes with improved photovoltaic efficiencies. All synthesized fluorophores
were characterized by NMR and Mass spectrometry. Photophysical properties were evaluated by UVeVis,
Keywords:
Near infrared dye
fluorimetry, and cyclic voltammetry. Fluorescence quantum yields were estimated by adopting a gradient
Fluorescence method. The well-defined sharp peaks in X-ray diffraction pattern confirmed the crystalline nature of 1A
Perylenebisimide and 1B. In contrast 2A and 2B were found non-crystalline. Thermal analysis by TG-DSC further explored
Regioisomer the stability and phase transitions in dyes. HOMO and LUMO molecular orbitals were depicted by using
Optical band gap density functional theory (DFT) at B3LYP/6e31(d,p). Electrochemical behaviors probed by cyclic vol-
Redox potential tammogram revealed dominant reversible oxidation reactions for 1,7 regioisomers (1A, and 2A) while
both reversible oxidations and reductions were observed in 1,6 isomers (1B and 2B). Other structural
analogues 1, 1PBr2, 2, 2PBr2 displayed reversible reductions. Thus a regular trend of changes in optical
and electrical properties was observed on bromine and piperidine substitution. The observed
outstanding properties clearly justify that our compounds might be promising candidates for various
future applications such as biosensors, biomarkers, semiconductors, charge transporters, and stable
fluorescent dyes.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction show remarkable photochemical and electrochemical stability [4].

NIR fluorescent dyes possess a wide range of potential applica-
tions as biosensors, semiconductors, photovoltaic cells, special
colorants and staining agents because of their significant optical
and electrochemical properties [1e3]. Perylenebisimides (PBIs)
* Corresponding author. Department of Chemistry, COMSATS Institute of Infor-
mation Technology, Abbottabad 22060, Pakistan.
** Corresponding author. State Key Laboratory of Electroanalytical Chemistry,
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Chang-
chun, 130022, PR China.
E-mail addresses: sashahzad@ciit.net.pk (S.A. Shahzad), congyu@ciac.ac.cn
(C. Yu).
PBIs also demonstrate intense fluorescence and high electron
mobility [3]. They are excellent promising candidates for such type
of applications because of their structural diversity which can be
accomplished by modifying PBI's imide and bay positions by alkyl
chains and functional groups [5,6]. Many substituents such as
halogens, alkyl chains, aromatic functional moieties, and hetero-
cyclic rings were used to tune desired properties [7e9]. The sub-
stitution of piperidine on the bay position completely alters the
photophysical properties of the PBIs [4,10]. Generally, substitution
at bay positions is carried out via bromination of perylene-3,4,5,6-
tataracarboxyalic acid [11]. Pure regioisomers can be produced via
derivatization of the brominated bisimides [12,13]. Despite the

http://dx.doi.org/10.1016/j.dyepig.2017.08.002
0143-7208/© 2017 Elsevier Ltd. All rights reserved.
212 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224
Fig. 1. Chemical structures of the peylenebisimide fluorescent dyes.
recent developments in the synthesis of several NIR absorbing dyes,
nevertheless, rapidly growing scientific research further demands
for more efficient, easily soluble, highly stable fluorochromes with
high fluorescence quantum yields, longer life time, considerable
redox potentials and greater Stokes shift for better sensitivity.
PBIs are being used extensively for different applications. Some
of the photostable and water soluble NIR absorbing halogenated
PBIs with considerable fluorescence quantum yields were synthe-
sized and used for the selective staining of cellular organelles.
Moreover, perylene monoimide chromophores were further
modified for covalent labeling of target proteins [2]. Our ongoing
research focuses on PBIs as biosensing probes to develop new
bioanalytical techniques for real time monitoring of biological
systems and desired changes in fluorescence signal are tuned
through controlled self-assembly of small molecule probes [14]. For
example, an organic probe 1 was employed for the selective sensing
of a targeted protein PDGF via nucleic acid induced self-assembly
[15]. And the same perylene probe 1 was successfully exploited
for colorimetric based sensing of alkaline phosphatase activity and
inhibitor screening [16]. In fact, probe 1 was further utilized for
many other applications [17e19] that reveals PBIs are versatile and
have broad spectrum of applications. Perylenebisimide nano-
particles having broad absorption peak in the range of 600e800 nm
were explored as photoacoutic agents for deep brain tumor imag-
ing and its real time application was successfully tested in living
mice [20]. Water soluble green PBI dyes were used as potential
sensitizers for photodynamic therapy [21]. Furthermore
photosensitizer-doped perylene nanoparticles were prepared for
simultaneous enhanced diagnosis and photodynamic therapy [22].
In fact, the inherent thermal and photochemical stability of PBIs
making them as promising materials for light absorption in NIR
region, in photosensitizers and biosensors. In addition, such com-
pounds could display substantially high fluorescence quantum
yields.
These interesting applications draw our attention to synthesize
and investigate key salient characteristics of new PBIs for more
advanced applications. Considering the growing demand for next
generation applications we are reporting the piperidine substituted
PBI regioisomers with different alkyl chain lengths as green and
blue NIR absorbing fluorescent dyes 1A, 1B, 2A, 2B along with some
other structural analogues as depicted in Fig. 1. For comparative
purposes, crystalline, spectroanalytical and electrochemical prop-
erties were investigated to explore their potentials as future
promising candidates for a wide range of applications like bio-
sensors, charge carriers, semiconductors, staining agents and
photosensitizer.
2. Results and discussion
2.1. Synthesis
The green and blue NIR fluorescent dyes 1A, 1B, 2A, and 2B were
prepared by substituting piperidine on the bay position of per-
ylenebisimide (PBI) from the corresponding mixture of 1,7 and 1,6
dibromo PBIs 1PBr2 and 2PBr2. The mixture of 1,6 and 1,7 dibromo
PBIs 1PBr2 and 2PBr2 were obtained by imidization of brominated
perylene bisanhydride. The bromination of perylene-3,4,9,10-
tetracarboxylic dianhydride (PTCDA) was accomplished using
literature procedures [23]. The synthetic route is illustrated in
Scheme 1.
The formation of 1,6 and 1,7 regioisomers of piperidine
substituted PBIs were identified by NMR spectroscopy. The
 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224 213

