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Bis-naphthalimides bridged by electron acceptors:

optical and self-assembly characteristics†
Cite this: RSC Adv., 2016, 6, 71638
Ankita Saini and K. R. Justin Thomas*

Received 17th May 2016
Accepted 11th July 2016
DOI: 10.1039/c6ra12776b
www.rsc.org/advances
The self-assembly of small organic molecules into molecular stacks plays a vital role in the construction of
stable supramolecular structures. The self-assembly of highly linear and rigid naphthalimide-based electron
deficient small molecules, which are synthesized via a Pd-catalyzed Sonogashira cross coupling reaction,
leads to the formation of controlled morphologies and well-defined nanostructures, which are
developed from the J-aggregated solid state packing mode. Their optical properties evidence the
molecular self-aggregation in solution and the solid state. Fluorescence lifetime decay measurements for
the monomeric and aggregated state of the dyes demonstrate the effect of aggregation on the radiative
and non-radiative decay rates. Electrochemical studies reveal that these electron deficient compounds
possess suitable energy levels for them to be used as airstable n-type semiconductors. The electronic
features and coplanar arrangement of the functional entities, which were determined via density
functional theoretical computations, ensure a close packing arrangement of molecules in the solid state.
Field emission scanning electron microscopy was used to unravel the nanostructure formation of the as
synthesized samples and those obtained from different solvents. The formation of one-dimensional (1D)
to three dimensional (3D) nano to micro-scale fibers, rods, cubes or flower-like structures is attributed
to the non-covalent p–p intermolecular stacking of the aromatic moieties and packing of the
hydrophobic alkyl chains. Dynamic light scattering studies reveal the nanoscale dimension of the
aggregates. Fluorescence images of the compounds were observed under an optical fluorescence
microscope, which exhibit multicolor emission under different light sources. Furthermore, thermal
analysis and powder X-ray diffraction characterization of the small molecules indicate high thermal
stability, crystallinity and effective p–p interplanar morphology. The present study demonstrates the use
of intermolecular interactions to achieve organized nanostructure designs with different morphologies
and sizes.

unique optical and electronic properties.2 Nano and micro-

Introduction
In the eld of materials science, small organic molecules
exhibit dened chemical structures, which make them quite
attractive in terms of ease of synthesis and purication, and this
greatly improves processing and device-fabrication reproduc-
ibility as compared to polymers and inorganic materials.1 They
exhibit a strong affinity to self-aggregate into low dimensional
structures through different assembly processes. Assembled
morphologies, which result in supramolecular materials, have
agged their importance due to their high aspect ratios, and
Organic Materials Laboratory, Department of Chemistry, Indian Institute of
Technology Roorkee, Roorkee-247667, India. E-mail: krjt8fcy@iitr.ac.in
† Electronic supplementary information (ESI) available: Thin lm absorption
spectra of dyes, THF : H2O titration spectra, uorescence lifetime spectroscopy
measurements, CV recorded in DCM, optimized geometries of the compounds,
FESEM images of samples, optical microscopy images, compiled tabular data
for absorption and emission of dyes, DLS, PXRD, thermal analysis, and
Cartesian coordinates of the optimized compounds, 1H and 13C NMR spectra of
dyes. See DOI: 10.1039/c6ra12776b
structures with controllable hierarchical architectures are of
increasing interest because of their utilization in broad appli-
cation elds ranging from medicine to electronics to optoelec-
tronics.3 The morphologies of the formed assemblies are closely
related to the stacking mode of the building blocks and can be
controlled through the alteration of intermolecular interac-
tions, which are affected by a number of factors such as
concentration, temperature and solvent dependence.4
Currently, various approaches, such as the use of templates,
reprecipitation, electrochemical methods, and various solution
techniques involving weak non-covalent interactions, such as
hydrogen bonding, p–p stacking, electrostatic and hydrophobic
interactions, are efficiently used for the construction of nano-
structures.5 However, only a few examples among the numerous
tedious strategies for designing self-assembled nanostructures
have been found capable of producing nanostructures for use as
potential molecular materials. Moreover, when compared with
the synthetic approaches of inorganic nanostructures, very few
approaches have been developed for the fabrication of organic

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small-molecule nanostructures.1j,2h,2j,3c,3d In 2001, Frank
Würthner for rst time demonstrated the self-assembling
properties of organic molecules due to the formation of J-
aggregates6 in perylene bisimide with a narrow J-band.7 Later,
a number of such molecules were highlighted to show self-
assembling supramolecular systems with the aid of various
methods, as mentioned earlier. However, only a few reports are
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known for the self-assembled well dened nano-morphology of
as-synthesized organic chromophores.1f,2a,8
p–p intermolecular stacking and hydrophobic interactions
are highly explored in organic materials due to the presence of
an aromatic core and easy incorporation of hydrophobic alkyl
chains.5f,7,8i The general strategy for designing a molecular
system for effective intermolecular interactions is to have
a large, planar and extended p-core which enhances p-stacking
and reduces steric interactions. The supramolecular assembly
of extended p-conjugated chromophores,8 such as various pol-
yaromatic hydrocarbons (PAHs),9 including anthracene,10 pyr-
ene,11 perylene,12 perylene diimides (PDI),13 naphthalene
diimides (NDI),14 many amide-based conjugated molecules,15
and heteroaromatic systems,16 into dened dimensional nano-
structures provides a potential strategy to tune their optical and
electronic properties. It is found that the incorporation of the
alkyne group between aromatic building blocks is more adapt-
able to conformational and steric constraints than the alkene
moiety due to the electronic symmetry and planarity induction
in the molecule.17 Acetylene based functionalized large
aromatic core assemblies enhance p–p interactions, reduce the
intermolecular spacing between molecules and therefore
strengthen the non-covalent interactions.18
It is well known that in organic electronics, n-type semi-
conductors lag far behind compared to their p-type counterparts
due to their low mobility, poor stability and poor solubility for
solution processing.19 Moreover, only a small amount of litera-
ture has addressed crystalline nano or microscale n-type organic
semiconductors. Among the known frameworks, imides and
p-conjugated molecules15a have received considerable attention
as promising n-type organic semiconducting candidates. We
Fig. 1 Structures of the naphthalimide end-capped small molecules.
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used 1,8-naphthalimide20 because it possesses high carrier
mobility, high electron affinity, promising uorescence proper-
ties, chemical and thermal stability and easy functionalization at
active C-4 and N-atom positions. Moreover, it facilitates long-
range intermolecular charge delocalization of the p-electron
cloud and can be explored successfully as a highly organized
skeleton in various applications such as biological and cell bio-
imaging,21 uorescent sensors22 and optoelectronic devices.23
Herein, we describe the synthesis and characterization of
4-ethynyl-1,8-naphthalimide based planar chromophores (3a–
3d), which are shown in Fig. 1. They form self-assembled 1D to
3D nanostructures in a facile manner, which is attributed to
effective intermolecular p–p stacking. These small molecules
exhibit remarkable optical, electrochemical and thermal prop-
erties. The planar skeletons show a high degree of crystallinity
and solubility in various organic solvents owing to the n-ethyl-
hexyl chain introduced at the N-position.
Experimental
General methods and instrumentation
All commercial chemicals were used as received. Column
chromatography was performed using silica gel (100–200 mesh)
as the stationary phase. All solvents used in the synthesis and
spectroscopic measurements were distilled over appropriate
drying and/or degassing reagents. 1H and 13C NMR spectra were
obtained on a Bruker FT-NMR and JEOL spectrometer operating
at 500 MHz and 100 MHz, respectively, in CDCl3. Me4Si (0.00
ppm) or residual signals for CHCl3 (1H NMR, d ¼ 7.26 ppm; 13C
NMR, d ¼ 77.23 ppm) served as the internal standard. IR spectra
were obtained on an FT-IR spectrometer. High resolution mass
spectra were obtained using the electron spray ionization (ESI)
mode on a Bruker TOF-Q ESI mass spectrometer operating in
positive ion mode. UV-Vis spectra were obtained at RT in quartz
cuvettes on a Cary UV-100 spectrophotometer. Fluorescence
measurements were conducted using freshly prepared diluted
solutions and performed on an RF-5301-PC Shimadzu spectro-
uorophotometer. Drop-cast thin lms on quartz plates were
RSC Adv., 2016, 6, 71638–71651 | 71639

