6-Dyes and Pigments-2017
6-Dyes and Pigments-2017
6-Dyes and Pigments-2017
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.
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
recent developments in the synthesis of several NIR absorbing dyes, region, in photosensitizers and biosensors. In addition, such com-
nevertheless, rapidly growing scientific research further demands pounds could display substantially high fluorescence quantum
for more efficient, easily soluble, highly stable fluorochromes with yields.
high fluorescence quantum yields, longer life time, considerable These interesting applications draw our attention to synthesize
redox potentials and greater Stokes shift for better sensitivity. and investigate key salient characteristics of new PBIs for more
PBIs are being used extensively for different applications. Some advanced applications. Considering the growing demand for next
of the photostable and water soluble NIR absorbing halogenated generation applications we are reporting the piperidine substituted
PBIs with considerable fluorescence quantum yields were synthe- PBI regioisomers with different alkyl chain lengths as green and
sized and used for the selective staining of cellular organelles. blue NIR absorbing fluorescent dyes 1A, 1B, 2A, 2B along with some
Moreover, perylene monoimide chromophores were further other structural analogues as depicted in Fig. 1. For comparative
modified for covalent labeling of target proteins [2]. Our ongoing purposes, crystalline, spectroanalytical and electrochemical prop-
research focuses on PBIs as biosensing probes to develop new erties were investigated to explore their potentials as future
bioanalytical techniques for real time monitoring of biological promising candidates for a wide range of applications like bio-
systems and desired changes in fluorescence signal are tuned sensors, charge carriers, semiconductors, staining agents and
through controlled self-assembly of small molecule probes [14]. For photosensitizer.
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 2. Results and discussion
for colorimetric based sensing of alkaline phosphatase activity and
inhibitor screening [16]. In fact, probe 1 was further utilized for 2.1. Synthesis
many other applications [17e19] that reveals PBIs are versatile and
have broad spectrum of applications. Perylenebisimide nano- The green and blue NIR fluorescent dyes 1A, 1B, 2A, and 2B were
particles having broad absorption peak in the range of 600e800 nm prepared by substituting piperidine on the bay position of per-
were explored as photoacoutic agents for deep brain tumor imag- ylenebisimide (PBI) from the corresponding mixture of 1,7 and 1,6
ing and its real time application was successfully tested in living dibromo PBIs 1PBr2 and 2PBr2. The mixture of 1,6 and 1,7 dibromo
mice [20]. Water soluble green PBI dyes were used as potential PBIs 1PBr2 and 2PBr2 were obtained by imidization of brominated
sensitizers for photodynamic therapy [21]. Furthermore perylene bisanhydride. The bromination of perylene-3,4,9,10-
photosensitizer-doped perylene nanoparticles were prepared for tetracarboxylic dianhydride (PTCDA) was accomplished using
simultaneous enhanced diagnosis and photodynamic therapy [22]. literature procedures [23]. The synthetic route is illustrated in
In fact, the inherent thermal and photochemical stability of PBIs Scheme 1.
making them as promising materials for light absorption in NIR 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 and a singlet in the region of perylene core protons that represents
spectra recorded in CDCl3 revealed the downfield position of singlet the 70% and 30% composition of 1,6 and 1,7 regioisomers respec-
that is a characteristic of perylene protons of 1,7 regioisomers, i.e. a tively as shown in Fig. 2. The major isomer (1,7) of 1PBr2 revealed
singlet between the two doublets for corresponding perylene two doublets with chemical shifts of 9.49e9.47 and 8.71e8.70 and a
protons (Fig. S9 and Fig. S13). This is because the protons are less singlet at d value 8.93. The perylene protons of minor isomer (1,6) of
shielded due to plane of symmetry raised by symmetrically 1PBr2 appeared at d values of 9.50e9.47 and 8.72e8.70 for two
substituted piperidine moieties. Indeed each proton of singlet doublets while a singlet appeared at d value 8.93. The similar
experience the direct effect of neighboring piperidine substituent. behavior was observed in the chemical shift values of 2PBr2.