Scheme 1. a) Synthetic route for the preparation of green and blue dyes 1A, 1B, 2A, and 2B. b) Synthetic route for the preparation of amine precursor.

structures were additionally confirmed by mass spectrometry. NMR
spectra recorded in CDCl3 revealed the downfield position of singlet
that is a characteristic of perylene protons of 1,7 regioisomers, i.e. a
singlet between the two doublets for corresponding perylene
protons (Fig. S9 and Fig. S13). This is because the protons are less
shielded due to plane of symmetry raised by symmetrically
substituted piperidine moieties. Indeed each proton of singlet
experience the direct effect of neighboring piperidine substituent.
While in case of blue dyes (1,6 regioisomers) the singlet is observed
slightly up field as compared to green dyes because these protons
experience more shielding effect of asymmetrically substituted
electron rich piperidine moieties (Fig. S10 and Fig. S14). Despite the
several attempts to isolate regioisomers, 1PBr2 and 2PBr2 were
obtained as inseparable mixture of 1,7 (major) and 1,6 (minor)
regioisomers due to the small difference in polarity of the two
regioisomers. The NMR spectra contains two overlapped doublets
and a singlet in the region of perylene core protons that represents
the 70% and 30% composition of 1,6 and 1,7 regioisomers respec-
tively as shown in Fig. 2. The major isomer (1,7) of 1PBr2 revealed
two doublets with chemical shifts of 9.49e9.47 and 8.71e8.70 and a
singlet at d value 8.93. The perylene protons of minor isomer (1,6) of
1PBr2 appeared at d values of 9.50e9.47 and 8.72e8.70 for two
doublets while a singlet appeared at d value 8.93. The similar
behavior was observed in the chemical shift values of 2PBr2.
Doublets for perylene protons of major isomer appeared at d value
9.43e9.42 and 8.66e8.63. While the minor peaks at 9.43e9.42 and
8.65e8.63 represents 1,7 regioisomer. Singlet of both major and
minor isomer overlapped at d value 8.93 as shown in Fig. 2.
In planning the synthesis of perylenebisimide 1 and 2, a slightly
modified literature procedure [24] was used for the synthesis of the
perylenebisimide 1 and 2. Both perylenebisimide 1 and 2 were
formed in high yields by treating commercially available perylene-
214 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224

Fig. 2. NMR chemical shifts for 1PBr2 (a) and 2PBr2 (b) confirming 70% and 30% mixture of 1,7 (peaks labeled green) and 1,6 regiosiomers (peaks labeled red) respectively. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

