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Photochem. Photobiol. Sci., 2020, DOI: 10.1039/D0PP00232A.
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Photochemical & Photobiological Sciences Accepted Manuscript

ARTICLE

Radical Anion Formation Exhibiting “Turn-on” Fluorescence

Sensing of Hydrazine Using a Naphthalene Diimide (NDI)
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Received 00th January 20xx,

Accepted 00th January 20xx Derivative of Donor-Acceptor-Donor (D-A-D) Molecular Structure
DOI: 10.1039/x0xx00000x

P. Lasitha*a, b
In this paper, a synthesis of naphthalene diimide (NDI) derivative of donor-acceptor-donor (D-A-D) molecular structure
substituted with a long alkyl chain (12 carbons) containing naphthalene hydrazide at the imide position is reported. The
reduced emission quantum yield (f= 0.01-0.03) of the NDI derivative in various solvents indicates the perturbation of the
electronic state of -electron deficient NDI (A) by the peripheral naphthalene (D) units. The investigation of the influence
of alkyl chain and naphthalene substituent on the self-assembling properties of the NDI derivative reveals an isodesmic
mode of self-assembly in chloroform/methylcyclohexane (CHCl3/MCH, 1:9, v/v) mixture. The self-assembling nature of the
NDI derivative also results in the formation of the organogel in CHCl3/MCH (1:9, v/v) mixture, and gel formation is well-
comprehended by the techniques such as P-XRD, rheological studies, and FT-IR measurements. Further, radical anion (NDI.-
) formation of acidic NDI was used as a sensing tool for hydrazine by a fluorescent “turn-on” (f =0.12) method in
solution (DMSO), film, and gel state with a detection limit of 284.1 ppb in DMSO and 32 ppb in the gel state.

the NDI core and produces stable radical anions (NDI.-)13 or

Introduction dianion (NDI2-)14 which could be easily identified by absorption
and electron spin resonance (ESR) spectroscopy.15 Hydrazine
Hydrazine is a well-known reducing agent used mainly in
reduction of NDI also produces fluorescence changes, which is
catalysis, rocket fuel, explosives, pesticide, and textile dye
a “turn-on” response correspond to the formation of the
industries.1 Due to the health hazards on long exposure and
radical anion.16 While in a few reports emission properties of
use in making explosives, it is important to design cheap, real-
NDI have been explored for the detection of hydrazine in
time, and on-site detection techniques for hydrazine.2 There
solution phase, the emission of NDI.- in film or gel phase,17
are reports on hydrazine interaction via hydrogen bonding3 or
which is of more relevance to the practical applications,18 have
chemical reaction4 with different sensor molecules producing
not utilized much.
colourimetric5 or fluorescence responses.6 Hence,
fluorescence-based sensing techniques are extensively used
7

due to the very high sensitivity and selectivity over the other
sensing techniques such as electrochemical sensing.8
In recent past, -acidic (electron-deficient) naphthalene
diimide (NDI) molecule is used in many fields,9 especially as
sensors for different analytes.10 The electronic properties can
be tailored by the modification with electron donors (D) or
acceptors (A) to the core and/ imide position,11 of NDIs by
which the selective interaction of Lewis bases (electron donor)
can be sufficiently controlled. These D-A derivatives of NDI can
be used for sensing purposes as the addition of analyte can
result in the interaction with the accessible HOMO-LUMO
energy levels of the NDIs12 producing spectroscopic responses.
When analyte such as hydrazine interact with NDI; it reduces Scheme 1. Structure of compound used in the present study. Energy
optimized structure of NDI-DOD-I using a B3LYP/6-31G* level of theory
representing NDI in one plane and naphthalene groups in another plane
a. Department of chemistry. IIT-Madras, Chennai, India, 600036. (alkyl chain was replaced by methyl groups to reduce computation time).
b. Department of chemistry, IIT-Bombay, Mumbai, India, 400076.
Email: [email protected]
A previous literature report suggests that modification of
Electronic Supplementary Information (ESI) available: See imide position with naphthalene molecules in dendritic fashion
DOI: 10.1039/x0xx00000x

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affects the luminescence and self-assembling properties of NDI 1, 4, 5, 8 - Naphthalenetetracarboxylic dianhydride,