RSC Advances
prepared from a toluene solution and used for the measurement
of solid state photoluminescence. The solid state emissions of
the powders were recorded on a Horiba FluoroMax-4 spectro-
uorometer. Fluorescence quantum yields (FF) were determined
using the formula Fs ¼ (Fr  Ar  Is  hs2)/(As  Ir  hr2), where
A is the absorbance at the excitation wavelength, I is the inte-
grated area under the uorescence curve, and h is the refraction
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index. Subscripts r and s refer to the reference and the sample of
unknown quantum yield, respectively. For a 90% water–THF, the
refraction index (h) of 0.34 was calculated using the formula
hwater  Vwater + hTHF  VTHF/Vwater + VTHF. Coumarin-6 in
ethanol (FF ¼ 0.78) was taken as the reference. Absolute solid
state uorescent quantum yield (3% accuracy) was measured
via the integrating sphere method using an Edinburgh FLS980
uorescence spectrometer. Fluorescence lifetime decay
measurements were recorded in a 1 cm quartz cell on a Horiba
Jobin Yvon “FluoroCube Fluorescence Lifetime System” equip-
ped with NanoLEDs and LDs as the excitation source(s) and an
automated polarization accessory (Model 5000 U-02). Cyclic
voltammetry (CV) measurements were performed using a BASi
Epsilon electrochemical analyzer. All measurements in
dichloromethane (DCM) solution were conducted at room
temperature with the conventional three-electrode conguration
comprising a glassy carbon working electrode, a platinum wire
counter, and a nonaqueous acetonitrile Ag/AgNO3 reference
electrode under nitrogen atmosphere. Potentials are quoted
against a ferrocene internal standard. The solvent used in all
measurements was dichloromethane (DCM) and the supporting
electrolyte was 0.1 M tetrabutylammonium hexauorophosphate
(TBAP) at a scan rate of 100 mV s1. Thermogravimetric analyses
(TGA) were performed under nitrogen atmosphere at a heating
rate of 10  C min1 using an SII 6300 EXSTAR analyser. The
thermal transitions of the dyes were investigated on a Netzsch
DSC 204F1 Phoenix differential scanning calorimeter (DSC)
under nitrogen atmosphere at a heating rate of 10  C min1.
Powder X-ray diffraction was performed using a Bruker D8
Advance diffractometer over the 2q range of 5–90 and the scan
rate was 1 min1 for the copper target (Cu-Ka; l ¼ 1.5406 Å).
Scanning electron microscopy (SEM) images of the samples were
recorded using an FE-SEM Quanta 200 FEG instrument operated
at 15–20 kV on substrates sputtered by gold. Samples for the SEM
analysis were investigated in powder form or prepared via
a drop-cast method from dye aggregates in various solvent
systems on glass substrates. Dynamic light scattering (DLS)
particle size distribution was measured on a Malvern Zetasizer
Nano-ZS90, which was obtained from the intensity of the
aggregates. Fluorescence microscopic images were acquired
using a Nikon Eclipse LV100 microscope by air drying a drop of
the diluted samples on a glass slide under various excitation
lters such as B-2A (450–490 nm) and G-2A (510–560 nm) lter
excitation. All images were taken at 100 magnication.
Synthesis of 2-(2-ethylhexyl)-6-ethynyl-1H-benzo[de]isoquinoline-
1,3(2H)-dione, 2
To a two neck R.B. ask 6-bromo-2-(2-ethylhexyl)-1H-benzo[de]
isoquinoline-1,3(2H)-dione (1) (13.0 g, 33.5 mmol),
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triphenylphosphine (176 mg, 0.2 mmol, 2 mol%), cuprous
iodide (64 mg, 0.1 mmol, 1 mol%) and Pd(PPh3)2Cl2 (235 mg,
0.1 mmol, 1 mol%) were added and purged with N2 for 10 min.
Then, trimethylsilylacetylene (4.0 g, 40.2 mmol, 1.2 eq.) was
added and N2 was passed through the mixture for 5 min, then
distilled degassed TEA 160 mL was added immediately and the
mixture was kept stirring at r.t. Aer completion of the reaction
was conrmed by TLC, the TMS intermediate was extracted
using DCM and washed with brine water, dried over Na2SO4 and
the solvent evaporated to yield a brown liquid, which was
puried by silica column chromatography (eluent: CHCl3-
: hexane, 1 : 1) followed by deprotection in 50 mL distilled
methanol and to the resulting intermediate 30 mmol each of KF
and Bu4NBr and 10 mL distilled DCM was added and stirred for
30 minutes at 60  C. The reaction mixture was cooled and water
was added, which was extracted with DCM and washed thor-
oughly with water and dried to obtain a viscous liquid that
solidied on cooling and then adsorbed on silica for chroma-
tography (eluent: CHCl3 : hexanes, 1 : 1). Yellow solid; yield 7.0
g (77%); mp: 82–84  C; IR (KBr, cm1) 1698 (nC]O), 2098 (nC^C),
3218 (nC^CH); 1H NMR (CDCl3, 500 MHz) d 8.66 (d, J ¼ 8.5 Hz,
2H), 8.63 (d, J ¼ 7.0 Hz, 1H), 7.94 (d, J ¼ 7.5 Hz, 1H), 7.83 (t, J ¼
7.5 Hz, 1H), 4.14–4.07 (m, 2H), 3.73 (s, 1H), 1.96–1.91 (m, 1H),
1.40–1.29 (m, 8H), 0.93 (t, J ¼ 7.5 Hz, 3H), 0.87 (t, J ¼ 7.0 Hz, 3H);
13
C NMR (CDCl3, 100 MHz) d 164.5, 164.3, 132.3, 132.1, 131.94,
131.85, 130.4, 128.1, 127.9, 126.3, 123.1, 123.0, 86.7, 86.5, 44.4,
38.1, 30.9, 28.9, 24.2, 23.3, 14.3, 10.9; HRMS (ESI, m/z) [M]+ calcd
for C22H23NO2: 333.1723; found 333.1748.
General procedure for the synthesis of dyes 3b–d and byproduct
3a
Aryl dibromide (1 mmol), 2-(2-ethylhexyl)-6-ethynyl-1H-benzo
[de]isoquinoline-1,3(2H)-dione (2) (0.668 g, 2 mmol) was added
to a 100 mL two neck R.B. ask and N2 gas was passed through
the ask for 5 minutes, then Pd(PPh3)2Cl2 (14 mg, 0.02 mmol),
CuI (4 mg, 0.02 mmol), and PPh3 (11 mg, 0.04 mmol) were
added and purged with nitrogen for 10 minutes. Then, degassed
distilled triethylamine (20 mL) was added under a nitrogen
atmosphere. Furthermore, the reaction mixture was reuxed for
5–12 h and monitored using TLC, and upon completion water
was added to quench the reaction. The mixture was extracted
with DCM and washed thoroughly with water. Then, the solvent
was evaporated and absorbed on silica for purication.
6,60 -(Buta-1,3-diyne-1,4-diyl)bis(2-(2-ethylhexyl)-1H-benzo
[de]isoquinoline-1,3(2H)-dione), 3a. This was obtained as a side
product (yield: 0.15 g (23%)) during the preparation of 3b. It can
also be prepared using the following oxidative coupling strategy
in good yield.23a A mixture of 2 (0.668 g, 2 mmol), CuI (28 mg,
1.5 mmol) and triethylamine (10 mL) was allowed to react at
room temperature under an N2 atmosphere for 12 h. Aer the
completion of the reaction, the volatiles were removed under
vacuum. The residue was puried by column chromatography
using a CHCl3 : hexanes mixture (3 : 2) as the eluent.
Yield: 0.50 g (75%), yellow solid, mp: 119  C; IR (KBr, cm1)
1699 (nC]O); 1H NMR (CDCl3, 500 MHz) d 8.70 (d, J ¼ 8.5 Hz,
2H), 8.67 (d, J ¼ 8.5 Hz, 2H), 8.57 (d, J ¼ 7.5 Hz, 2H), 8.05
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(d, J ¼ 7.5 Hz, 2H), 7.89 (t, J ¼ 7.5 Hz, 2H), 4.17–4.08 (m, 4H),
1.97–1.92 (m, 2H), 1.41–1.28 (m, 16H), 0.94 (t, J ¼ 7.0 Hz, 6H),
0.88 (t, J ¼ 7.0 Hz, 6H); 13C NMR (CDCl3, 100 MHz) d 164.3,
164.0, 132.8, 132.5, 132.1, 132.1, 130.3, 128.3, 128.2, 125.3,
123.6, 123.4, 82.2, 81.7, 44.5, 38.1, 30.9, 28.9, 24.2, 23.3, 14.3,
10.8; HRMS (ESI, m/z) [M + H]+ calcd for C44H44N2O4: 665.3373;
found 665.3342.
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6,60 -((9-Oxo-9H-uorene-2,7-diyl)bis(ethyne-2,1-diyl))bis(2-
(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione), 3b.
Purication by silica column chromatography using a CHCl3-
: hexanes mixture (7 : 3) as the eluent to yield 0.3 g of the
desired orange solid and 0.4 g of yellow mono coupled bro-
moderivative solid. Yield: 30%; mp: 296  C; IR (KBr, cm1) 1699
(nC]O), 2200 (nC^C); 1H NMR (CDCl3, 500 MHz) d 8.68 (d, J ¼ 8.0
Hz, 2H), 8.65 (d, J ¼ 6.0 Hz, 2H), 8.55 (d, J ¼ 7.5 Hz, 2H), 7.97–
7.95 (m, 4H), 7.86 (t, J ¼ 7.5 Hz, 2H), 7.82 (d, J ¼ 8.5 Hz, 2H), 7.62
(d, J ¼ 8.5 Hz, 2H), 4.15–4.07 (m, 4H), 1.96–1.93 (m, 2H), 1.39–
1.30 (m, 16H), 0.93 (t, J ¼ 7.5 Hz, 6H), 0.87 (t, J ¼ 7.0 Hz, 6H); 13C
NMR (CDCl3, 100 MHz) d 191.8, 164.4, 164.1, 143.9, 138.4, 134.5,
132.1, 131.9, 131.6, 131.2, 130.4, 128.1, 127.9, 126.7, 123.9,
123.2, 122.6, 121.2, 97.9, 88.7, 44.4, 38.1, 30.9, 28.9, 24.2, 23.3,
14.3, 10.8; HRMS (ESI, m/z) [M]+ calcd for C57H50N2O5: 842.3714;
found 842.3724.
6,60 -(Benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-diyl))
bis(2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione),
3c. Purication by silica column chromatography using
a CHCl3 : hexanes mixture (1 : 1) as the eluent. Orange solid,
yield: 0.6 g (75%); mp: 272  C; IR (KBr, cm1) 1704 (nC]O), 2199
(nC^C); 1H NMR (CDCl3, 500 MHz) d 9.02 (d, J ¼ 8.5 Hz, 2H), 8.84
(d, J ¼ 7.0 Hz, 2H), 8.59 (d, J ¼ 8.5 Hz, 2H), 8.08 (d, J ¼ 8.5 Hz,
2H), 7.97 (d, 2H), 7.94 (t, J ¼ 7.5 Hz, 2H), 4.17–4.08 (m, 4H),
1.98–1.93 (m, 2H), 1.42–1.29 (m, 16H), 0.94 (t, J ¼ 7.5 Hz, 6H),
0.88 (t, J ¼ 7.0 Hz, 6H); 13C NMR (CDCl3, 100 MHz) d 164.4,
164.2, 154.6, 132.9, 132.6, 132.0, 131.9, 131.4, 130.5, 128.3,
128.2, 126.5, 123.2, 123.2, 117.4, 95.1, 94.4, 44.4, 38.0, 30.8, 28.8,
24.1, 23.2, 14.2, 10.7; HRMS (ESI, m/z) [M + H]+ calcd for
C50H46N4O4S: 799.3312; found 799.3298.
6,60 -(Dibenzo[a,c]phenazine-10,13-diylbis(ethyne-2,1-diyl))
bis(2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione),
3d. Recrystallized with hexanes and CHCl3. Orange solid; yield
0.92 g (97%); mp: 286  C; IR (KBr, cm1) 1698 (nC]O), 2200
(nC^C); 1H NMR (CDCl3, 500 MHz) d 8.88 (d, J ¼ 7.5 Hz, 2H), 8.68
(d, J ¼ 8.0 Hz, 2H), 8.36 (d, J ¼ 6.5 Hz, 2H), 8.27 (d, J ¼ 7.0 Hz,
Scheme 1 Synthesis of the compounds.
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2H), 8.12 (d, J ¼ 8.0 Hz, 2H), 7.62 (d, J ¼ 7.5 Hz, 2H), 7.59–7.50
(m, 6H), 7.35 (t, J ¼ 7.0 Hz, 2H), 4.11–4.00 (m, 4H), 1.98–1.93 (m,
2H), 1.44–1.35 (m, 16H), 0.98–0.91 (m, 12H); 13C NMR (CDCl3,
100 MHz) d 163.7, 163.5, 141.7, 140.8, 132.6, 131.9, 131.5, 130.8,
130.4, 130.3, 129.6, 128.8, 127.3, 127.2, 126.9, 126.5, 125.8,
122.9, 122.5, 121.9, 95.9, 94.1, 44.3, 38.1, 30.9, 28.9, 24.1, 23.4,
14.4, 10.7; HRMS (ESI, m/z) [M + Na]+ calcd for C64H54N4O4:
942.4139; found 942.4170.
Computational methods
The Gaussian 09 36 program package was employed to perform
all computations, which were fully optimized without any
symmetry constrains and employed DFT using Becke's three
parameters hybrid functional and Lee, Yang and Parr's corre-
lational functional B3LYP37 using the 6-31G* basis set on all
atoms in vacuum. Structure conrmation was performed by
vibrational analyses on the optimized structures. The excitation
energies and oscillator strengths for the lowest 10 singlet–
singlet transitions at the optimized geometry in the ground
state were obtained by TD-DFT calculations using the (M06-2x/
6-31G(d,p)) method.
Results and discussion
Synthesis and characterization
The synthetic pathway used to prepare the dyes (3a–3d) is
shown in Scheme 1. First, the acetylene derivative, 2 was
synthesized via a two-step reaction involving the Sonogashira
coupling of 6-bromo-2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-
1,3(2H)-dione (1) with trimethylsilyl acetylene. The latter
compound, 1, was synthesized via the imidization of 4-bromo-
naphthalene anhydride according to a literature procedure.24
Finally, the naphthalimide-based functional materials were
conveniently synthesized by the Sonogashira cross-coupling
reaction between 2-(2-ethylhexyl)-6-ethynyl-1H-benzo[de]iso-
quinoline-1,3(2H)-dione (2) and the respective aryl dibromides25
using the Pd(PPh3)2Cl2/PPh3/CuI catalytic system in good to
excellent yields. For 3b, 6-((7-bromo-9-oxo-9H-uoren-2-yl)
ethynyl)-2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione
was synthesized as the major product due to the low reactivity of
the respective arylene dibromide. The dye 3a was obtained as
a homocoupled byproduct in the cross coupling reactions tar-
geted for the synthesis of the other dyes 3b–3d. All the dyes are
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intensely colored (yellow or orange) and exhibit bright solid state
luminescence. Moreover, they are highly soluble in a wide variety
of solvents such as toluene (Tol), tetrahydrofuran (THF), and
dichloromethane (DCM). The dyes were thoroughly character-
ized using spectral methods (NMR, FTIR and HRMS) and the
data obtained is found to be consistent with the proposed
structures.
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All the dyes, except the uorenone derivative, are brightly
luminescent in dilute solutions. The uorescence spectra
recorded for compounds 3a–3d in dilute DCM solution is dis-
played in Fig. 2b. The emission peak wavelengths showed
a similar trend to that of the absorption with the exception of
3b. The emission proles of compounds 3a, 3c and 3d exhibited
vibronic features, which attest the rigidity of the molecules,17c