While in case of blue dyes (1,6 regioisomers) the singlet is observed Doublets for perylene protons of major isomer appeared at d value
slightly up field as compared to green dyes because these protons 9.43e9.42 and 8.66e8.63. While the minor peaks at 9.43e9.42 and
experience more shielding effect of asymmetrically substituted 8.65e8.63 represents 1,7 regioisomer. Singlet of both major and
electron rich piperidine moieties (Fig. S10 and Fig. S14). Despite the minor isomer overlapped at d value 8.93 as shown in Fig. 2.
several attempts to isolate regioisomers, 1PBr2 and 2PBr2 were In planning the synthesis of perylenebisimide 1 and 2, a slightly
obtained as inseparable mixture of 1,7 (major) and 1,6 (minor) modified literature procedure [24] was used for the synthesis of the
regioisomers due to the small difference in polarity of the two perylenebisimide 1 and 2. Both perylenebisimide 1 and 2 were
regioisomers. The NMR spectra contains two overlapped doublets 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 pure polyethoxy amine was obtained using common chromato-
amines as described in Scheme 2. The pure products 1 and 2 were graphic techniques such as column chromatography [25]. To avoid
obtained without any chromatography. purification problem, they used other alternative synthetic routes
Polyethoxy amine precursor was efficiently synthesized in high [25]. However, under our improved reaction conditions, polyethoxy
yield under mild reaction conditions as outlined in Scheme 1b. In amine precursor was formed in quantitative yield (99%) and desired
past some attempts have been made to obtain similar structural amine precursor was purified using simple solvent extraction
types of pure polyethoxy amine precursors using LiAlH4 as a strategy under acidic conditions. Finally, pure amine precursor was
reducing agent but results remain unsatisfactory due to contami- extracted with DCM after washing with basic aqueous solution. In
nation of many unidentified impurities and none of the desired comparison to previous attempts in the synthesis of polyethoxy
E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224 215
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) (M1 cm1) (Eg) 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. emission spectra of 1A, 1B, 2A and 2B. The fluorescence data are
However, in the polar solvent acetonitrile the values shifted to summarized in Table 2. The emission bands of newly synthesized
higher wavelength in the range of 650 nme661 nm. The numerical perylenebisimides are approximate mirror images of correspond-
values were tabulated in Table 3. 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
2.3. Fluorescence spectroscopic study
significantly changed its emission and excitation spectra. The
emission spectra of 1A, 1B, 2A and 2B reveal that there is a strong
In order to examine the fluorescence properties of the synthe-
broad emission band at 700e850 nm when excited at 435 nm.
sized dyes, fluorescence spectra of the compounds were recorded
Moreover, excitation spectra exhibited two intense broad bands
as shown in Figs. 7 and 8. To this purpose, emission spectra of 1,
around 683 nm and 437 nm at emission wavelength of 790 nm
1PBr2, 2, and 2PBr2 were recorded with excitation wavelength of
(Fig. S1, and Fig. S2: Supporting Information). It is observed that the
500 nm. Excitation wavelength of 435 nm was applied to record
E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224 217
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).
Fig. 7. Corrected emission spectra of 1, 1PBr2 (Concentration: 5 mM each, lex: 500 nm, The blue shift was observed in non-polar solvent (n-hexane). The
slit width: 2 nm), 1A and 1B (Concentration: 5 mM each, lex: 435 nm, slit width: 3 nm) emission peaks of the dyes were appeared around 700 nm in n-
in dry chloroform. 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).
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 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
The crystalline nature of green and blue dyes 1A, 1B, 2A and 2B at 2q ¼ 7, 15 20, 24, 31 and 45 with reflections of hkl (100), (200),
were studied along with non-substituted and brominated PBIs by (220), (330) and (442) exhibits the crystalline nature of 1A and 1B.
subjecting the powder samples to XRD diffractometer in the 2q
range from 5 to 90 using Cu Ka rays. The crystalline behavior of 2.7. Thermal analysis
1A and 1B was evident from well-defined sharp peaks in XRD
pattern (Fig. 14). This behavior might be induced by substitution of Thermal stability and phase transitions of 1A, 2A, 1B, and 2B
dimethyl-1,2-diamine on imide position. The absence of well- were studied by TG-DSC curves (Fig. 15) obtained by NETZSCH STA
defined sharp peaks in the XRD patterns of 2A and 2B indicated 449F3 simultaneous thermal analyzer with nitrogen as a carrier gas
its amorphous nature (Fig. 14). The presence of hollow broad peak at heating rate of 10 C and temperature range from 30 to 600 C.
extended from 10 to 30 is characteristics of the perylene core in PBIs were found thermally stable up to 400e450 C as revealed by
E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224 219
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 of reactions was monitored by TLC. Products were purified by col-
higher then 1A and 1B due to longer side chains of polexoyethylene. umn chromatography (silica gel 200e300 mesh). Diethyl ether was
It ensures 2A, and 2B are thermally more stable compare to 1A, and dried using sodium metal. Chloroform was dried over calcium
1B. The major weight loss of 50e60% for 2A and 2B might be due to hydride.