View Article64 %
Online
in both solution and solid-state.19 As an extension to the solution of hydrazine monohydrate, andDOI:tetrabutylammonium
10.1039/D0PP00232A
earlier work, alkyl chains were introduced to the donor salts of anions were purchased from Sigma Aldrich. Methyl-6-
(naphthalene) molecule through an ether linkage and hydroxy-2-naphthoate and 1-Bromododecane were purchased

Photochemical & Photobiological Sciences Accepted Manuscript

covalently attached to NDI molecule at the imide position from TCS chemicals. Solvents used for the photophysical
forming a donor-acceptor-donor (D-A-D) molecular structure. studies were of spectroscopic grade, bought from
The structure of the compound, NDI-DOD-I is given in Spectrochem Ptv. Ltd., India, and used without further
Scheme1. purification.
The introduction of alkyl chains is expected to enhance the Fluorescence measurements were carried out on Horiba Jobin
solubility and self-assembling properties of the NDI derivative Yvon Fluoromax-4 spectrofluorometer and absorption and
by intermolecular van der Waals interactions and temperature-dependent absorption measurements were
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interdigitation mechanisms within assemblies.20 Whilst the carried out on JASCO V-660 spectrophotometer using a cuvette of
presence of donor molecules is expected to tune the lower path length 1 cm with a Peltier control. 1H-NMR and 13C-NMR
occupied molecular orbital (LUMO) level of NDI making it more measurements were recorded on Bruker FT-NMR operating at
suitable for selective analyte sensing. Hence, NDI-DOD-I is 500 MHz in CDCl3 and DMSO-d6 as solvents. Electron spin
expected to produce a selective response for analytes via a - resonance (ESR) measurements were carried out on the ESR
acid-Lewis base interaction. As studies on the intermolecular spectrometer JEOL Model JES FA200 instrument. Field
assemblies of charge transfer (CT) complexes of NDI and Emission scanning electron microscope (FE-SEM) studies were
naphthalene are widely explored in literature,21 this paper conducted on model HITACHI S4800. FT-IR measurements
address both intra- and intermolecular influence of imide were carried out on the JASCO-FTIR-4100 spectrometer using
substituted long alkyl chain (12 carbons) functionalized KBr pellet. Mass spectra were recorded using a Micromass Q-
naphthalene on the spectroscopic and self-assembling TOF mass spectrometer and Matrix-assisted Laser desorption/
properties of the NDI-DOD-I in solution and gel state. Further, ionization (MALDI) on a Voyager-DE PRO MALDI/TOF mass
the selective sensing of hydrazine using NDI-DOD-I in solution spectrometer with 2, 5-dihydroxy benzoic acid (DHB) as the
and gel were also studied. matrix. Powder XRD measurement was recorded on a Bruker
The thermal stability of NDI-DOD-I studied using D8 Advance X-ray diffractometer using Cu-Kα radiation (λ =
thermogravimetric analysis (TGA) indicates high thermal 1.54 Å). Thermogravimetric analysis (TGA) was performed on
stability with 86 % of weight loss around 500 °C (Figure S1a). TGA Q500 V20.10 build 36 instrument and the differential
The higher thermal stability is attributed to the rigid aromatic scanning calorimetry measurements were done on a Q200 V
core and the presence of naphthalene substituents in the 24.4 built 116 MDSC instruments both with a heating rate of
compound. This indicates that NDI-DOD-I can be used in 10 °C min−1. Mesophase images were recorded on a Carl Zeiss
higher temperature-related applications. Further the Axiocam MRC5 hot-stage polarizing microscope (HOPM)
differential scanning calorimetric (DSC) thermogram of the equipped with a Linkam THMS 600 stage with a TMS 94
second heating and cooling cycle of NDI-DOD-I indicate a temperature controller and the photographs were taken by
transition to isotropic state (Tiso) at 122 °C with a small Imager A2M digital camera. Cyclic voltammetry experiments
enthalpy of transition (H) -2.22 J/g (Figure S1b). This indicates were carried out using a CHI708 IC electrochemical
that at 122 °C the compound melts into an isotropic liquid workstation in dichloromethane (DCM) with a three-electrode
state and there is no mesophase associated with the molecule, cell and tetrabutylammonium hexafluorophosphate (TBAPF6)
which is supported by the absence of birefringence under as supporting electrolyte. Glassy carbon was used as a counter,
optical polariser after cooling from the melt (Figure S1c,d). The Ag/AgCl couple as a reference and Pt wire as a working
amorphous nature of the compound was further confirmed by electrode. Rheological measurements were carried out on an
using the powder XRD measurements with d values of 40.6 Å, Anton Paar Modular Compact Rheometer (MCR) 102 with a CP
20.59 Å, 6.63 Å, and 4.09 Å, exhibiting a lamellar type 40 cone and plate.
arrangement in the powder state (Figure S1e). The diffuse Computation Methods
peak at the higher theta value is due to the alkyl chain and the Optimization of the structure was performed using Becke
absence of sharp peaks also indicates the amorphous nature of three-parameter Lee–Yang–Parr hybrid functional, B3LYP/6-
the molecular stacks. This was corroborated by the optimized 31G* level of theory/ basis set using a Gaussian 09 suite
structure obtained using B3LYP/6-31G* level of theory which program. The highest occupied molecular orbital (HOMO) and
shows that both the naphthalene groups are on a different lowest unoccupied molecular orbital (LUMO) energies were
plane than the NDI due which highly ordered molecular stacks also obtained by the same level of theory. Since alkyl chain
are not formed (Scheme1). does not influence much the electronic state of NDI, the long
alkyl chain was replaced by methyl group during optimization
to ease the calculation.22
Experimental
Material and method