3,4,9,10-tetracarboxylic dianhydride (PTCDA) with respective
amines as described in Scheme 2. The pure products 1 and 2 were
obtained without any chromatography.
Polyethoxy amine precursor was efficiently synthesized in high
yield under mild reaction conditions as outlined in Scheme 1b. In
past some attempts have been made to obtain similar structural
types of pure polyethoxy amine precursors using LiAlH4 as a
reducing agent but results remain unsatisfactory due to contami-
nation of many unidentified impurities and none of the desired
pure polyethoxy amine was obtained using common chromato-
graphic techniques such as column chromatography [25]. To avoid
purification problem, they used other alternative synthetic routes
[25]. However, under our improved reaction conditions, polyethoxy
amine precursor was formed in quantitative yield (99%) and desired
amine precursor was purified using simple solvent extraction
strategy under acidic conditions. Finally, pure amine precursor was
extracted with DCM after washing with basic aqueous solution. In
comparison to previous attempts in the synthesis of polyethoxy
 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224
Scheme 2. Schematic illustration for the synthesis of symmetric perylenebisimides 1 and 2.
Fig. 3. Steady state UVeVis absorption spectra of 1, 1PBr2, 1A, and 1B recorded in
chloroform solution (Concentration: 10 mM each).
Fig. 4. Steady state UVeVis absorption spectra of 2, 2PBr2, 2A, and 2B recorded in
chloroform solution (Concentration: 10 mM each).
amines, our optimized synthetic route does not require strict re-
action conditions which make this method easier to handle.
2.2. Steady state UVeVis absorption spectroscopic study
The electronic absorption spectra of PBI dyes were recorded in
chloroform as shown in Figs. 3 and 4. The comparative optical
properties were tabulated in Table 1. It is observed that bromination
on the bay position of PBIs has little influence on the band positions
215
in absorption spectra. Absorption maxima of PBIs without bromine
substitution and with bromine substitutions at bay area are com-
parable. However, a strong bathochromic (red) shift was observed
for piperidinyl substituted dyes 1A, 1B, 2A, 2B due to the presence
of electron donating piperidine moiety on bay position, compared
with 1, 1PBr2, 2 and 2PBr2. Equally important, the aggregation
tendency of the PBIs can be reduced by introduction of appropriate
substituents on the bay-position. Such substitution may lead to a
twisted molecular conformation which allows excellent controlled
over aggregation properties. In other words, aggregation caused
fluorescence quenching and solubility complications of PBIs in
organic solvents can be avoided for further improved applications.
Usually, green and blue dyes demonstrate a broad absorption band
in the 500 nme800 nm range with low optical band gaps due to
charge transfer absorption [26]. In general, optical properties of
PBIs regioisomers differ significantly. As expected, the presence of a
characteristic shoulder band near 550 nm in the absorption spectra
of 1,6 isomers 1B and 2B makes it completely different from 1,7
isomers 1A and 2A. On the other hand, intense peak around 430 nm
was observed in 1,7 isomers 1A and 2A. The extended p-conjuga-
tion in 1,7 isomers is dominant over 1,6 isomers. The lone pair of
nitrogen of piperidinyl functional group is involved in conjugation
with aromatic ring system. The symmetric substitution of piperi-
dine moieties in 1,7 isomers make conjugation more effective. In 1,6
isomers less symmetry of molecule weakens the conjugation. These
are main differences in absorption bands which are the basis for the
large difference in observed colors i.e. green for 1,7 and blue for 1,6
isomers. The lmax of 1A is 37 nm red shifted relative to that of 1B.
The red shift of 160 nm was observed in 1A relative to 1, and 1PBr
while 1B revealed relative red shift of 128 nm. Similarly, due to
piperidine moiety on the bay positions 2A and 2B showed red shifts
of 135, and 131 nm respectively, relative to 2, and 2PBr. These
findings justify the piperidine as an ideal substituent to fine tune
the NIR absorbing properties in PBIs. The optical band gap values of
piperidine substituted PBIs differ from other structural analogues
with an average value of 0.6 eV. These dyes are soluble in a variety
of organic solvents for example chloroform, DCM, THF and acetone.
The solubility (mg/mL) of dyes was measured in chloroform as
given in Table 1. The dyes were found highly soluble in chloroform.
1A and 1B are water soluble in slightly acidic pH because of their
ability of cation formation by extracting protons from acidic media.
Such dyes can form various self-assembled H-type and J-type ag-
gregates through preferential solvations [27,28]. The picture of
color displayed by chloroform solution of dyes is presented in Fig. 5.
The steady state absorption spectra obtained in solvents of
different polarity showed variable solvent dependent behaviors for
1A, 1B, 2A, and 2B (Fig. 6, and Fig. S3). In non-polar solvents such as
n-hexane absorption peak is blue shifted. However, in polar sol-
vents red shift was observed for these dyes. The absorption maxima
216 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224

Table 1
Spectroscopic properties of perylenebisimides.

Entry Color of solution Solubility in chloroform lmax (nm) Molar absorbtivity l2 (nm) l3 (nm) Optical band gap
(mg/mL) (M
1 cm
1) (Eg) eV

1 Orange red 125 527 1.11  105 490 459 2.20

1PBr2 Orange red 116 527 1.37  105 490 462 2.25
1A Green 100 687 1.34  104 437 e 1.60
1B Blue 90 655 2.5  104 399 381 1.61
2 Orange 155 526 1.01  105 490 459 2.25
2PBr2 Orange 145 524 3.42  105 491 e 2.21
2A Green 96 660 1.62  104 428 e 1.64
2B Blue 89 655 1.36  104 399 e 1.61

Eg is calculated from the onset of UV (Eg ¼ 1239.84/lonset eV).

Fig. 5. The chloroform solutions of perylenebisimide dyes displaying the color spectrum. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)

Fig. 6. Steady state UVeVis absorption spectra of 1A (left) and 1B (right) in solvents of different polarity (Concentration: 10 mM each).

of the dyes were found in the range of 613 nme628 nm in hexane.
However, in the polar solvent acetonitrile the values shifted to
higher wavelength in the range of 650 nme661 nm. The numerical
values were tabulated in Table 3.
2.3. Fluorescence spectroscopic study
In order to examine the fluorescence properties of the synthe-
sized dyes, fluorescence spectra of the compounds were recorded
as shown in Figs. 7 and 8. To this purpose, emission spectra of 1,
1PBr2, 2, and 2PBr2 were recorded with excitation wavelength of
500 nm. Excitation wavelength of 435 nm was applied to record
emission spectra of 1A, 1B, 2A and 2B. The fluorescence data are
summarized in Table 2. The emission bands of newly synthesized
perylenebisimides are approximate mirror images of correspond-
ing absorption spectra. The piperidine substituted dyes have larger
values of Stokes shift as illustrated for 2 and 2A in Fig. 9.
The substitution of piperidine moiety on PBIs dyes at bay area
significantly changed its emission and excitation spectra. The
emission spectra of 1A, 1B, 2A and 2B reveal that there is a strong
broad emission band at 700e850 nm when excited at 435 nm.
Moreover, excitation spectra exhibited two intense broad bands
around 683 nm and 437 nm at emission wavelength of 790 nm
(Fig. S1, and Fig. S2: Supporting Information). It is observed that the
 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224 217