1
degradation of polyethoxy ethylene side chains. However, TG of 1A H and 13C NMR spectra were obtained at 500 MHz using
and 1B revealed two fractions of mass losses each of 15% that might BRUKER NMR spectrometer in CDCl3. Chemical shifts were recor-
corresponds for the sequential degradation of dimethyl ethylene ded relative to TMS as an internal standard. Mass spectra were
side chains. The DSC results revealed phase transitions for 1A and recorded on Bruker Mass spectrometer (Bruker Daltonic flex
1B at 280 C (DH ¼ 1.168 J/g) and 326 C (DH ¼ 1.89 J/g). However, analysis).
2A and 2B did not show any glass transition. Hence, XRD and DSC
results together ensure the amorphous nature of 2A and 2B.
3.2. Spectro-analytical study
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.
[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 221
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 for 24 h at 85 C. Excess bromine was removed by using N2 stream.
mstd are gradients from the plot of absorbance verses integrated 20 mL of water was added to cool the mixture and filtered. Washed
emission intensity for test compound and standard respectively. with 85% H2SO4 followed by washing with distilled water several
hcompound and hstd denotes the refractive indexes of solvents used times. 3.39 g of dark red compound (96%) was obtained that was
for the preparation of solutions. dried in oven at 100 C for 12 h. The obtained brominated com-
pound (3) was used for further reactions without characterization.
3.4. Cyclic voltammetry
3.6.2. 3,6,9,12-Tetraoxapentadecane-15-nitrile (R-CN)
Cyclic voltammograms were recorded by using three electrode R-CN was synthesized using a reported procedure [25]. 50 mg of
systems. A glassy carbon electrode served as working electrode. Pt NaOMe was added to the stirring mixture of 12 mL of 2-[2-(2-
wire made electrode served as counter electrode. And a reference ethoxyethoxy)ethoxy]ethanol and 14 mL of acrylonitrile in a
Ag/AgCl electrode was used. 100 mM tetra-n-butylammonium 100 mL of round bottom flask. The reaction mixture was heated up
hexafluorophosphate (TBAPF6) was used as supporting electrolyte to 60 C for 10 min and gradually cooled to room temperature. After
for the measurement of cyclic voltammograms in chloroform at additional stirring for 1 h, acetic acid (0.25 mL) was added to the
scan rate of 0.1 V S-1. All solutions were purged by argon gas prior to resulting pale yellow mixture. Unreacted acrylonitrile was removed
measurement in order to overcome the interference of dissolved under reduced pressure. Crude product was filtered to remove
oxygen. yellow precipitates. The obtained product was purified by column
chromatography using methylene chloride/petroleum ether (10/1)
3.5. XRD analysis 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),
Powdered samples of blue and green dyes were subjected to 2.62 (t, 2H), 1.2 (t, 3H) (Fig. S5).
XRD analysis by using wide-angle Bruker D8 ADVANCE X-ray
diffractometer (CU target wavelength: 1.54 oh). XRD patterns were 3.6.3. 3,6,9,12-Tetraoxapentadecan-15-amine (R-NH2)
collected in 2q range 0e100 by using Cu Ka ray. 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
3.6. Synthesis and characterization ether and added slowly to the stirring solution. The reaction
mixture was further stirred for 10 min at an ambient condition. A
3.6.1. 1,7(6)-Dibromoperylene-3,4,9,10-tetracaboxylic dianhydride solution of 3.04 g of 3,6,9,12-tetraoxapentadecane-15-nitrile (RCN)
(3) in 20 mL of diethyl ether was added drop wise to the reaction
Compound 3 was synthesized using literature procedure mixture and stirred at room temperature for 4 h. Reaction mixture
[23,36]. 2.5 g of PTCDA was added into a round bottom flask con- was cooled to 0 C and quenched with 100 mL of 3 M HCl and
taining 35 mL of H2SO4 (Conc.) and stirred for a period of 30 h at stirred for 1 h. Unreacted nitrile was removed through extraction
55 C. 0.061 g of iodine (I2) was added to the reaction mixture and using diethyl ether. Aqueous layer was basified with NaOH (added
further stirred for 5 h at same temperature. 0.7 mL of bromine (Br2) NaOH till pH of the solution reached to >10). 3,6,9,12-
was added drop wise within 30 min. Reaction mixture was stirred 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): (Fig. S8).
d (ppm) 5.29 (s, 2H), 3.63 (m, 16H), 2.79 (t, 2H), 1.75 (m, 2H), 1.21 (t,
3H) (Fig. S6).