whereas 3b featured broad structureless emission. The Stokes

Optical properties shi is also signicantly large for 3b in the series. In addition,
the quantum yield of 3b is the lowest in the group. The above-
The UV-Vis absorption and emission spectra of the dyes were
mentioned observations suggest that the dye 3b probably
measured in DCM solution and are displayed in Fig. 2 and
undergoes structural relaxation in the excited state prior to
the corresponding optical parameters are listed in Table 1.
emission.17c
The absorption spectra of the dyes are complex with multiple
Furthermore, the UV-Vis absorption and emission spectra of
overlapping p–p* transition bands ranging from 350 to 500
the compounds in thin lm and solid state (Fig. 3a and b, S1
nm. The naphthalimide moiety shows an absorbance band at
and Table S1†) were obtained to understand the intermolecular
350–366 nm.20j In the present dyes, additional red-shied
interaction and self-assembly process. A red-shied absorption
absorption peaks were noticed. Among the dyes, the dyes
band at 20–70 nm was observed in the thin lm as compared to
containing benzothiadiazole (3c) and dibenzo[a,c]phenazine
the solution spectra, which is attributed to the stronger elec-
(3d) in the conjugation pathway exhibited the most red-
tronic interaction between the individual molecular skeletons
shied absorption peaks. This bathochromic shi is attrib-
in the solid state.5b,18b,27 Moreover, a broad featureless absorp-
uted to the extension of conjugation by the introduction of
tion band with the emergence of a new band was observed,
an additional electron accepting p-conjugating chromo-
which are attributed to the intermolecular p–p packing inter-
phore. Additional peaks attributable to the localized
actions or J-aggregation well reported in the literature.20e Such
absorptions originating from the uorenone and dibenzo
an ordered packing of small molecules is effective for long
[a,c]phenazine chromophores were observed for compounds
range charge carrier mobility and self-aggregation. It is well
3b and 3d.16h,26

Fig. 2 (a) Absorption and (b) emission spectra of the dyes recorded in DCM.

Table 1 Optical and electrochemical data of dyes 3a–3d recorded in DCM

Dye lmax, nm (3max, M1 cm1  103) lema, nm (FF%) Stokes shi, cm1 Eoxb, V Eredb, V HOMOd, eV LUMOc, eV E0-0e, eV

3a 423 (42.4), 392 (47.8), 371 (28.9) 438, 464 (62) 810 1.51 1.43 6.31 3.37 2.94
3b 445 (20.9) s, 400 (70.0), 291 (41.8) 540 (24) 6798 1.17, 1.31 1.50, 1.66 5.97 3.30 2.66
3c 463 (39.8), 439 (46.4), 380 (18.1), 354 490, 518 (70) 1237 1.23 1.32, 1.84 6.03 3.48 2.55
(15.6), 329 (14.6), 279 (14.6)
3d 470 (41.5), 447 (41.9), 422 (39.5), 398 500, 526 (82) 1322 1.16 1.48, 1.84 5.96 3.32 2.65
(35.8), 302 (32.7)
a
Relative quantum yield was obtained by comparison with the standard coumarin-6. b Redox potentials are reported with reference to the ferrocene
internal standard using tetrabutylammonium perchlorate as the electrolyte. c Deduced from the reduction potential using the formula LUMO ¼ 4.8
 |Ered|. d Obtained from the DPV oxidation potential peak. e Calculated using the formula E0-0 ¼ EHOMO  ELUMO.