Fig. 7. Corrected emission spectra of 1, 1PBr2 (Concentration: 5 mM each, lex: 500 nm,
slit width: 2 nm), 1A and 1B (Concentration: 5 mM each, lex: 435 nm, slit width: 3 nm)
in dry chloroform.
109 nm, and 120 nm for 1A, 1B, 2A, and 2B respectively. As a matter
of fact, observed spectral properties revealed that the absorption
and emission properties of perylenebisimides are substantially
changed through substitution of piperidine moiety at bay area of
PBIs. The peak intensities are concentration dependent obeying
Lambert Beer's law. Furthermore, systematic variations of substi-
tution with appropriate functionality at bay area of PBIs would
allow a fine tuning of their absorption and emission properties as
summarized in Table S1.
Fluorescence quantum yields were estimated by adopting a
gradient method, which revealed that piperidine substituted PBIs
are comparably less fluorescent. Non-substituted and brominated
perylenebisimides have shown higher fluorescence quantum yields
as tabulated in Table 2.
The emission spectra recorded in different solvents revealed
that fluorescence of green (1A, 2A) and blue dyes (1B and 2B) were
influenced by the microenvironment of solvent (Fig. 10 and Fig. S4).
The blue shift was observed in non-polar solvent (n-hexane). The
emission peaks of the dyes were appeared around 700 nm in n-
hexane. However, in polar solvents emission peak intensities shif-
ted towards higher wavelength. The peak intensities of dyes were
appeared around 773, 749, 663, and 660 nm for 1A, 1B, 2A, and 2B
in acetonitrile (Table 3).

2.4. Electrochemical analysis

The electrochemical properties of the synthesized compounds

were studied by recording the cyclic voltammograms in chloro-
form. Typical voltammograms of the newly synthesized perylene
bisimides are outlined in Figs. 11 and 12. The respective electro-
chemical behaviors in terms of redox potentials, and HOMO and
LUMO are tabulated in Table 4 following the trend reported for
other PBIs [29,30]. The onset potentials were shifted to the more
positive in piperidinyl substituted PBIs because of electron
donating mesomeric effect of piperidine. Non-substituted and
brominated PBIs exhibited reversible reductions. It was observed
that 1B and 2B exhibited two reversible reductions, and two
reversible oxidations. 1A and 2A exhibited dominant reversible
Fig. 8. Corrected emission spectra of 2, 2PBr2 (Concentration: 5 mM each, lex: 500 nm, oxidation reaction with E1/2 of 0.951 V and 0.818 V respectively that
slit width: 2 nm), 2A and 2B (Concentration: 5 mM each, lex: 435 nm, slit width: 3 nm) might be due to dominancy of the mesomeric effect of symmetri-
in dry chloroform. cally substituted piperidine [31]. 1B showed two positive onset
potential with E1/2 of 0.847 (eV), and 1.34 (eV). In fact, 2B showed
almost similar behavior of positive onset potentials with E1/2 value
Table 2
Summary of fluorescence emission properties of the perylenebisimides.
of 0.982 (eV), and 1.65 (eV). The HOMO values for 1A, and 2B were
found to be
5.05 (eV) and
5.81 (eV) respectively, while LUMO
Entry lem (nm) lem (nm) lex (nm) Stokes shift (nm) Fa values of
3.45 (eV), and
4.20 (eV) were observed for 2A and 2B.
1 541 576 526 15 0.54 The small differences in the HOMO and LUMO values might be due
1PBr2 548 590 528 22 0.47 to symmetry difference between two compounds. The experi-
1A 774 e e 87 0.38
mentally calculated HOMO and LUMO energy levels can be corre-
1B 775 e e 120 0.26
2 536 574 526 10 0.58 lated with the ionization potential (IP) and electron affinity (EA) of
2PBr2 550 586 526 26 0.54 corresponding PBIs [32]. This indicates that these PBIs are appro-
2A 769 e e 109 0.34 priate candidates as charge transport materials for various elec-
2B 775 e e 120 0.35
tronic devices.
a
Determined with quinine sulfate (4 ¼ 0:55) as reference.

2.5. Quantum chemical computation

fluorescence spectra of 1PBr2 and 2PBr2 are slightly red shifted
relative to non-substituted structural analogues 1, and 2 respec-
tively. In contrast to conventional dyes, large Stokes shifts were
observed for newly synthesized green and blue dyes as tabulated in
Table 2. The dyes 1, and 2 showed lowest Stokes shift values of
15 nm and 10 nm respectively. 1PBr2, and 2PBr2 revealed Stokes
shift values of 22 nm, and 26 nm. However, piperidine substituted
PBIs showed higher values of Stokes shifts with 87 nm, 120 nm,
Molecular structures of 1A and 1B were further evaluated by
using density functional theory (DFT) at B3LYP/6-31G(d,p) level.
Highest occupied molecular orbitals (HOMO) and lowest unoccu-
pied molecular orbitals (LUMO) were depicted in Fig. 13. HOMOs of
all compounds were delocalized on piperidine nitrogen and per-
ylene core, while LUMOs are extended toward dianhydride group
from the perylene core.
218 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224

Fig. 9. Normalized absorbance and emission spectra of compound 2 (left) and 2A (right) showing significant difference in Stokes shift. (Concentration: 5 mM each, lex for 2: 500 nm,
lex for 2A: 435 nm, slit width: 3 nm).

Fig. 10. Emission spectra of 1A (left) and 1B (right) in solvents of different polarity (Concentration: 5 mM each, lex: 435 nm, slit width: 4 nm).