3.6.6. 1,7(6)-Dipiperidine-N,N-bis[2-(dimethylamino)ethyle]
perylene-3,4,9,10-tetracaboxyldiimide (1A and 1B)
3.6.4. N,N-bis[2-(dimethylamino)ethyle]perylene-3,4,9,10- 100 mg of 1PBr2 was dissolved in 5 mL piperidine and the
tetracaboxyldiimide (1) resulting solution was refluxed at 90 C for 12 h. Excess piperidine
Compound 1 was synthesized according to reported method was removed in vacuum using rotary evaporator and then obtained
[24]. 1H NMR (CF3COOD, 400 MHz): d (ppm) 8.52 (d, 4H), 8.46 (d, residue was further dried under vacuum. Green (65%) and blue
4H), 4.42 (s, 4H), 3.39 (s, 28H), 2.83 (s, 12H) (Fig. S7). (25%) colored compounds were collected by column chromatog-
raphy using acetone as solvent and identified as 1,7 and 1,6
3.6.5. 1,7(6)-Dibromo-N,N-bis[2-(dimethylamino)ethyle]perylene- regioisomers respectively. 1A: (Rf ¼ 0.12, acetone). 1H NMR (CDCl3,
3,4,9,10-tetracaboxyldiimide (1PBr2) 500 MHz): d (ppm) 9.63 (d, 2H), 8.47 (s, 2H), 8.43 (d, 2H), 4.37 (t,
550 mg of compound 3 was stirred in 30 mL of isopropyl alcohol. 4H), 3.50 (m, 4H), 2.94 (t, 4H), 2.93 (t, 4H), 2.71 (t, 4H), 2.40 (s, 12H),
1.5 mL of N0 ,N0 -dimethylethane-1,2-diamine was added to the re- 1.61 (m, 12H) (Fig. S9). 13C NMR (126 MHz, CDCl3) d 163.65, 163.53,
action mixture and refluxed at 90 C for 24 h. The reaction mixture 150.70, 135.35, 129.77, 128.04, 124.14, 123.68, 123.11, 122.74, 122.24,
was allowed to cool at ambient temperature, filtered, washed and 120.72, 57.00, 52.74, 45.73, 38.16, 29.70, 25.72, 23.78; MS (ESI): m/z
obtained residue was further purified by column chromatography (relative intensity) 699.4 (Mþ,100). 1B: (Rf ¼ 0.33, acetone). 1H NMR
using silica gel in DCM/methanol (15/1, v/v. Rf ¼ 0.47) as solvent (CDCl3, 500 MHz): d (ppm) 9.67 (d, 2H), 8.60 (d, 2H), 8.36 (s, 2H),
system. Compound 1PBr2 was obtained in 86% yield as mixture of 4.65 (t, 2H), 4.61 (t, 2H), 3.56 (m, 4H), 3.37 (m, 4H), 2.68 (t, 4H), 2.11
1,7 (major) and 1,6 (minor) regioisomers. Major 1PBr2: 1H NMR (s, 12H), 1.61 (m, 12H) (Fig. S10). 13C NMR (126 MHz, CDCl3) d 163.89,
(CDCl3, 500 MHz): d (ppm) 9.47 (d, 2H), 8.93 (s, 2H), 8.70 (d, 2H), 163.76, 153.32, 136.18, 131.73, 130.87, 128.91, 128.02, 123.76, 123.15,
4.40 (t, 4H), 2.27 (t, 4H), 2.42 (s, 12H). Minor 1PBr2: d (ppm) 9.49 (d, 123.10, 122.44, 120.73, 120.10, 57.02, 56.99, 53.14, 45.72, 25.81,
2H), 8.93 (s, 2H), 8.72 (d, 2H), 4.40 (t, 4H), 2.27 (t, 4H), 2.42 (s, 12H) 23.79; MS (ESI): m/z (relative intensity) 699.4 (Mþ,100).