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Results and discussion solvents is also compared by the scanning electron microscope
View Article Online
(SEM) images obtained by drop-castingDOI: a 10 -4 M solution of
10.1039/D0PP00232A
Photophysical properties
NDI-DOD-I on silicon wafer from CHCl3 (non-polar) and DMSO
Photophysical properties were measured in the solution state (polar) (Figure 1c, d). The irregular structures observed in the

Photochemical & Photobiological Sciences Accepted Manuscript

to understand the optical behaviour of NDI-DOD-I. The case of CHCl3 indicate an excessive solubility NDI molecules
absorption measurements were performed by dissolving NDI- and lack of ordered assembly formation in CHCl3. On the other
DOD-I in different solvents (10-5 M) {Dimethyl sulphoxide hand in polar DMSO solvent, the alkyl chain arranges inwardly
(DMSO), Terahyfdrofuran (THF), Chloroform (CHCl3), promoted by the intermolecular hydrogen-bonding of
Dichloromethane (DCM) and Toluene} with varied polarity hydrazide groups forming vesicular assemblies of 1-8 m size.
(Figure 1a). The absorption at 250-310 nm region is due to the A cartoon representation of vesicle formation is also shown in
naphthalene units and at 300-400 nm is due to the 0-0, 0-1 Figure 1. These studies unequivocally indicate the possibility of
and 0-2 transitions (π-π* transition) representing monomer
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controlling the self-assembly of NDI-DOD-I by varying the