Table 3
Summary of absorbance and fluorescence emission properties of green and blue dyes in solvents of different polarity.

Solvent 1A 1B 2A 2B
l ab-max/lem (nm) l ab-max/lem (nm) l ab-max/lem (nm) l ab-max/lem (nm)
Hexane 622/708 613/700 628/697 618/697
DCM 683/762 656/771 672/754 648/754
Acetone 655/759 644/773 649/757 638/754
Acetonitrile 661/773 650/779 654/763 646/760
Toluene 664/738 639/749 60/740 636/735

2.6. Crystalline properties
The crystalline nature of green and blue dyes 1A, 1B, 2A and 2B
were studied along with non-substituted and brominated PBIs by
subjecting the powder samples to XRD diffractometer in the 2q
range from 5 to 90 using Cu Ka rays. The crystalline behavior of
1A and 1B was evident from well-defined sharp peaks in XRD
pattern (Fig. 14). This behavior might be induced by substitution of
dimethyl-1,2-diamine on imide position. The absence of well-
defined sharp peaks in the XRD patterns of 2A and 2B indicated
its amorphous nature (Fig. 14). The presence of hollow broad peak
extended from 10 to 30 is characteristics of the perylene core in
PBIs [33] The inter-planer spacing and hkl reflections for 1A and 1B
are tabulated (Table S2, and Table S3). The well-defined sharp peaks
at 2q ¼ 7, 15 20, 24, 31 and 45 with reflections of hkl (100), (200),
(220), (330) and (442) exhibits the crystalline nature of 1A and 1B.
2.7. Thermal analysis
Thermal stability and phase transitions of 1A, 2A, 1B, and 2B
were studied by TG-DSC curves (Fig. 15) obtained by NETZSCH STA
449F3 simultaneous thermal analyzer with nitrogen as a carrier gas
at heating rate of 10  C and temperature range from 30 to 600  C.
PBIs were found thermally stable up to 400e450  C as revealed by
 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224
Fig. 11. Cyclic voltammograms of 1, 1PBr2, 1A, and 1B measured in chloroform with 100 mM TBAPF6 as supporting electrolyte. Scan speed 100 mV/s, potential vs. Ag/AgCl as
reference electrode.
TG curves. The degradation temperature of 2A and 2B is relatively
higher then 1A and 1B due to longer side chains of polexoyethylene.
It ensures 2A, and 2B are thermally more stable compare to 1A, and
1B. The major weight loss of 50e60% for 2A and 2B might be due to
degradation of polyethoxy ethylene side chains. However, TG of 1A
and 1B revealed two fractions of mass losses each of 15% that might
corresponds for the sequential degradation of dimethyl ethylene
side chains. The DSC results revealed phase transitions for 1A and
1B at 280  C (DH ¼ 1.168 J/g) and 326  C (DH ¼ 1.89 J/g). However,
2A and 2B did not show any glass transition. Hence, XRD and DSC
results together ensure the amorphous nature of 2A and 2B.
3. Experimental section
3.1. General
2-[2-(2-ethoxyethoxy)ethoxy]ethanol, sodium methoxide
(NaOCH3), LiAlH4, AlCl3, iodine (I2), bromine (Br2), perylene-
3,4,9,10-teteracarboxalic dianhydride (PTCDA), N0 ,N0 -dimethyl-
ethane-1,2-diamine, piperidine and all other reagents were pur-
chased from commercial suppliers and used as specified. Progress
219
of reactions was monitored by TLC. Products were purified by col-
umn chromatography (silica gel 200e300 mesh). Diethyl ether was
dried using sodium metal. Chloroform was dried over calcium
hydride.
1
H and 13C NMR spectra were obtained at 500 MHz using
BRUKER NMR spectrometer in CDCl3. Chemical shifts were recor-
ded relative to TMS as an internal standard. Mass spectra were
recorded on Bruker Mass spectrometer (Bruker Daltonic flex
analysis).
3.2. Spectro-analytical study
UVeVis absorption spectra were recorded on Cary-50 spectro-
photometer. Emission and excitation spectra were collected by
Fuoromax-4 spectrofluorometer. All solutions for spectroscopic
studies were prepared in dry chloroform.
3.3. Fluorescence quantum yields
The photoluminescence quantum yield of the newly synthe-
sized compounds was estimated by adopting a gradient method
220 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224

Fig. 12. Cyclic voltammograms of 2, 2PBr2, 2A, and 2B measured in chloroform with 100 mM TBAPF6 as supporting electrolyte. Scan speed 100 mV/s, potential vs. Ag/AgCl as
reference electrode.

Table 4
Electrochemical potentials and energy levels (HOMO, and LUMO) of the PBIs.

Entry E1/2(PBI/PBI
) E1/2(PBI
/PBI2
) E1/2(PBI/PBIþ) E1/2(PBIþ/PBI2þ) ELUMOa (eV) HHOMOb (eV)

1
0.506 e 0.072 (Irrev) 1.173 (Irrev)
3.89
6.09

1PBr2
0.384 e e e
4.02
6.27
1A e e 0.951 e
3.45
5.05
1B
0.202
0.503 0.847 1.340
4.20
5.81
2
0.577
0.768 e e
3.82
6.07
2PBr2
0.508
0.704 e e
3.89
6.10
2A
0.756 e 0.818 e
3.64
5.24
2B
0.185
0.550 0.982 1.450
4.20
5.81
a
ELUMO ¼ 4.4eV-Ered1.
b
EHOMO ¼ ELUMO e Eg, E1/2(V vs Ag/AgCl).