E. Hussain et al. / Dyes and Pigments 147 (2017) 211e224 223
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- 3.44 (q, 4H), 1.99 (m, 4H), 1.13 (t, 6H), Minor 2PBr2: d (ppm) 9.44 (d,
tetracaboxyldiimide (2) 2H), 8.86 (s, 2H), 8.64 (d, 2H), 4.26 (t, 4H), 3.54 (m, 28H), 3.44 (q,
200 mg of PTCDA was stirred in 10 mL of pyridine. Subsequently 4H), 1.99 (m, 4H), 1.13 (t, 6H) (Fig. S12).
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
3.6.9. 1,7(6)-Dipiperidine-N,N-bis[3,6,9,12-tetraoxapentadecanyl]
mixture was allowed to cool, and dissolved in DCM. The reaction
perylene-3,4,9,10-tetracaboxyldiimide (2A and 2B)
mixture was filtered in order to remove unreacted PTCDA. Resulting
70 mg of 2PBr2 was refluxed in 5 mL of piperidine at 120 C for
filtrate was concentrated and dried. Compound 2 was obtained in
6 h. Solvent was removed using rotary evaporation. Green (62%)
67% (280 mg) yield as red brown solid. 1H NMR (CDCl3, 500 MHz): and blue (24%) colored compounds were separated through silica
d (ppm) 8.67 (d, 4H), 8.58 (d, 4H), 4.32 (t, 4H), 3.56 (m, 28H), 3.51 (q, gel column chromatography using petroleum ether/acetone (5/1)
4H), 2.06 (m, 4H), 1.19 (t, 6H) (Fig. S11). 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,
3.6.8. 1,7(6)-Dibromo-N,N-bis[3,6,9,12-tetraoxapentadecanyl] petroleum ether/acetone, 5: 1). 1H NMR (CDCl3, 500 MHz): d (ppm)
perylene-3,4,9,10-tetracaboxyldiimide (2PBr2) 9.65 (d, 2H), 8.48 (s, 2H), 8.43 (d, 2H), 4.31 (t, 4H), 3.58 (m, 32H),
350 mg of compound 3 was dissolved in 20 mL of NMP and 3.51 (t, 8H), 2.94 (t, 4H), 2.06 (m, 4H) 1.78 (m, 12H) 1.19 (t, 6H)
stirred in a round bottom flask. 400 mg of 3,6,9,12- (Fig. S13). 13C NMR (126 MHz, CDCl3) d 163.52, 163.45, 150.70,
tetraoxapentadecan-15-amine and 0.5 mL of glacial acetic acid 135.27, 129.73, 127.91, 124.04, 123.55, 123.09, 122.67, 122.26, 120.74,
were added to the round bottom flask and refluxed at 90 C for 12 h. 70.65, 70.59, 70.13, 69.81, 69.34, 66.61, 52.73, 37.96, 29.70, 28.30,
After cooling, the reaction mixture was diluted with 150 mL of 25.71, 23.77, 15.17; MS (ESI): m/z (relative intensity) 992.5 (Mþ,
water and filtered. The solid residue was processed for chroma- 100). 2B: (Rf ¼ 0.35, petroleum ether/acetone, 5: 1). 1H NMR (CDCl3,
tography on silica gel using chloroform/methanol (40/1, v/v, 500 MHz): d (ppm) 9.97 (d, 2H), 8.62 (d, 2H), 8.40 (s, 2H), 4.32 (t,
Rf ¼ 0.65) and reddish brown colored product 2PBr2 was obtained 4H), 3.64 (m, 32H), 3.51 (t, 8H), 2.87 (t, 4H), 2.08 (m, 4H) 1.80 (m,
in 36% yield (220 mg) as mixture of 1,7 (major) and 1,6 (minor) 12H) 1.20 (t, 6H). (Fig. S14). 13C NMR (126 MHz, CDCl3) d 163.83,
regioisomers. 1H NMR (CDCl3, 500 MHz): Major 2PBr2: d (ppm) 163.70, 153.34, 136.15, 130.80, 129.92, 128.84, 125.21, 123.78, 123.21,
9.44 (d, 2H), 8.86 (s, 2H), 8.65 (d, 2H), 4.26 (t, 4H), 3.54 (m, 28H), 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
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Science and Technology Development Project (International
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