peak of NDI. The absorption spectra of NDI-DOD-I show a solvent polarity or using a solvent mixture.
redshift (~ 4 nm) in toluene, compared to the spectra in other
solvents (DMSO, THF, CHCl3, and DCM), under identical Aggregation in solvent mixture and kinetics of aggregation
conditions. The -deficient NDI molecules tend to aggregate or
The aggregation propensity studies of the NDI derivative were
form D-A charge transfer (CT) type interaction23 in a non-polar
conducted in CHCl3 (moderately polar) and methylcyclohexane
aromatic solvent, such as toluene depicted by the changes in
(MCH, non-polar) mixture by varying the ratios of the solvents
the electronic transition intensity, i.e., 0-0 < 0-1.
(0-99 %) (Figure S3a). As MCH is a non-competitive solvent for
The emission spectra of NDI-DOD-I (10-5 M) excited at 350 nm
hydrogen bonding,26 the intermolecular hydrogen bonding
shows weak emission covering from 360-450 nm and a
involving hydrazine groups along with several other non-
shoulder peak around 550 nm in all the solvents representing
covalent interactions are promoted in solvent mixture with
monomer and excimer24 emission respectively (Figure 1b). The
increased MCH concentration.27 The addition of aliquots of
excited-state interaction of NDI which results in excimer
MCH to a dilute solution of NDI in CHCl3 [10-5 M] results in an
formation was present even at the lower concentration
initial increase in absorbance (till 20 %) and then decreases at
indicated by the concentration-dependent emission study of
a higher percentage (> 20 %). At 99 % of MCH, NDI molecules
NDI-DOD-I in CHCl3 from 0.5 x 10-3 -10-6 M (Figure S2).
aggregate completely, indicated by the loss of vibronic
features in the absorption spectra. An increase in the
absorbance at 400 nm (absorption for aggregates) is plotted
against the % MCH (Figure S3b) which shows the fluctuation in
absorption values possibly due to the structural
transformation, mostly associated planar confirmation during
aggregation. It is supported by the observation that
aggregation tendency is lower when polar and hydrogen
bonding competitive solvent such as methanol was added to
the chloroform solution (2 x 10-5 M) of NDI-DOD-I (Figure
S3c).27 It could be seen that methanol addition into the CHCl3
solution of NDI does not show any aggregate formation as
methanol competes for hydrogen bonding with hydrazide
groups.
It is always important to understand the mechanism of the
formation of self-assembled structures along with the
thermodynamic parameters associated with the self-assembly
to design functional materials of useful applications. Hence,
the kinetics of aggregation in CHCl3/MCH (10-5 M, 1:9, v/v)
mixture was studied using temperature-dependent absorption
from 350 - 298 K (at -2.1 °C/ min cooling rate) (Figure 2). As the
Figure 1. a) Absorption and b) emission spectra of NDI-DOD-I in different temperature decrease, a clear isosbestic point was observed at
solvents (10-5 M, exc =350 nm). Below, cartoon representation and SEM
image of NDI-DOD-I measured by drop-casting a 10-4 M solution, a) in CHCl3
376 nm indicating the transformation of one form of self-
and b) in DMSO on a silicon wafer. assembled structure to another. During cooling, the solution
shows a bathochromic shift in absorption which indicates the
formation of -stacked aggregates of NDI. From the absorption
The excimer formation along with the charge/electron transfer measurements, a degree of aggregation (αagg) against
interactions between the D-A-D compound could be the temperature (in Kelvin) was plotted and a good fit corresponds
reason for the observed low quantum yield (f = 0.01-0.03) of to an isodesmic model of self-assembly (equal-K model)29 was
NDI-DOD-I in different solvents (Table S1).24 The effect of obtained (Figure 2b). Due to the lack of initial nucleation step

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during self-assembly, the chance of a cooperative mechanism polymerization (DPN) of 1.41 and 6.24 at 322.23 K View
andArticle
302.00 K
Online
is ruled out in this case. The calculated melting temperature, respectively. The gradual growth of the stacks
DOI: of assembly
10.1039/D0PP00232A
Tm (at αagg 0.5) of the aggregates was 322.23 K, which reflects with the decrease in temperature could be understood from
the overall stability of the aggregates. the increase in DPN value indicative of isodesmic assembly

Photochemical & Photobiological Sciences Accepted Manuscript

formation.

Gelation study in CHCl3 /MCH mixture

As the NDI-DOD-I show aggregation tendency, gelation studies

were performed in the CHCl3/MCH mixture (See SI). The
comparison of absorption spectra of NDI gel with the solution
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(in CHCl3, 10-5 M) indicates that due to the increased