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Fig. 3 Emission spectra of the dyes as (a) drop-cast thin films and (b) solid powder.
known that uorescence spectral shis and changes in the
quantum yield for a solid with respect to its solution depend on
the molecular packing in the solid state.20h,28 The presence of
strong p–p interactions between cofacially stacked molecules
lead to red-shied uorescence and a decrease in emission
efficiency. In the thin lm emission spectra of the compounds
(Fig. 3a), the bathochromic spectral shi and broadening clearly
indicates the presence of intermolecular interactions. Further-
more, the emission of the compounds in the solid state (Fig. 3b)
is further red-shied when compared to that in the thin lm and
is accompanied by a signicant broadening of the uorescence
band with a large full width half maximum (FWHM) (90 nm),
which is common for solid emitting materials.29 Moreover the
quantum yield for the solid (FF) is found to be quenched (Table
S1†) in comparison to the uorescence quantum yield (FF) in
DCM solvent, which supports molecular self-assembly arising
from strong p–p intermolecular interactions.
Self-assembly studies by absorption and emission spectra
The self-assembly of the compounds was investigated via
absorption and emission measurements in a binary THF : H2O
solvent system (Fig. 4 and S2–4†). The aggregation behaviours of
the compounds were conrmed by the gradual change in the
ratio of water to solvent. The solution color of the dyes was
found to change from 100% THF to 40–60% H2O accompanied
by a new 20–30 nm red shied absorption shoulder as
compared to the p–p* transitions in pure THF solvent. On
moving from 100% THF to 90% water, the absorption spectra
showed a hypochromic shi upon an increase in water content,
which suggests p-stacking among the chromophores. The
levelling off of the spectra observed in the longer wavelength
region at high water content is attributed to the scattering of
light due to the formation of aggregates. This result clearly
points towards the occurrence of p–p stacking in the aggregates
due to the formation of self-assembled structures.
In the uorescence spectra, the aggregate emission bath-
ochromically shis towards the solid state emission region. The
uorescence emission intensity in THF solution is 3–5 folds
higher than that of the (1 : 1) THF : H2O system. Such red-
shied and quenched emission intensity at high water
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content (Fig. S5†) could be attributed to the presence of p–p
stacking interactions that induce the self-assembly. This
supports the formation of aggregates driven by non-covalent
interactions, which is corroborated by the red shied absorp-
tion and emission bands and emission quenching in the solid
state.
Effect of aggregation on excited state decay dynamics
To investigate and analyze the effect of aggregation on radia-
tive and non-radiative transition rates (kr and knr), time
resolved uorescence lifetime decay measurements were
conducted for the compounds in THF solution and a 90%
water–THF mixture (Fig. 5, Table 2). The uorescence lifetime
measurements display the multi-exponential behavior of
emission decay, which was best tted with a double or triple
exponential function (Table S2†). According to Sillen et al. the
amplitude average lifetime is an effective parameter to derive
the transition rate constants of multi-exponential decays
caused by the exposure of uorescent molecules to different
environments.30 The calculated average lifetime27a (savg) of the
excited state of the dyes in solution is found to be long lived
compared with the corresponding aggregates. This can be
correlated to the quenching of FF in the aggregated and solid
state. Furthermore, the lifetime calculated is found to be
consistent with the order of quantum yields observed in
solution, aggregates and solid state of the dyes. The correlated
data reveal that the long lifetime value of 3.58 ns in solution
for 3d is attributed to delayed radiative rate decay, i.e., high
quantum yield. Moreover, in the aggregated state the lifetime
acquired is shorter, indicating a more efficient non-radiative
decay pathway. This is clearly reected by the magnitude of
knr, which is signicantly larger than the kr value for the
aggregates. Moreover, F. C. Spano et al. theoretically studied
exciton delocalization in molecular aggregates due to exciton-
vibration coupling.31 Thus, on comparing the radiative decay
rate of solution (0.4 ns1) and aggregates for 3b (1 ns1) and 3c
(8 ns1), the radiative decay rate is greatly enhanced, which is
characteristic for J-aggregates and is referred to as super-
radiance.32 This is clear evidence of the formation of
J-aggregates in the solid state, whereas the non-radiative decay
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Fig. 4 (a and b) Absorption and emission spectra of 3c from THF : H2O titration studies, respectively. (c) Normalized absorption and emission
spectra in THF solution, thin film and solid state. (d) Images of the solutions (top: under normal light and bottom: under UV light) obtained by
varying the water concentration in THF solvent for 3c (left to right – increasing water concentration 0–90%).

rate for the aggregation state is observed to be faster than the Electrochemical properties
corresponding knr values in solution, which reects effective Electrochemical analysis of the dyes was carried out using
intermolecular interactions that result in a signicant decline
cyclic voltammetry (CV) and differential pulse voltammetry
in uorescence quantum yield.
(DPV) measurements and the results are summarized in Table
If we look into the calculated lifetimes of the dyes, the rst
1. All the compounds exhibit a reversible redox couple attrib-
lifetime (sa) is equivalent to that of the 3a lifetime and
uted to the reduction of the naphthalimide unit (Fig. S6a†).20j
therefore can be ascribed to the emission from the naph-
Compound 3a exhibits a single two-electron reduction, while
thalimide skeleton,20j whereas the lifetime of less than a 1 ns
the other dyes show two or more reduction couples. This
time scale with ultrafast decay channels can be correlated to clearly indicates that the reduction propensity of the molecules
the non-emissive aggregated state of the dyes. We found it is enhanced upon the introduction of an additional acceptor in
interesting to correlate this uorescence decay analysis with
the conjugation pathway. However, it is interesting that only
the degree of assembling properties of the dyes. The long
the benzothiadiazole derivative 3c possessed a reduction
lifetime value of 1.84 ns for the aggregates of 3d as compared
potential larger than the dimer 3a, whereas the elongation of
to 0.01 ns for the other two dyes in the 90% water–THF system
conjugation with the incorporation of uorenone and dibenzo
reects the better self-assembly properties and solid state
[a,c]phenazine in 3b and 3d, respectively, contributes to the
quantum yield of the corresponding dye, whereas for 3a sagg is
decrement in the bandgap.16h,26 The benzothiadiazole deriva-
0.7 ns longer than in solution, i.e., the monomeric state. This tive, 3c displays a third reduction couple, which is attributable
could be due to stronger intermolecular interactions in the to the reduction of the benzothiadiazole moiety.16f The LUMO
excited state.18b Moreover, the longer life time in the aggre-
energy values deduced from the reduction potentials are close
gated state and micro structured ower-like morphology for
to 3.3 eV, which lie among those of typical air stable n-type
this dye is possibly due to the involvement of a large number
organic semiconductors.15c The high electron affinity across
of molecules in the aggregates. Thus, the uorescence lifetime
the p-conjugated backbone afforded by the two naph-
decay data for solution and aggregates offer us sufficient
thalimides and an electron decient central unit helps to
evidence for the existence of molecular aggregation in the
deepen the HOMO energy level, which lies in the range from
solid state. 5.9 eV to 6.3 eV. All the dyes exhibit an irreversible

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Theoretical studies
To understand the electronic features of the compounds,
density functional theoretical computations were performed on
model structures of the compounds in which the lengthy alkyl
chains are replaced by a methyl group to save on computational
time (Fig. 6). The geometry of the compounds was optimized
using the B3LYP functional and 6-31G(d,p) basis set (Fig. S7†).
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The optimized structures were then used for TDDFT computa-

tions at the (M06-2x/6-31G(d,p)) level (Table S6†). The optimized
structures assume a coplanar arrangement of functional enti-
ties, which ensures a close packing arrangement of molecules in
the solid state.8j,18b,23d The HOMO of the molecules is mainly
contributed by the p-linker and the naphthalene segment of
naphthalimide, whereas the HOMO1 orbital is mainly spread
over the naphthalimide unit. In compound 3d, the dibenzo[a,c]
phenazine unit also contributes to the formation of HOMO1.
The LUMO is mainly constructed by the central p-linker with
little contribution from the naphthalimide units. Interestingly,
the LUMO+1 is restricted to the naphthalimide unit in all the
compounds. The observed electronic distributions in the
molecules suggest the electron-withdrawing nature of the
constituting units. The prominent contribution of the p-linker
to the LUMO suggests the electron deciency of the central
bridge over the naphthalimide periphery.

Morphological properties
The morphologies of the as-synthesized compounds and those
obtained from the solvent system were investigated via eld
Fig. 5 Fluorescence decay profiles of the dyes in (a) THF solution and
emission scanning electron microscopy (FESEM). SEM images
(b) 90% water–THF mixture for 2  105 M aggregate solution. of the as synthesized samples (Fig. 7) reveal the presence of an
ample amount of rod-like nanostructures with diameters and
lengths in the range of hundreds of nanometers (nm) to several
Table 2 Time-resolved fluorescence and photophysical data for the micrometers (mm), respectively, and the rods/belts have
dyes in THF and 90% water–THF mixture a uniform nano sized diameter along their lengths. SEM images
show that the typical diameter of the nanostructures is
(savga), ns FFb krc, ns1 knrd, ns1 approximately 120  20 nm.
Dye Sol. Agg. Sol. Agg. Sol. Agg. Sol Agg. The dyes 3b–3d possessing a skeleton derived from elon-
gated conjugation, exhibits nanorods/belts, whereas 3a forms
3a 1.73 2.43 0.66 0.06 0.38 0.03 0.20 0.39 microowers (6  1 mm) composed of a number of nanoakes
3b 1.40 0.01 0.52 0.01 0.37 1.00 0.34 99.00 as petals in nanodimensions. Thus, the morphological differ-
3c 1.83 0.01 0.74 0.08 0.40 8.00 0.14 92.00
3d 3.58 1.84 0.90 0.15 0.25 0.08 0.03 0.46
ence between these chromophores is attributed to the differ-
ence in conjugation length. Moreover, it is observed that the
a
savg ¼ uorescence lifetime decay measured as savg ¼ (A1  s1) + (A2  SEM images of compound 3d reveal the formation of well-
s2) + (A3  s3) in ns. b Fluorescence relative quantum yield calculated
using coumarin 6 as a reference (0.78 in EtOH). c Radiative decay dened nanorods compared to the others for the as synthe-
rates (kr) calculated using k ¼ FF/s. d Non-radiative decay rate (knr) sized compounds due to the effective intermolecular interac-
calculated using F ¼ kr/(kr + knr). tions arising from the more extended planar p-conjugated
aromatic system. The mechanism for the formation of rods
arises from the effective p–p intermolecular head to tail
stacking between the molecules, whereas the ower-like
oxidation peak. It is worth mentioning that the electronic
morphology for 3a is formed by the arrangement of a number
structure of the naphthalimide core is nely tuned by the
of nanopetals and is driven by the intermolecular interactions,
introduction of electron withdrawing moieties and the energy
which can be correlated to the results obtained from UV-Vis
levels of all the dyes are favorable for them to act as n-type
spectroscopy and powder XRD analysis. It is also observed
semiconducting materials in organic light emitting diodes
that as the density of sample increases, the number of aggre-
(OLEDs), organic solar cells (OSCs) and organic thin lm
gates increases, as observed at the core center in the SEM
transistors (OTFTs).19b,23
images, which results in the formation of heaps of clusters.