[34]. Quinine sulfate (4 ¼ 0:55) was used as standard fluorophore samples of each compound in chloroform solution were prepared
[35]. In brief, five samples of quinine sulfate in 0.1 M H2SO4 were and determined the gradient (mcompound ) from the plot of absor-
prepared. The concentration range was optimized in order to keep bance verses integrated fluorescence intensity (Fig. S23). Finally the
optical densities in the range of 0.01e0.1 to avoid self absorption quantum yield is calculated by using the following equation.
effect. Absorbance was recorded using UVeVis spectrometer. In-
tegrated emission spectra of all five samples were recorded at
 h2 !
mcompound compound
excitation wavelength of 350 nm. The value of gradient (mstd ) for 4compound ¼ 4std
standard was determined by linear plot of optical densities verses mstd h2std
integrated emission intensities setting intercept at zero. Five
Where 4compound is the quantum yield of compound being tested,
 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224
Fig. 13. Computed frontier molecular orbital of 1A and 1B (LUMOs upper graphs and HOMOs lower graphs).
4std is quantum yield of standard (Quinine sulfate), mcompound and
mstd are gradients from the plot of absorbance verses integrated
emission intensity for test compound and standard respectively.
hcompound and hstd denotes the refractive indexes of solvents used
for the preparation of solutions.
3.4. Cyclic voltammetry
Cyclic voltammograms were recorded by using three electrode
systems. A glassy carbon electrode served as working electrode. Pt
wire made electrode served as counter electrode. And a reference
Ag/AgCl electrode was used. 100 mM tetra-n-butylammonium
hexafluorophosphate (TBAPF6) was used as supporting electrolyte
for the measurement of cyclic voltammograms in chloroform at
scan rate of 0.1 V S-1. All solutions were purged by argon gas prior to
measurement in order to overcome the interference of dissolved
oxygen.
3.5. XRD analysis
Powdered samples of blue and green dyes were subjected to
XRD analysis by using wide-angle Bruker D8 ADVANCE X-ray
diffractometer (CU target wavelength: 1.54 oh). XRD patterns were
collected in 2q range 0e100 by using Cu Ka ray.
3.6. Synthesis and characterization
3.6.1. 1,7(6)-Dibromoperylene-3,4,9,10-tetracaboxylic dianhydride
(3)
Compound 3 was synthesized using literature procedure
[23,36]. 2.5 g of PTCDA was added into a round bottom flask con-
taining 35 mL of H2SO4 (Conc.) and stirred for a period of 30 h at
55  C. 0.061 g of iodine (I2) was added to the reaction mixture and
further stirred for 5 h at same temperature. 0.7 mL of bromine (Br2)
was added drop wise within 30 min. Reaction mixture was stirred
221
for 24 h at 85  C. Excess bromine was removed by using N2 stream.
20 mL of water was added to cool the mixture and filtered. Washed
with 85% H2SO4 followed by washing with distilled water several
times. 3.39 g of dark red compound (96%) was obtained that was
dried in oven at 100  C for 12 h. The obtained brominated com-
pound (3) was used for further reactions without characterization.
3.6.2. 3,6,9,12-Tetraoxapentadecane-15-nitrile (R-CN)
R-CN was synthesized using a reported procedure [25]. 50 mg of
NaOMe was added to the stirring mixture of 12 mL of 2-[2-(2-
ethoxyethoxy)ethoxy]ethanol and 14 mL of acrylonitrile in a
100 mL of round bottom flask. The reaction mixture was heated up
to 60  C for 10 min and gradually cooled to room temperature. After
additional stirring for 1 h, acetic acid (0.25 mL) was added to the
resulting pale yellow mixture. Unreacted acrylonitrile was removed
under reduced pressure. Crude product was filtered to remove
yellow precipitates. The obtained product was purified by column
chromatography using methylene chloride/petroleum ether (10/1)
as solvent system. Colorless oil was obtained in 92% yield. 1H NMR
(CDCl3, 500 MHz): d (ppm) 3.72 (t, 2H), 3.64 (m, 12H), 3.52 (q, 2H),
2.62 (t, 2H), 1.2 (t, 3H) (Fig. S5).
3.6.3. 3,6,9,12-Tetraoxapentadecan-15-amine (R-NH2)
500 mg of LiAlH4 was stirred in 20 mL of dry diethyl ether in a
two neck flask. 2.3 g of AlCl3 was dissolved in 25 mL of dry diethyl
ether and added slowly to the stirring solution. The reaction
mixture was further stirred for 10 min at an ambient condition. A