intermolecular interaction during gelation and possible CT
interaction between D-A groups, the absorption spectra
became structure-less with strong absorption above 400 nm
(Figure S4a). The opaque nature of the gel indicates closely
packed molecular aggregates of NDI favoured by hydrogen-
bonded NH groups and the interdigitated alkyl chains. Further,
a comparison of FT-IR measurements of NDI gel (with solvent)
with the xerogel (with-out solvent) also indicates the presence
of strongly hydrogen-bonded NH groups at 3327 cm-1 in both
cases (Figure S4b).32 A broad peak around 3405 cm-1 in the
case of gel represents free NH groups32 which was completely
absent in xerogel indicating relatively stronger hydrogen
bonding in the dried state. The broad peak at 1689 cm-1
represents symmetric stretching of the carbonyl group and a
relatively sharp peak at 1624 cm-1 represents hydrogen-
bonded carbonyl groups. A C=O stretching frequency
corresponds to the imide peak at 1731 cm-1 and symmetric
Figure 2. a) Temperature-dependent absorption spectra in CHCl3/MCH (10-5 bending of NH peak around 1582 cm-1 was also observed in
M, 1:9, v/v), and b) Isodesmic fitting of agg vs temperature plot of NDI-DOD- both cases. These observations indicate the possibility of two
I at 370 nm (350-298 K) (inset shows the absorption changes at 330-390 nm
region). types of hydrogen bonding involving intermolecular amide
C=O…NH hydrogen bonding and weak CH…O interaction
involving imide C=O and adjacent NDI groups.
Other thermodynamic parameters obtained correspond to A further comparison of the XRD pattern of the solid powder
molar enthalpy (ΔH), molar entropy change (ΔS), and Gibbs with xerogel indicates that self-assembly changes after
free energy (ΔG) for aggregate formation was - 82.17 k J mol-1, gelation. The lamellar pattern in the powder form is now
- 174.75 J mol-1 K-1, and - 26.03 k J mol-1 respectively. At changed into a tetragonal pattern after gelation (see Figure
302.00 K the values were - 51.38 k J mol-1, - 76.88 J mol-1 K-1, - S1e and Figure S5). The xerogel shows the d values 36.13 Å,
28.16 k J mol-1 respectively. The higher contribution of 25.2 Å, 22.0 Å, and 3.96 Å, corresponds to the ratio
enthalpy compared to entropy toward the negative free 1:1/√2:1/√3 which indicate a tetragonal assembly. It could be
energy change indicates that aggregation, in this case, is an clearly seen that the π-stacking distances decrease during
enthalpy driven process.30 Enthalpy gain obtained by the gelation as it changes from 4.09 Å in powder form to 3.96 Å in
hydrogen bonding interaction will be compensated by the the xerogel.
decrease in entropy upon the aggregation of NDI. The The log-log plot for rheological studies indicating the changes
temperature-dependent UV studies also yielded an association in storage (G′, elastic behaviour) and loss modulus (G′′, flow
constant for the formation of aggregates with K values of 7.45 behaviour) is given in Figure 3. Both G′ and G” remain constant
x 104 M-1 and 1.71 x 104 M-1 at 302.00 and 322.23 K initially when measured at 1 rad/sec starts dropping till a cross
respectively using the equation 7 (supplementary over (c critical strain) occurs at 6 % strain indicating the
information). The association constant (K) value is enhanced transition from gel to sol state. The angular frequency
upon cooling the solution indicates the formation of tighter dependency measurements at the constant strain of 0.1 % also
aggregates. The formation of aggregates is greatly influenced indicate the dominance of G′ value over G′′ over the measured
by the hydrogen bonding, but also by the steric factor which frequency range of 1 to 100 rad/s with a linear viscosity region
restricts the conformational freedom of the molecule and (LVR). The mechanical strength of the gel is indicated by the
results in the molecular assembly with less order.31 This was obtained G’ value, 5.7 kPa, and tan  (= G’’/G’) value which is
indicated by the low value of the number-average degree of 0.13. Overall, the gel exhibits good mechanical strength and

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viscoelastic properties. The scanning electron microscopy After the addition of 0.021 M HY, the weakView orange-red
Article Online
(SEM) (see Figure 5b) image of NDI-DDO-I solution drop-casted emission contribution from the 402 nm and DOI:the shoulder band
10.1039/D0PP00232A
on the silicon wafer just before gelation indicates flake type at 556 nm of NDI-DOD-I changes to a green emission with
morphology without any long rage order of self-assembly, distinctive emission maxima at 440 and 513 nm (Figure S6).