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Fig. 6 Electronic distribution in the frontier molecular orbitals of the model compounds 3a–3d.
Fig. 7 FESEM images of the as synthesized compounds (a–d) 3a–3d,
respectively; scale bar: (a) (i) 10 mm, (ii) 1 mm; (b–c) (i) 2 mm, (ii) 1 mm and
(iii) DLS-determined size distribution profiles for the aggregates
formed from (a–d) 3a–3d in THF/H2O (1 : 9; 2  105 M), respectively.
When the stacking forces between the molecules are too large,
ill-dened super structural assemblies are formed. This is also
conrmed by the SEM images of the compounds, as shown in
Fig. S8.†
In Fig. 8, the FESEM images of the aggregates of 3c obtained
from the binary THF : H2O solvent system at 50% and 90% H2O,
which were prepared for absorption and emission studies,
clearly support the formation of aggregates due to sol-
vophobicity and p–p intermolecular interactions resulting in
long-range ordering and nally induces the formation of
nanostructures. Very long and thin brous nano to micro scale
structures of several micrometer lengths are obtained for the
sample in the 50% THF : H2O system, whereas for the 90% H2O
system a bunch of nanosized rigid aggregates are observed,
revealing the formation of nanorods. Moreover, aer 1 week at
room temperature the same sample solution gives nano to
micro scale crystalline SEM images in the form of typical rods
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and cubes of nano dimensions due to the facile crystallization
induced by the conjugated core, hydrophobicity of the alkyl
chains and effective intermolecular forces between the aromatic
moieties.
Furthermore, the ne and uniform nanostructures obtained
for compound 3d allow us to investigate the SEM images of the
drop-casted precipitates obtained from DMF solution at the low
concentration of 1 mM, which give spindle shaped thin and
long bers of diameter 120  10 nm and length of approxi-
mately 10 mm throughout the sample area under investigation.
Moreover, the presence of strong intermolecular interactions
and formation of thin brous network-like assemblies moti-
vated us to organogelate the compound.13f,14e,18b,33 Therefore,
a supersaturated sample of 1 wt% (16 mM) DMF solution
concentration was prepared via the heating–cooling method;
however, due to the crystalline nature of the compound it rep-
recipitated out during the cooling process. SEM images of the
reprecipitated crystalline compound show uniform sized cubic
Fig. 8 FESEM images of 3c (a) long entangled fibres in 50% THF : H2O;
scale bar: (i) 5 mm and (ii) 2 mm; inset showing a long fibrous strand;
scale bar 2 mm. (b) Formation of nanorods in 90% THF : H2O; scale bar:
(i) 5 mm and (ii) 2 mm; inset showing magnified image of nanorods at the
scale bar of 1 mm. (c) (i–iv) Formation of crystalline 3-D rods and cubes
at different scale bars: 50, 10, 5, and 1 mm respectively from 90%
THF : H2O after 1 week.
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properties of these small molecules are useful for the design

and fabrication of displays and at screens.

Powder X-ray diffraction analysis

To investigate the molecular arrangement in the solid state,
powder X-ray diffraction (PXRD) was carried out, which is
depicted in Fig. 10 and the calculated d-spacing values are
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summarized in Table S4.† The pattern obtained clearly shows

Fig. 9 FESEM images of (a) 3d from 1 mM DMF showing spindle
intensive and sharp peaks within the range of 2q ¼ 5 to <50 ,
shaped nanofibers; scale bar (i) 10 mm and (ii) 2 mm, inset 1 mm. (b) (i–iv)
3d crystalline 3-D structures from 1 wt% DMF. (c) 3a from 1 mM DMF; suggesting a well-ordered crystalline structure. The intermo-
scale bar (i) 10 mm and (ii) 2 mm. (d) Precipitates of 3a from 1 wt% DMF lecular distance calculated from the peak positions is found to
as sheets and flowers; scale bar (i) 100 mm, inset 50 mm and (ii) 50 mm, be effective for p–p intermolecular interactions.2g,19h The sharp
inset 20 mm. diffraction peak at 2q ¼ 25 corresponds to the d-spacing of
3.49 Å, 3.43 Å, 3.55 Å and 3.49 Å for 3a–3d, respectively, and can
be attributed to the p–p stacking intermolecular distance
crystals of approximately 1  1 mm2 throughout the glass plate, responsible for the self-assembling, whereas the sharp diffrac-
which assemble to form large crystals in the form of cuboids tion peak at 2q ¼ 6 analogous to the d-spacing of 13 Å can
and rods, and is driven by the minimization of the surface area, be attributed to the translational slip stacking of the small
as shown in Fig. 9a and b. We tried to grow crystals of the dyes molecules into J-aggregates, as reported in earlier reports.16i,23f
in a number of solvent systems for single crystal X-ray diffrac- Therefore, we conclude that the pattern obtained reects an
tion studies but were unsuccessful in obtaining crystals that organized assembly and crystallinity of these p-conjugated
could diffract, and instead ended up with bers or a mosaic. On molecules in the solid state, which are suitable for excellent
the other hand, 3a (Fig. 9c and d) exhibits clusters of nanoakes charge transportation by an enhanced intermolecular transfer
as heaps in 1 mM DMF, while it precipitates out as supramo- rate.
lecular sheets and owers from the 1 wt% DMF solution system.
These morphological changes are due to the concentration Thermal properties
dependence of self-aggregation.
The thermal stability of materials based on nanostructures is of
Thus, it can be stated that the facile tunable morphology at
paramount importance for the construction of electronic
the nanoscale of the planar and rigid end-capped naph-
devices to withstand high temperatures. Therefore, we investi-
thalimide based organic n-type semiconductors is of great
gated the melting temperature (Tm) and decomposition
importance for a large number of efficient device applications.
temperatures (Td) of the compounds via differential scanning
calorimetry (DSC) and thermo-gravimetric analysis (TGA). The
Dynamic light scattering analysis
relevant traces are shown in Fig. 11 and the data is summarized
Dynamic light scattering (DLS) was used to determine the in Table S5.† The endothermic sharp peak in the DSC plots
particle size distribution of the aggregates of the dyes in represents Tm, which increases in the order of 3a < 3c < 3d < 3b
THF : H2O mixtures (2  105 M) with water fractions (fw) of and points to the increasing trend of molecular interactions and
90%, which indicates a homogenous dispersion (Fig. 3, iii). The presence of some degree of molecular ordering within the
median diameter (dm) and average diameter (davg) for the
aggregates was found to be in range of 125–155 nm and >200
nm, respectively (Table S3†), which is in good agreement with
the SEM data. The particle size distribution peak for 3b–3d is
narrower than 3a, suggesting a well-ordered particle distribu-
tion.34 Bimodal distributions are observed for 3a, whereas the
others exhibited unimodal distributions. The additional less
intense peak observed for the 3a dispersion centered at 6 mm
is attributed to the diameter of the ower like morphology, as
observed in the FESEM images.

Fluorescence microscopy analysis

Furthermore, uorescence images of the dyes (Fig. S9†) were
obtained using optical uorescence microscopy, exhibiting
multicolor emission35 under different light sources due to the
broad emission region. The drop-casted lm obtained from
dichloromethane solution (1 mM) shows bright yellow-green
and orange-red uorescence upon excitation with blue and
green light, respectively. Therefore, the multicolor emission Fig. 10 PXRD of the small molecules (3a–3d).