solution of 3.04 g of 3,6,9,12-tetraoxapentadecane-15-nitrile (RCN)
in 20 mL of diethyl ether was added drop wise to the reaction
mixture and stirred at room temperature for 4 h. Reaction mixture
was cooled to 0  C and quenched with 100 mL of 3 M HCl and
stirred for 1 h. Unreacted nitrile was removed through extraction
using diethyl ether. Aqueous layer was basified with NaOH (added
NaOH till pH of the solution reached to >10). 3,6,9,12-
tetraoxapentadecan-15-amine was extracted with DCM and
222 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224
Fig. 14. XRD spectra of (a) 1A, (b) 1B, (c) 2A, and (d) 2B exhibiting the crystalline and amorphous morphologies.
obtained 3.1 g (99%) of yellow oil. 1H NMR (CDCl3, 500 MHz):
d (ppm) 5.29 (s, 2H), 3.63 (m, 16H), 2.79 (t, 2H), 1.75 (m, 2H), 1.21 (t,
3H) (Fig. S6).
3.6.4. N,N-bis[2-(dimethylamino)ethyle]perylene-3,4,9,10-
tetracaboxyldiimide (1)
Compound 1 was synthesized according to reported method
[24]. 1H NMR (CF3COOD, 400 MHz): d (ppm) 8.52 (d, 4H), 8.46 (d,
4H), 4.42 (s, 4H), 3.39 (s, 28H), 2.83 (s, 12H) (Fig. S7).
3.6.5. 1,7(6)-Dibromo-N,N-bis[2-(dimethylamino)ethyle]perylene-
3,4,9,10-tetracaboxyldiimide (1PBr2)
550 mg of compound 3 was stirred in 30 mL of isopropyl alcohol.
1.5 mL of N0 ,N0 -dimethylethane-1,2-diamine was added to the re-
action mixture and refluxed at 90  C for 24 h. The reaction mixture
was allowed to cool at ambient temperature, filtered, washed and
obtained residue was further purified by column chromatography
using silica gel in DCM/methanol (15/1, v/v. Rf ¼ 0.47) as solvent
system. Compound 1PBr2 was obtained in 86% yield as mixture of
1,7 (major) and 1,6 (minor) regioisomers. Major 1PBr2: 1H NMR
(CDCl3, 500 MHz): d (ppm) 9.47 (d, 2H), 8.93 (s, 2H), 8.70 (d, 2H),
4.40 (t, 4H), 2.27 (t, 4H), 2.42 (s, 12H). Minor 1PBr2: d (ppm) 9.49 (d,
2H), 8.93 (s, 2H), 8.72 (d, 2H), 4.40 (t, 4H), 2.27 (t, 4H), 2.42 (s, 12H)
(Fig. S8).
3.6.6. 1,7(6)-Dipiperidine-N,N-bis[2-(dimethylamino)ethyle]
perylene-3,4,9,10-tetracaboxyldiimide (1A and 1B)
100 mg of 1PBr2 was dissolved in 5 mL piperidine and the
resulting solution was refluxed at 90  C for 12 h. Excess piperidine
was removed in vacuum using rotary evaporator and then obtained
residue was further dried under vacuum. Green (65%) and blue
(25%) colored compounds were collected by column chromatog-
raphy using acetone as solvent and identified as 1,7 and 1,6
regioisomers respectively. 1A: (Rf ¼ 0.12, acetone). 1H NMR (CDCl3,
500 MHz): d (ppm) 9.63 (d, 2H), 8.47 (s, 2H), 8.43 (d, 2H), 4.37 (t,
4H), 3.50 (m, 4H), 2.94 (t, 4H), 2.93 (t, 4H), 2.71 (t, 4H), 2.40 (s, 12H),
1.61 (m, 12H) (Fig. S9). 13C NMR (126 MHz, CDCl3) d 163.65, 163.53,
150.70, 135.35, 129.77, 128.04, 124.14, 123.68, 123.11, 122.74, 122.24,
120.72, 57.00, 52.74, 45.73, 38.16, 29.70, 25.72, 23.78; MS (ESI): m/z
(relative intensity) 699.4 (Mþ,100). 1B: (Rf ¼ 0.33, acetone). 1H NMR
(CDCl3, 500 MHz): d (ppm) 9.67 (d, 2H), 8.60 (d, 2H), 8.36 (s, 2H),
4.65 (t, 2H), 4.61 (t, 2H), 3.56 (m, 4H), 3.37 (m, 4H), 2.68 (t, 4H), 2.11
(s, 12H), 1.61 (m, 12H) (Fig. S10). 13C NMR (126 MHz, CDCl3) d 163.89,
163.76, 153.32, 136.18, 131.73, 130.87, 128.91, 128.02, 123.76, 123.15,
123.10, 122.44, 120.73, 120.10, 57.02, 56.99, 53.14, 45.72, 25.81,
23.79; MS (ESI): m/z (relative intensity) 699.4 (Mþ,100).
 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224
Fig. 15. TG-DSC curves of 1A, 1B, 2A, and 2B heated at rate of 10  C with nitrogen as carrier gas.
3.6.7. N,N-bis[3,6,9,12-tetraoxapentadecanyl]perylene-3,4,9,10-
tetracaboxyldiimide (2)
200 mg of PTCDA was stirred in 10 mL of pyridine. Subsequently
250 mg of 3,6,9,12-tetraoxapentadecan-15-amine was added to the
reaction mixture and refluxed for 24 h at 110  C. The reaction
mixture was allowed to cool, and dissolved in DCM. The reaction
mixture was filtered in order to remove unreacted PTCDA. Resulting
filtrate was concentrated and dried. Compound 2 was obtained in
67% (280 mg) yield as red brown solid. 1H NMR (CDCl3, 500 MHz):
d (ppm) 8.67 (d, 4H), 8.58 (d, 4H), 4.32 (t, 4H), 3.56 (m, 28H), 3.51 (q,
4H), 2.06 (m, 4H), 1.19 (t, 6H) (Fig. S11).
3.6.8. 1,7(6)-Dibromo-N,N-bis[3,6,9,12-tetraoxapentadecanyl]
perylene-3,4,9,10-tetracaboxyldiimide (2PBr2)
350 mg of compound 3 was dissolved in 20 mL of NMP and