Photochemical & Photobiological Sciences Accepted Manuscript

which clearly supports the earlier observations from the These emission changes are attributed to the formation of
kinetic model of assembly (vide supra). stable NDI.- which is in equilibrium with the NDI monomer. The
radical anion formation results in the increase in the quantum
yield (f) by an order giving a value of 0.12 compared to the
value obtained 0.025 in DMSO without HY. The electron spin
resonance (ESR) spectroscopy measurements also confirm the
NDI.- formation. At unreduced state, ESR measurement of NDI-
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DOD-I in DMSO (10-4 M) shows no signal and after the addition

of HY (0.13 M) a strong signal corresponds to NDI.- with a g-
tensor value of 1.998 was observed.37 Lack of hyperfine
spitting of ESR spectrum indicates the strong intermolecular
delocalization of π-electron along the reduced assemblies of
NDI (Figure 4b).38 Further, reduction ability of some selected
Lewis basic anions (tetrabutylammonium salts of F-, Cl-, Br-, I-,
OAC-, SO4-, PF6-, NO3-, and H2PO4-), and amine compounds
(ammonia, N-methyl ethylenediamine, propylamine, aniline,
and hydroxylamine) were also compared with hydrazine
hydrate. The addition of ~40 mM of anions and amines do not
show any absorption and emission changes correspond to the
NDI.- formation (Figure S7). Though the addition of F- shows
some initial spectral changes, but does not form NDI.-
indicating that the strong Lewis base such as F- is not able to
access the LUMO levels of NDI-DOD-I.

Figure 3. Plot of G', G'' dependency against the a) % strain, and b) angular
frequency of NDI-DOD-I gel (CGC, 5 mg/mL). (A photograph of gel is also
shown).

Hydrazine sensing in solution state

Further studies are conducted to understand the sensing of
hydrazine using a DMSO solution of NDI-DOD-I (5x10-5 M). A
64 % hydrazine monohydrate (HY) (NH2.NH2.H2O) was used for
all the studies. The poor emission quantum yield of NDI-DOD-I
in both solution and solid-state makes this compound an
effective candidate for the sensing of analytes by a “turn-on”
mechanism. DMSO was chosen for the detection studies due
to the better solubility of the NDI-DOD-I and the possible
stabilization of the relatively polar excited state by polar DMSO
solvent.34 Figure 4a shows the absorption changes of NDI-
DOD-I upon the addition of different molar equivalents (0-0.63
M) of HY. The addition of HY results in the formation of the
stable radical anion (NDI.-) indicated by the appearance
absorption peaks at 474 nm, 608 nm, 678 nm, and 754 nm.34
The NDI radical anions are highly stable at ambient conditions Figure 4. a) Absorption spectra of NDI-DOD-I in DMSO (5 x10-5 M) after the
addition of different molar equivalents of HY (0 - 0.63 M), and b) ESR spectra
even in the presence of air. Further addition of large excess of of NDI-DOD-I in DMSO (10-4 M) before and after the addition of HY (0.13 M).
HY (0.63 M) to the solution does not result in the formation of
dianion (NDI2-) as the characteristic set of absorption peaks
(397 nm, 417 nm, 550 nm, and 600 nm) correspond to NDI2- It is evident that other amines and anions are also not
were not observed.36 interacting electronically with the NDI core and NDI-DOD-I is

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highly selective only for HY.39 Comparison of the colour change The aromatic peak appears in the region of View 7-9 ppm
Article Online
of NDI-DOD-1 solution (5 x 10-5 M) before and after the representing NDI and naphthalene protons, and the NH peak
DOI: 10.1039/D0PP00232A
addition of HY (40 mM) indicates that colour of the solution appears at 11.7 ppm. After the addition of 0.85 equ of HY the
also changes from light brown to dark brown after the addition aromatic peak corresponds to NDI and NH peak at 11.7 ppm