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Fig. 11 (a) TGA and (b) DSC curves of the compounds.
molecules, which are favorable for charge transportation,
whereas the broad exothermic peak above 300  C corresponds
to the weight loss of the compound because of the deimidiza-
tion process. Furthermore, the crystalline behavior of
compounds is proven by the absence of a glass transition
temperature (Tg).23a,23f Their excellent thermal stability is
conrmed from the two-step decomposition pathway with Td at
10% weight loss above 400  C. The weight loss in the rst step
between 400 and 550  C may be due to the degradation of the
alkyl chains and other labile units, whereas the second step
between 500 and 700  C corresponds to the loss of aromatic
residue and other stronger bonds. Thus, the thermal analysis
clearly reects both the crystalline behavior and high thermal
stability of the non-covalent interactions based self-assembled
small molecules.
Conclusions
In summary, we shed light on the self-assembly properties of
rigid, linear and highly electron decient p-conjugated naph-
thalimide derivatives synthesized via the Sonogashira coupling
reaction. The solution, thin lm and solid state optical prop-
erties of the dyes support the presence of intermolecular
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interactions and p–p stacking, which enhance charge transport
properties. This is further supported by the powder XRD anal-
ysis of the as synthesized samples. Fluorescence lifetime decay
measurements highlight the effect of aggregation on the decay
dynamics of the excited state. Furthermore, the thermal and
electrochemical data indicate high thermal stability, crystal-
linity and suitable energetics, which support the high electron
deciency of the molecules with high electron affinity and deep
HOMO energy levels that make the molecules suitable for use as
electron accepting semiconductors. Density functional theo-
retical investigations highlight the electronic properties and
ensure the coplanar geometries of the compounds. The
morphology patterns observed in the FESEM images of these
organic molecules conrm p–p stacking interactions and
establish the well-dened formation of nanostructures with rod
shaped or ower like morphologies in the solid state. It is also
found that the morphology varies with concentration and
solvent. DLS analysis further strengthens the formation of the
nanomorphology for the aggregates. Therefore, it is possible to
use varying aromatic units that exhibit planarity and rigidity as
a tool to control the molecular packing, orientation, and inter-
molecular spacing of aromatics in the solid state. Judiciously
and efficiently tuning the properties of such class of nano-
structural materials could be benecial for n-type organic
semiconducting materials to study electronic transport prop-
erties in a number of solution processed nano-optoelectronic
devices. Application of these small molecules as emitters and
electron transporting layers in OLEDs and non-fullerene
acceptors in OSCs is ongoing work in our laboratory.
Acknowledgements
KRJT is thankful to CSIR (Ref. No. 02/(0230)/15/EMR-II dated 05-
06-2015), New Delhi for generous nancial support. AS
acknowledges a research fellowship from Ministry of Human
Resources and Development (MHRD), Government of India. We
are also thankful to DST for the purchase of ESI mass spec-
trometer via the FIST grant to the Chemistry Department, IIT
Roorkee.
Notes and references
1 (a) W. Yao and Y. S. Zhao, Nanoscale, 2014, 6, 3467; (b) Y. Lin,
Y. Li and X. Zhan, Chem. Soc. Rev., 2012, 41, 4245; (c)
J. L. Atwood and J. W. Steed, Organic Nanostructures, Wiley,
New York, 2008; (d) L. Magginia and D. Bonifazi, Chem.
Soc. Rev., 2012, 41, 211; (e) B. K. An, S. H. Gihm,
J. W. Chung, C. R. Park, S. K. Kwon and S. Y. Park, J. Am.
Chem. Soc., 2009, 131, 3950; (f) Y. S. Zhao, H. B. Fu,
F. Q. Hu, A. D. Peng, W. S. Yang and J. N. Yao, Adv. Mater.,
2008, 20, 79; (g) P. S. Weiss, Acc. Chem. Res., 2008, 41, 1772;
(h) F. Würthner, Supramolecular Dye Chemistry, Topics in
Current Chemistry, Springer, Berlin, 2005, p. 258; (i)
S. I. Stupp, Chem. Rev., 2005, 105, 1023; (j) D. B. Xiao,
X. Lu, W. S. Yang, H. B. Fu, Z. G. Shuai, Y. Fang and
J. N. Yao, J. Am. Chem. Soc., 2003, 125, 6740.
This journal is © The Royal Society of Chemistry 2016

Paper
2 (a) Q. Yan, Z. Luo, K. Cai, Y. Ma and D. Zhao, Chem. Soc. Rev.,
2014, 43, 4199; (b) M. R. Molla and S. Ghosh, Phys. Chem.
Chem. Phys., 2014, 16, 26672; (c) A. Das and S. Ghosh,
Angew. Chem., Int. Ed., 2014, 53, 2038; (d) A. C. Mendes,
E. T. Baran, R. L. Reis and H. S. Azevedo, Wiley Interdiscip.
Rev.: Nanomed. Nanobiotechnol., 2013, 5, 582; (e)
B. Rybtchinski, ACS Nano, 2011, 5, 6791; (f)
Published on 11 July 2016. Downloaded by Indian Institute of Technology Roorkee on 28/07/2016 11:20:51.
D. G. Rodrı́guez and A. P. H. J. Schenning, Chem. Mater.,
2011, 23, 310; (g) T. Nakanishi, Chem. Commun., 2010, 46,
3425; (h) S. Yagai and A. Kitamura, Chem. Soc. Rev., 2008,
37, 1520; (i) J. W. Steed, D. R. Turner and K. J. Wallace,
Core concepts in supramolecular chemistry and
nanochemistry, Wiley, 2007; (j) F. J. M. Hoeben,
P. Jonkheijm, E. W. Meijer and A. P. H. J. Schenning,
Chem. Rev., 2005, 105, 1491; (k) C. P. Poole, Introduction to
nanotechnology, John Wiley & Sons, Hoboken, New Jersey,
USA, 2003; (l) R. K. Castellano and J. Rebek, J. Am. Chem.
Soc., 1998, 120, 3657; (m) M. Li, H. Schnablegger and
S. Mann, Nature, 1999, 402, 393; (n) J.-M. Lehn,
Supramolecular Chemistry: Concepts and Perspectives, Wiley,
New York, 1995.
3 (a) Y. S. Zhao, Organic Nanophotonics: Fundamentals and
Applications, Wiley, New York, 2014; (b) B. Z. Tian, J. Liu,
T. Dvir, L. H. Jin, J. H. Tsui, Q. Qing, Z. G. Suo, R. Langer,
D. S. Kohane and C. M. Lieber, Nat. Mater., 2012, 11, 986;
(c) C. Zhang, Y. S. Zhao and J. Yao, Phys. Chem. Chem.
Phys., 2011, 13, 9060; (d) H. Zheng, Y. Li, H. Liu, X. Yin
and Y. Li, Chem. Soc. Rev., 2011, 40, 4506; (e) F. S. Kim,
G. Ren and S. A. Jenekhe, Chem. Mater., 2011, 23, 682; (f)
Y. Zhao, H. Fu, A. Peng, Y. Ma, Q. Liao and J. Yao, Acc.
Chem. Res., 2010, 43, 409; (g) H. Liu, J. Xu, Y. Li and Y. Li,
Acc. Chem. Res., 2010, 43, 1496; (h) A. Mishra, C.-Q. Ma and
P. Bauerle, Chem. Rev., 2009, 109, 1141; (i) L. Zang, Y. Che
and J. F. Moore, Acc. Chem. Res., 2008, 41, 1596.
4 (a) Y. Li, T. Liu, H. Liu, M. Z. Tian and Y. Li, Acc. Chem. Res.,
2014, 47, 1186; (b) R. J. Li, W. P. Hu, Y. Q. Liu and D. B. Zhu,
Acc. Chem. Res., 2010, 43, 529; (c) Z. Chen, A. Lohr, C. R. Saha-
Möller and F. Würthner, Chem. Soc. Rev., 2009, 38, 564; (d)
J. Lv, H. B. Liu and Y. L. Li, Pure Appl. Chem., 2008, 80,
639; (e) L. Zang, Y. Che and J. S. Moore, Acc. Chem. Res.,
2008, 41, 1596; (f) C. Li, T. Hatano, M. Takeuchi and
S. Shinkai, Chem. Commun., 2004, 20, 2350.
5 (a) C. Sutton, C. Risko and J.-L. Bredas, Chem. Mater., 2016,
28, 3; (b) S. Mukherjee and P. Thilagar, Chem.–Eur. J., 2014,
20, 8012; (c) S. Ehrlich, J. Moellmann and S. Grimme, Acc.
Chem. Res., 2012, 46, 916; (d) L. C. Palmer and S. I. Stupp,
Acc. Chem. Res., 2008, 41, 1674; (e) A. C. Grimsdale and
K. Müllen, Angew. Chem., Int. Ed., 2005, 44, 5592; (f)
F. Würthner, Chem. Commun., 2004, 14, 1564; (g)
T. Q. Nguyen, R. Martel, P. Avouris, M. L. Bushey, L. Brus
and C. Nuckolls, J. Am. Chem. Soc., 2004, 126, 5234.
6 (a) E. E. Jelley, Nature, 1936, 138, 1009; (b) G. Scheibe, Angew.
Chem., 1937, 50, 212.
7 F. Würthner, C. Thalacker, S. Diele and C. Tschierske,
Chem.–Eur. J., 2001, 7, 2245.
8 (a) R. Hu, J. W. Y. Lam, H. Deng, Z. Song, C. Zheng and
B. Z. Tang, J. Mater. Chem. C, 2014, 2, 6326; (b) L. Chen,
This journal is © The Royal Society of Chemistry 2016
View Article Online
RSC Advances
C. Li and K. Müllen, J. Mater. Chem. C, 2014, 2, 1938; (c)
M. R. Rao and S.-S. Sun, Langmuir, 2013, 29, 15146; (d)
B. K. An, J. Gierschner and S. Y. Park, Acc. Chem. Res.,
2012, 45, 544; (e) D. G. Rodrı́guez and
A. P. H. J. Schenning, Chem. Mater., 2011, 23, 310; (f)
N. Sakai, J. Mareda, E. Vauthey and S. Matile, Chem.
Commun., 2010, 46, 4237; (g) Z. Chen, A. Lohr, C. R. Saha-
Mçller and F. Würthner, Chem. Soc. Rev., 2009, 38, 564; (h)
A. Mishra, C.-Q. Ma and P. Bauerle, Chem. Rev., 2009, 109,
1141; (i) A. Ajayaghosh and V. K. Praveen, Acc. Chem. Res.,
2007, 40, 644; (j) F. J. M. Hoeben, P. Jonkheijm,
E. W. Meijer and A. P. H. J. Schenning, Chem. Rev., 2005,
105, 1491.
9 (a) J. E. Park, M. Son, M. Hong, G. Lee and H. C. Choi, Angew.
Chem., Int. Ed., 2012, 51, 6383; (b) T. Jiu, Y. Li, H. Liu, J. Ye,
X. Liu, L. Jiang, M. Yuan, J. Li, C. Li, S. Wang and D. Zhu,
Tetrahedron, 2007, 63, 3168; (c) S. Yagai, Y. Goto, X. Lin,
T. Karatsu, A. Kitamura, D. Kuzuhara, H. Yamada,
Y. Kikkawa, A. Saeki and S. Seki, Angew. Chem., Int. Ed.,
2012, 51, 6643.
10 (a) J. Zhu, K. Zhong, Y. Liang, Z. Wang, T. Chen and L. Y. Jin,
Tetrahedron, 2014, 70, 1230; (b) C. Wang, Y. Liu, Z. Ji,
E. Wang, R. Li, H. Jiang, Q. Tang, H. Li and W. Hu, Chem.
Mater., 2009, 21, 2840–2845; (c) Y. S. Zhao, J. J. Xu,
A. D. Peng, H. B. Fu, Y. Ma, L. Jiang and J. N. Yao, Angew.
Chem., Int. Ed., 2008, 47, 7301–7305.
11 (a) J. Xiao, X. Xiao, Y. Zhao, B. Wu, Z. Liu, X. Zhang, S. Wang,
X. Zhao, L. Liu and L. Jiang, Nanoscale, 2013, 5, 5420; (b)
Y. Sagara, T. Mutai, I. Yoshikawa and K. Araki, J. Am.
Chem. Soc., 2007, 129, 1520; (c) X. J. Zhang, X. H. Zhang,
W. S. Shi, X. M. Meng, C. Lee and S. Lee, J. Phys. Chem. B,
2005, 109, 18777.
12 (a) Y. Yan, C. Zhang, J. Yao and Y. S. Zhao, Adv. Mater., 2013,
25, 3627; (b) Y. L. Lei, Q. Liao, H. B. Fu and J. N. Yao, J. Phys.
Chem. C, 2009, 113, 10038; (c) C. Ego, D. Marsitzky, S. Becker,
J. Zhang, A. Grimsdale, K. Müllen, J. MacKenzie, C. Silva and
R. Friend, J. Am. Chem. Soc., 2003, 125, 437.
13 (a) F. Würthner, C. R. Saha-Möller, B. Fimmel, S. Ogi,
P. Leowanawat and D. Schmidt, Chem. Rev., 2015, 116, 962;
(b) S. Chen, P. Slattum, C. Wang and L. Zang, Chem. Rev.,
2015, 115, 11967; (c) L. Xu, D. Gao, J. Song, L. Shen,
W. Chen, Y. Chen and S. Zhang, New J. Chem., 2015, 39,
5553; (d) C. Li and H. Wonneberger, Adv. Mater., 2012, 24,
613; (e) D. Görl, X. Zhang and F. Würthner, Angew. Chem.,
Int. Ed., 2012, 51, 6328; (f) J. Lambrecht, T. P. I. Saragi and
J. Salbeck, J. Mater. Chem., 2011, 21, 18266; (g)
K. Balakrishnan, A. Datar, R. Oitker, H. Chen, J. M. Zuo
and L. Zang, J. Am. Chem. Soc., 2005, 127, 10496; (h)
G. D. Sharma, M. S. Roy, J. A. Mikroyannidis and
K. R. J. Thomas, Org. Electron., 2012, 13, 3118; (i)
A. S. Sayyad, K. Balakrishnan and P. M. Ajayan, Nanoscale,
2011, 3, 3605; (j) K. Balakrishnan, A. Datar, T. Naddo,
J. L. Huang, R. Oitker, M. Yen, J. C. Zhao and L. Zang, J.
Am. Chem. Soc., 2006, 128, 7390; (k) P. Yan, A. Chowdhury,
M. W. Holman and D. M. Adams, J. Phys. Chem. B, 2005,
109, 724; (l) X.-Q. Li, V. Stepanenko, Z. Chen, P. Prins,
L. D. A. Siebbeles and F. Würthner, Chem. Commun., 2006,
RSC Adv., 2016, 6, 71638–71651 | 71649