stirred in a round bottom flask. 400 mg of 3,6,9,12-
tetraoxapentadecan-15-amine and 0.5 mL of glacial acetic acid
were added to the round bottom flask and refluxed at 90  C for 12 h.
After cooling, the reaction mixture was diluted with 150 mL of
water and filtered. The solid residue was processed for chroma-
tography on silica gel using chloroform/methanol (40/1, v/v,
Rf ¼ 0.65) and reddish brown colored product 2PBr2 was obtained
in 36% yield (220 mg) as mixture of 1,7 (major) and 1,6 (minor)
regioisomers. 1H NMR (CDCl3, 500 MHz): Major 2PBr2: d (ppm)
9.44 (d, 2H), 8.86 (s, 2H), 8.65 (d, 2H), 4.26 (t, 4H), 3.54 (m, 28H),
223
3.44 (q, 4H), 1.99 (m, 4H), 1.13 (t, 6H), Minor 2PBr2: d (ppm) 9.44 (d,
2H), 8.86 (s, 2H), 8.64 (d, 2H), 4.26 (t, 4H), 3.54 (m, 28H), 3.44 (q,
4H), 1.99 (m, 4H), 1.13 (t, 6H) (Fig. S12).
3.6.9. 1,7(6)-Dipiperidine-N,N-bis[3,6,9,12-tetraoxapentadecanyl]
perylene-3,4,9,10-tetracaboxyldiimide (2A and 2B)
70 mg of 2PBr2 was refluxed in 5 mL of piperidine at 120  C for
6 h. Solvent was removed using rotary evaporation. Green (62%)
and blue (24%) colored compounds were separated through silica
gel column chromatography using petroleum ether/acetone (5/1)
as solvent system. These dyes 2A and 2B were identified by NMR
spectroscopy as 1, 7 and 1, 6 regioisomers respectively. 2A: (Rf ¼ 0.2,
petroleum ether/acetone, 5: 1). 1H NMR (CDCl3, 500 MHz): d (ppm)
9.65 (d, 2H), 8.48 (s, 2H), 8.43 (d, 2H), 4.31 (t, 4H), 3.58 (m, 32H),
3.51 (t, 8H), 2.94 (t, 4H), 2.06 (m, 4H) 1.78 (m, 12H) 1.19 (t, 6H)
(Fig. S13). 13C NMR (126 MHz, CDCl3) d 163.52, 163.45, 150.70,
135.27, 129.73, 127.91, 124.04, 123.55, 123.09, 122.67, 122.26, 120.74,
70.65, 70.59, 70.13, 69.81, 69.34, 66.61, 52.73, 37.96, 29.70, 28.30,
25.71, 23.77, 15.17; MS (ESI): m/z (relative intensity) 992.5 (Mþ,
100). 2B: (Rf ¼ 0.35, petroleum ether/acetone, 5: 1). 1H NMR (CDCl3,
500 MHz): d (ppm) 9.97 (d, 2H), 8.62 (d, 2H), 8.40 (s, 2H), 4.32 (t,
4H), 3.64 (m, 32H), 3.51 (t, 8H), 2.87 (t, 4H), 2.08 (m, 4H) 1.80 (m,
12H) 1.20 (t, 6H). (Fig. S14). 13C NMR (126 MHz, CDCl3) d 163.83,
163.70, 153.34, 136.15, 130.80, 129.92, 128.84, 125.21, 123.78, 123.21,
123.11, 122.36, 120.18, 70.65, 70.62, 70.60, 70.13, 69.82, 69.35, 69.25,
224 E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224
66.62, 53.16, 29.70, 29.66, 28.33, 28.27, 25.81, 23.79, 15.17; MS (ESI):
m/z (relative intensity) 992.5 (Mþ, 100).
4. Conclusions
This report presents a series of new perylenebisimide near
infrared (NIR) absorbing regioisomers obtained by incorporating
piperidinyl functional groups at the bay positions. The optical and
electrochemical properties of the newly synthesized dyes were
compared with the corresponding bromine substituted and
unsubstituted perylenebisimides. Interestingly, green and blue
dyes exhibit broad absorption peaks in the range of
500 nme800 nm. The strong bathochromic shift in the piperidine
substituted dyes is due to mesomeric effect of electron rich bay
substituent. Comparatively bromine substituted and unsubstituted
perylenebisimides exhibit higher quantum yields. However, 1,7
(green) and 1,6 (blue) regioisomers have large values of Stokes shift.
The cyclic voltammograms of green and blue dyes reveal more
positive onset potentials. While the symmetrical and bromo
substituted structural analogues revealed only reversible re-
ductions. XRD pattern shows that 1A and 1B are crystalline in na-
ture while 2A and 2B are found to have amorphous morphology.
TG-DSC analysis ensured the thermal stability and morphological
behaviors of PBIs. It is very likely that the investigated properties of
the newly synthesized compounds could provide an interesting
starting point in the development of new biosensors, photovoltaic
cells, and staining agents for next-generation applications.
Acknowledgments
This work is supported by CAS-TWAS President's PhD Fellow-
ship Program (2015CTF031), the National Natural Science Founda-
tion of China (21561162004, 21550110196), the Jilin Provincial
Science and Technology Development Project (International
Collaboration Program, 20160414040GH), and the Natural Science
Foundation of Jilin Province (20150101183JC).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.dyepig.2017.08.002.
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