Photochemical & Photobiological Sciences Accepted Manuscript

of HY (photographs are shown in Figure S8). Hence, the disappears, indicating that the addition of HY affects both NH
presence of HY can also be visually distinguished among the and NDI resonance peaks. These changes could be due to the
other anions and amines. interaction of HY with the NH groups and the possible change
Excitation spectra measurements were also conducted to in the electron density of the NDI core after the reduction. As
understand the excited state properties of the NDI-DOD-I after not much change in the peaks corresponds to naphthalene
reduction (Figure S9). The excitation spectra (excited between (8.5-7 ppm) was observed, it is assumed that HY does not
260 - 500 nm) of unreduced NDI obtained at emission maxima interact directly with naphthalene groups. The change in the
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550 nm shows a broad peak at 415 nm which represents electron density is also evident from the FT-IR spectra
ground state dimers of NDI. After the addition of HY, the measured in DMSO indicated by the shift of C=O stretching
excitation spectra show two maxima 373 nm and 465 nm, frequency from 1666 cm-1 to 1630 cm-1 after the reduction
represents the unreduced and reduced species of NDI with HY (0.13 M) (Figure S12). The comparison was also made
respectively.40 The schematic representation of the reduction to see the morphological changes in vesicular assemblies of
of NDI-DOD-I using HY is also shown in Figure S9 indicating the NDI-DOD-I obtained from DMSO (10-4 M) after the HY
highly delocalized state of electronic charge of NDI.-. Further, addition. The addition of HY (10 L, 0.13 M) results in the
the MALDI analysis using a DHB matrix also reveals an NDI- disruption of intermolecular interaction evident from the
DOD-I.2HY interaction giving mass (m/z) of 1131 (Figure S10). destruction of vesicular structures in the SEM image (Figure
The detection limit of the hydrazine in DMSO was calculated S13).
by titrating aliquots of HY to a 7.4 x 10-5 M solution of NDI- The frontier molecular orbital (FMO) energy of NDI-DOD-I was
DOD-I in DMSO (Figure S11a). From the plot of absorption estimated using cyclic voltammetry (CV) against the ferrocene/
correspond to the NDI.- (471 nm) against the equivalents of HY, ferrocenium couple in DCM. The reduction occurs at -0.977 V
a detection limit of 284.1 ppb was obtained by considering the and the LUMO level was estimated by the subtraction of -4.8
concentration where the sudden inflection in the absorption eV for Fc/Fc+ below the vacuum level of ferrocene giving a
takes place (Figure S11b). Such a low value of detection LUMO value of -3.8 eV.15
threshold limit could be an indication of the practical
application of this NDI derivative as HY sensor.41

1H- NMR, FT-IR and computation measurements

Next, the 1H-NMR titration experiment was carried out by

adding 0-20 equivalents of HY to a DMSO-d6 solution of NDI-
DOD-I (8.3 x 10-3 M) (Figure 5).

Figure 6. HOMO and LUMO levels of NDI-DOD-I obtained by optimizing the

structure using B3LYP-6-31G* level of theory and Cyclic voltammogram of
NDI-DOD-I (10-3 M) in DCM.

The oxidation peak was not detectable in the CV studies,

hence the associated HOMO level was calculated using B3LYP-
6-31G* level of theory. It is clearly seen that HOMO level was
located on the donor naphthalene groups at - 5.75 eV and the
LUMO level on the NDI at - 3.36 eV, which is close to the value
obtained from the CV studies (Figure 6). The band-gap energy
Figure 5.1H-NMR titration spectra of NDI-DOD-I in DMSO-d6 (8.3 x10-3
(Eg) calculated using EHOMO-ELUMO is at - 2.39 eV. As the redox
M) after the addition of different equivalents of HY.
energy level of hydrazine, – 5.20 eV is at lower energy than the
LUMO level of NDI, hence the direct injection of the electron
from hydrazine to the positive quadrupole of NDI is

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thermodynamically unfavourable.15, 42 Therefore it is assumed The huge enhancement in emission in gel and Viewfilm
Article state
Online
as indicated by the 1H-NMR studies that hydrazine initially compared to the emission from DMSO solution is evident as no
DOI: 10.1039/D0PP00232A
interacts with the NH groups of NDI-DOD-I followed by the interference of NDI emission around 450 nm (monomer) is
electron injection causing the reduction of the NDI. observed which is accounted for the formation stable NDI.- in