RSC Advances
3871; (m) R. Dobrawa and F. Würthner, Chem. Commun.,
2002, 1878; (n) F. Würthner, A. Sautter and J. Schilling, J.
Org. Chem., 2002, 67, 3037; (o) G. R. J. Müller, C. Meiners,
V. Enkelmann, Y. Greerts and K. Müllen, J. Mater. Chem.,
1998, 8, 61.
14 (a) M. Mastalerz, E. Menke, Y. Vaynzof and V. Lami, Chem.
Commun., 2016, 52, 1048; (b) H. Kar, D. W. Gehrig,
Published on 11 July 2016. Downloaded by Indian Institute of Technology Roorkee on 28/07/2016 11:20:51.
F. Laquai and S. Ghosh, Nanoscale, 2015, 7, 6729; (c)
R. Fernando, Z. Mao and G. Sauve, Org. Electron., 2013, 14,
1683; (d) E. Ahmed, G. Ren, F. S. Kim, E. C. Hollenbeck
and S. A. Jenekhe, Chem. Mater., 2011, 23, 4563; (e)
S. Basak, N. Nandi, A. Baral and A. Banerjee, Chem.
Commun., 2015, 51, 780.
15 (a) Z. Liu, G. Zhang, Z. Cai, X. Chen, H. Luo, Y. Li, J. Wang
and D. Zhang, Adv. Mater., 2014, 26, 6965; (b) Y. Li,
P. Sonar, L. Murphy and W. Hong, Energy Environ. Sci.,
2013, 6, 1684; (c) H. Usta, A. Facchetti and T. Marks, Acc.
Chem. Res., 2011, 44, 501; (d) X. Zhan, A. Facchetti,
S. Barlow, T. Marks, M. Ratner, M. Wasielewski and
S. Marder, Adv. Mater., 2011, 23, 268; (e) C. B. Nielsen,
M. Turbiez and I. McCulloch, Adv. Mater., 2013, 25, 1859;
(f) Y. Zhao, Y. Guo and Y. Liu, Adv. Mater., 2013, 25, 5372;
(g) Y. Li, P. Sonar, L. Murphy and W. Hong, Energy Environ.
Sci., 2013, 6, 1684.
16 (a) W. Yao, Y. Yan, L. Xue, C. Zhang, G. Li, Q. Zheng,
Y. S. Zhao, H. Jiang and J. Yao, Angew. Chem., Int. Ed.,
2013, 52, 8713; (b) N. Chandrasekhar and R. Chandrasekar,
Angew. Chem., Int. Ed., 2012, 51, 3556; (c) Y. Wang, H. Fu,
A. Peng, Y. Zhao, J. Ma, Y. Ma and J. Yao, Chem. Commun.,
2007, 1623; (d) Z. Tian, Y. Chen, W. Yang, J. Yao, L. Zhu
and Z. Shuai, Angew. Chem., Int. Ed., 2004, 43, 4060; (e)
S. Chen, N. Chen, Y. Yan, T. Liu, Y. Yu, Y. Li, H. Liu,
Y. Zhao and Y. Li, Chem. Commun., 2012, 48, 9011; (f)
S. Chen, Y. Li, W. Yang, N. Chen, H. Liu and Y. Li, J. Phys.
Chem. C, 2010, 114, 15109; (g) Y. Wang, J. L. Liu,
H. D. Tran, M. Mecklenburg, X. N. Guan, A. Z. Stieg,
B. C. Regan, D. C. Martin and R. B. Kaner, J. Am. Chem.
Soc., 2012, 134, 9251; (h) J. Xu, S. Semin, D. Niedzialek,
P. H. J. E. Kouwer, E. Fron, E. Coutino, M. Savoini, Y. Li,
J. Hoens, H.-I. Uji, D. Beljonne, T. Rasing and
A. E. Rowan, Adv. Mater., 2013, 25, 2084; (i) A. Ghodbane,
S. D'Altério, N. Saffon, N. D. McClenaghan,
L. Scarpantonio, P. Jolinat and S. F. Forgues, Langmuir,
2012, 28, 855; (j) S. Sampath, A. A. Boopathi and
A. B. Mandal, Phys. Chem. Chem. Phys., 2016, DOI: 10.1039/
c6cp02662a.
17 (a) D. Gudeika, J. V. Grazulevicius, D. Volyniuk, G. Juska,
V. Jankauskas and G. Sini, J. Phys. Chem. C, 2015, 119,
28335; (b) P. Gautam, R. Maragani, S. M. Mobin and
R. Misra, RSC Adv., 2014, 4, 52526; (c) K. R. J. Thomas,
N. Kapoor, M. N. K. P. Bolisetty, J.-H. Jou, Y.-L. Chen and
Y.-C. Jou, J. Org. Chem., 2012, 77, 3921; (d)
A. L. Thompson, T. S. Ahn, K. R. J. Thomas,
S. Thayumanavan, T. J. Martinez and C. J. Bardeen, J. Am.
Chem. Soc., 2005, 127, 16348; (e) J. T. Bloking, X. Han,
A. T. Higgs, J. P. Kastrop, L. Pandey, J. E. Norton, C. Risko,
71650 | RSC Adv., 2016, 6, 71638–71651
View Article Online
Paper
C. E. Chen, J. L. Brédas, M. D. McGehee and A. Sellinger,
Chem. Mater., 2011, 23, 5484.
18 (a) P. Josse, C. Dalinot, Y. Jiang, S. Dabos, J. Roncali,
P. Blanchard and C. Cabanetos, J. Mater. Chem. A, 2016, 4,
250; (b) X. Cao, L. Meng, Y. Mao, H. Lan, L. Chen, Y. Fan
and T. Yi, Langmuir, 2014, 30, 11753; (c) M. Kivala and
F. Diederich, Acc. Chem. Res., 2009, 42, 235.
19 (a) A. F. Furcate, T. Higashino, D. Lorcy and T. Mori, J. Mater.
Chem. C, 2015, 3, 3569; (b) H. Usta, A. Facchetti and
T. J. Marks, Acc. Chem. Res., 2011, 44, 501; (c) X. Gao and
Y. Hu, J. Mater. Chem. C, 2014, 2, 3099; (d) A. Lv,
S. R. Puniredd, J. Zhang, Z. Li, H. Zhu, W. Jiang, H. Dong,
Y. He, L. Jiang, Y. Li, W. Pisula, Q. Meng, W. Hu and
Z. Wang, Adv. Mater., 2012, 24, 2626; (e) L. Tan, Y. Guo,
G. Zhang, Y. Yang, D. Zhang, G. Yu, W. Xu and Y. Liu, J.
Mater. Chem., 2011, 21, 18042; (f) Y. Hu, X. Gao, C. Di,
X. Yang, F. Zhang, Y. Liu, H. Li and D. Zhu, Chem. Mater.,
2011, 23, 1204; (g) T. Kono, D. Kumaki, J. Nishida,
S. Tokito and Y. Yamashita, Chem. Commun., 2010, 46,
3265; (h) H. Wada, K. Shibata, Y. Bando and T. Mori, J.
Mater. Chem., 2008, 18, 4165.
20 (a) C. Peebles, C. D. Wight and B. Iverson, J. Mater. Chem. C,
2015, 3, 12156; (b) A. R. Mallia, P. S. Salini and M. Hariharan,
J. Am. Chem. Soc., 2015, 137, 15604; (c) Q. Zhang, H. Zhuang,
J. He, S. Xia, H. Li, N. Li, Q. Xu and J. Lu, J. Mater. Chem. C,
2015, 3, 6778; (d) T. Inari, M. Yamano, A. Hirano, K. Sugawa
and J. Otsuki, J. Phys. Chem. A, 2014, 118, 5178; (e)
S. Mukherjee and P. Thilagar, Phys. Chem. Chem. Phys.,
2014, 16, 20866; (f) B. Ventura, A. Bertocco, D. Braga,
L. Catalano, S. d'Agostino, F. Grepioni and P. Taddei, J.
Phys. Chem. C, 2014, 118, 18646; (g) H. Herrera, P. de
Echegaray, M. Urdanpilleta, M. J. Mancheño, E. Mena-
Osteritz, P. Bäuerle and J. L. Segura, Chem. Commun., 2013,
49, 713; (h) D. L. Reger, A. Debreczeni, J. J. Horger and
M. D. Smith, Cryst. Growth Des., 2011, 11, 4068; (i)
P. Kucheryavy, G. Li, S. Vyas, C. Hadad and K. D. Glusac, J.
Phys. Chem. A, 2009, 113, 6453; (j) M. S. Alexiou,
V. Tychopoulos, S. Ghorbanian, J. H. P. Tyman,
R. G. Brown and P. I. Brittain, J. Chem. Soc. Perkin Trans. 2,
1990, 837; (k) S. Jinnai, Y. Le, M. Karakawa, T. Aernouts,
Y. Nakajima, S. Mori and Y. Aso, Chem. Mater., 2016, 28,
1705; (l) P. Gautam, R. Misra, S. Biswas and G. D. Sharma,
Phys. Chem. Chem. Phys., 2016, 18, 13918–13926; (m)
J. Zhang, H. Xiao, X. Zhang, Y. Wu, G. Li, C. Li, X. Chen,
W. Ma and J. Bo, J. Mater. Chem. C, 2016, 4, 5656–5663.
21 (a) G. Chen, J. Song, H. Zhang, Y. Jiang, W. Liu, W. Zhang
and B. Wang, Nanoscale, 2015, 7, 14393; (b) S. Banerjee,
E. B. Veale, C. M. Phelan, S. A. Murphy, G. M. Tocci,
L. J. Gillespie, D. O. Frimannsson, J. M. Kelly and
T. Gunnlaugsson, Chem. Soc. Rev., 2013, 42, 1601; (c)
M. H. Lee, J. Y. Kim, J. H. Han, S. Bhuniya, J. L. Sessler,
C. Kang and J. S. Kim, J. Am. Chem. Soc., 2012, 134, 12668;
(d) L. Ingrassia, F. Lefranc, R. Kiss and T. Mijatovic, Curr.
Med. Chem., 2009, 16, 1192.
22 (a) M. Kumar, N. Kumar and V. Bhalla, Chem. Commun.,
2013, 49, 877; (b) R. M. Duke, E. B. Veale, F. M. Pfeffer,
This journal is © The Royal Society of Chemistry 2016