Photochemical & Photobiological Sciences Accepted Manuscript

Hydrazine sensing in film and gel state the aggregates of NDI-DOD-I. The film and gel could detect a
concentration of about 73 ppm of hydrazine visually under UV
Hydrazine detection was further performed by drop-casting a light and 32 ppb of hydrazine using fluorescence technique
chloroform solution (10-3 M) of NDI-DOD-I to form a film and (Figure S16), hence could be used for real-life applications.
by pasting the gel on a quartz plate. A weak orange-red Approximately a 10 fold improvement in the detection limit of
emission could be observed from the film and gel when hydrazine in NDI-DOD-I gel compared to the DMSO solution is
excited at 365 nm under UV lamp (Figure S14). Further, about due to the formation of stable NDI.- and lack of emission
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10 L of 0.13 M of different analytes were added over the dissipation via any non-radiative pathways in the three-
compound on the quartz palate and monitored under the UV dimensional gel networks.
lamp. It is observed that only after the addition of HY a bright Further, FT-IR measurements of NDI-DOD-I gel after reduction
green emission was seen from the NDI film and as well as from using HY shows the change of C=O stretching frequency from
gel. The absorption spectrum of NDI-DOD-I in film state show 1683 cm-1 to a broad peak at 1586 cm-1 (Figure S17). Such a
peaks at 307 nm, 360 nm, 380 nm, and a broad absorption huge shift in the C=O stretching frequency indicates the highly
above 400 nm. After the reduction using HY, the broad peak at delocalized and stable state NDI.- within the three-dimensional
307 nm shifts to 363 nm and new peaks emerge with gel network. The SEM image shows that the flake type
absorption at 445 nm and 465 nm (Figure S15). In the case of morphological pattern of gel transforms into ribbon type
the gel, a ~2-5 nm red shift in absorption was observed after morphology after the reduction in the presence of HY (Figure
reduction presumably due to the difference in self-assembled 7c). The morphological changes indicate how the
structures of NDI-DOD-I in gel compared to the film state. The intermolecular interactions of NDI-DOD-I are affected by the
orange-red emission of maxima 465 nm and 620 nm also HY addition. It further indicates the possible use of this
changes to bright green emission of 500 nm maximum in film compound in electrical conductivity related applications.18
state and with an approximately 5 nm red-shifted emission, Since NDI-DOD-I can selectively sense HY, the formation of
505 nm in the gel state (Figure 7a). NDI.- can be easily monitored using absorption and emission
studies along with the visual detection techniques, indicate the
advanced application of the sensor for practical use.

Conclusion
In conclusion, a D-A-D NDI derivative containing naphthalene
donor with peripheral alkyl chains were synthesized. The
spectroscopic investigation indicates the influence of
peripheral substitution on the absorption, emission, and
aggregation properties NDI-DOD-I. Evaluation of self-
assembling properties in CHCl3/MCH (1:9, v/v) mixture found
to follow an equal-K model where self-assembly is governed by
the enthalpy changes over entropy. NDI-DOD-I also forms
stable organogel in CHCl3/MCH (1:9, v/v) indicated by the
viscoelastic properties. Sensing properties employed using
NDI-DOD-I in DMSO indicate a selective “turn-on” and
colorimetric sensing of hydrazine with a detection limit of
284.1 ppb in DMSO and 32 ppb in the gel state.

Conflicts of interest
There are no conflicts to declare.
Figure 7. a) Emission spectra of film and gel of NDI-DOD-I before and after
the reduction using 10 L of 0.13 M of HY (exc=350 nm). SEM images of
NDI-DOD-I gel, b) before, and c) after the addition of HY (10 L, 0.13 M). A Acknowledgements
schematic representation of the formation of the NDI.- in the presence of HY
is also shown. LP wants to acknowledge UGC for fellowship and Prof.
Edamana Prasad (Ph.D. guide) for the support and guidance.
The author would like to acknowledge the Department of

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Chemical Engineering, IIT Madras for FE-SEM facility, Prof. R. L. 10 S. V. Bhosale, S. V. Bhosale, M. B. Kalyankar, S. View
J. Langford, A
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Gardas, Department of Chemistry, IIT Madras for rheological Core-Substituted Naphthalene DiimideDOI: Fluoride Sensor, Org.
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The author also acknowledges Dr.T. Narasimhaswamy, CLRI, fluorescent ‘‘2 in 1’’ proton sensor and polarity probe based

Photochemical & Photobiological Sciences Accepted Manuscript

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