Paper
P. E. Krugerc and T. Gunnlaugsson, Chem. Soc. Rev., 2010,
39, 3936.
23 (a) J. Zhang, X. Zhang, G. Li, H. Xiao, W. Li, S. Xie, C. Li and
Z. Bo, Chem. Commun., 2016, 52, 469; (b) X. Zhang, J. Zhang,
H. Lu, J. Wu, G. Li, C. Li, S. Li and Z. Bo, J. Mater. Chem. C,
2015, 3, 6979; (c) P. Gopikrishna, D. Das and P. K. Iyer, J.
Mater. Chem. C, 2015, 3, 9318; (d) H.-C. Wu, J. Zhang, Z. Bo
Published on 11 July 2016. Downloaded by Indian Institute of Technology Roorkee on 28/07/2016 11:20:51.
and W.-C. Chen, Chem. Commun., 2015, 51, 14179; (e)
R.-Q. Lu, Y. Q. Zheng, Y. N. Zhou, X. Y. Yan, T. Lu, K. Shi,
Y. Zhou, J. Pei, L. Zoopi, K. K. Baldridge, J. S. Seigel and
X. Y. Cao, J. Mater. Chem. A, 2014, 2, 20515; (f) G. Wang,
S. Miao, Q. Zhang, H. Liu, H. Li, N. Li, Q. Xu, J. Lu and
L. Wang, Chem. Commun., 2013, 49, 9470; (g) O. K. Kwon,
M. A. Uddin, J.-H. Park, S. K. Park, T. L. Nguyen,
H. Y. Woo and S. Y. Park, Adv. Mater., 2016, 28, 910–916;
(h) J. Zhang, X. Zhang, H. Xiao, G. Li, Y. Liu, C. Li,
H. Huang, X. Chen and Z. Bo, ACS Appl. Mater. Interfaces,
2016, 8, 5475.
24 H. G. Rule and S. B. Thompson, J. Chem. Soc., 1937, 1764.
25 (a) P. Singh, A. Baheti and K. R. J. Thomas, J. Org. Chem.,
2011, 76, 6134; (b) E. K. Unver, S. Tarkuc, Y. A. Udum,
C. Tanyeli and L. Toppare, J. Polym. Sci., Part A: Polym.
Chem., 2010, 48, 1714; (c) X. Zhang, J.-B. Han, P.-F. Li, X. Ji
and Z. Zhang, Synth. Commun., 2009, 39, 3804; (d)
K. R. J. Thomas, M. Velusamy, J. T. Lin, C.-H. Chuen and
Y.-T. Tao, Chem. Mater., 2005, 17, 1860; (e) K. Pilgram,
M. Zupan and R. Skiles, J. Heterocycl. Chem., 1970, 7, 629.
26 (a) J. Shi, J. Chen, Z. Chai, H. Wang, R. Tang, K. Fan, M. Wu,
H. Han, J. Qin, T. Peng, Q. Li and Z. Li, J. Mater. Chem., 2012,
22, 18830; (b) L. A. Estrada and D. C. Neckers, Org. Lett.,
2011, 13, 3304.
27 (a) J. R. Lakowicz, Principles of Fluorescence Spectroscopy,
Springer Science + Business Media, New York, 3rd edn,
2006; (b) H.-T. Feng, J.-B. Xiong, Y.-S. Zheng, B. Pan,
C. Zhang, L. Wang and Y. Xie, Chem. Mater., 2015, 27, 7812.
28 (a) Z. Chen, U. Baumeister, C. Tschierske and F. Würthner,
Chem.–Eur. J., 2007, 13, 450; (b) K. Balakrishnan, A. Datar,
R. Oitker, H. Chen, J. Zuo and L. Zang, J. Am. Chem. Soc.,
2005, 127, 10496.
29 (a) B. M. Krasovitskii and B. M. Bolotin, Organic Luminescent
Materials, VCH: Weinheim, Germany, 2002; (b) E. A. Silinsh,
This journal is © The Royal Society of Chemistry 2016
View Article Online
RSC Advances
Organic Molecular Crystals, Springer-Verlag, Berlin, 1980; (c)
J. B. Birks, Photophysics of Aromatic Molecules, Wiley,
London, 1970.
30 A. Sillen and Y. Engelborghs, Photochem. Photobiol., 1998, 67,
475.
31 F. C. Spano, J. Am. Chem. Soc., 2009, 131, 4267.
32 (a) F. Würthner, T. E. Kaiser and C. R. Saha-Müller, Angew.
Chem., Int. Ed., 2011, 50, 3376; (b) T. Kobayashi, J-
Aggregates, World Scientic, Singapore, 1996.
33 (a) S. S. Babu, S. P. Kumar and A. Ajayaghosh, Angew. Chem.,
Int. Ed., 2012, 51, 1766; (b) X. Q. Li, V. Stepanenko, Z. J. Chen,
P. Prins, L. D. A. Siebbeles and F. Würthner, Chem. Commun.,
2006, 3871; (c) P. Terech and R. G. Weiss, Chem. Rev., 1997,
97, 3133.
34 A. K. Mandal, S. Sreejith, T. He, S. K. Maji, X.-J. Wang,
S. L. Ong, J. Joseph, H. Sun and Y. Zhao, ACS Nano, 2015,
9, 4796.
35 Y. S. Zhao, H. Fu, F. Hu, A. D. Peng and J. Yao, Adv. Mater.,
2007, 19, 3554.
36 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone,
B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng,
J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota,
R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery,
J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd,
E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi,
J. Normand, K. Raghavachari, A. Rendell, J. C. Burant,
S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, N. J. Millam,
M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo,
J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev,
A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski,
R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth,
P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels,
O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and
D. J. Fox, Gaussian 09, Revision A.02, Gaussian, Inc.,
Wallingford, CT, 2009.
37 R. G. Parr and W. Yang, Annu. Rev. Phys. Chem., 1995, 46, 701.
RSC Adv., 2016, 6, 71638–71651 | 71651