Journal of Molecular Liquids 291 (2019) 111266

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Effect of stereo electronic factors of coumarin derivatives during their

interaction with TiO2 nanoparticles
J.M. Nirupama- a, N.I. Khanapurmath b, L.S. Chougala a, M.V. Kulkarni b, J.S. Kadadevarmath a,⁎
a
Department of Physics, Karnatak University, Dharwad 580003, Karnataka, India
b
Department of Chemistry, Karnatak University, Dharwad 580003, Karnataka, India

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

Article history: The effect of stereo electronic factors of coumarin derivatives, 6-methoxy-4-azido methyl coumarin (6MCA) and
Received 11 May 2019 7-methoxy-4-azido methyl coumarin (7MCA) during their interaction with the TiO2 nanoparticles in ethyl ace-
Received in revised form 5 June 2019 tate, tetrahydrofuran, methanol, dimethyl formamide and acetonitrile solvents has been studied using uv-vis ab-
Accepted 29 June 2019
sorption spectroscopy, fluorescence quenching, FRET and electrochemical analysis. Benesi-Hildebrand plots
Available online 02 July 2019
confirm that interaction between 6MCA and TiO2 is stronger in solvents with low dielectric constant whereas
Keywords:
for 7MCA and TiO2 system, interaction is stronger in solvents with high dielectric constant. The steady state
TiO2 nanoparticles and time resolved S-V plots are linear for both the systems. For 6MCA system, quenching rate parameter is de-
Hyperchromic effect creasing with increasing dielectric constant of the solvent and for 7MCA system these values are in increasing
Resonance energy transfer order with increasing dielectric constant of the solvents. FRET study also confirms that nature of interaction be-
Electron transfer tween these two systems is different. Electrochemical analysis reveals the role of electron transfer from coumarin
Cyclic Voltammogram derivative to TiO2 nanoparticles and shows that azido group (-N3) of 7MCA and 6MCA are responsible for electron
transfer. The magnitude of free energy change for electron transfer confirms that quenching is more efficient for
7MCA system. The higher magnitude of quenching rate parameter of 7MCA compared to 6MCA is due to its stable
and polar structure.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
The nature and position of substitution has a profound effect on the
photo physical properties of coumarin derivatives. Fluorescence inten-
sity, lifetime, quantum yield and excited state dipole moment of
substituted coumarins depend on the structure and nature of substitu-
ent pattern. For example, the acetoxy substituent at C-7 of coumarin
shows enhanced fluorescence whereas methyl group at position 4
shows reduction in fluorescence intensity [1]. In non-rigid coumarin de-
rivatives, formation of TICT state depends on substitution group at C-7
[2]. Coumarins with electron donating groups at C-7 and electron
accepting groups at C-3 are excellent Laser dyes [3]. In all the above in-
vestigations, it is observed that groups at different positions of coumarin
change the fluorescence property. Some authors have observed that
same substituent group at different positions of coumarin also changes
the photo physical properties of coumarin derivative. For example, ex-
cited state dipole moment of 6-methyl 4-azidomethyl coumarin is
greater than that of 7-methyl 4-azidomethyl coumarin [4].
⁎ Corresponding author.
E-mail address: jagadishsk1956@gmail.com (J.S. Kadadevarmath).
Recently, some authors have studied the interaction of TiO2 nano-
particles with iodine substituted at different positions of 4-
aryloxymethyl coumarin (1IPMBC, 4IPMBC and 4IPMMC). Iodine
substituted 4-aryloxymethyl coumarin exhibited anticancer and anti-
mycobacterial activities. TiO2 nanoparticles (NPs) are used as carriers
of drug and interaction of TiO2 with these coumarin derivatives help
in drug delivery system. Interaction of TiO2 NPs with coumarin deriva-
tives are solvent sensitive and hence can be used in sensor applications
[5]. The study of interaction of metal nanoparticles with biologically ac-
tive organic molecules is used in the development of diagnostic tech-
niques. Various reactive oxygen species are liberated on the surface of
TiO2 NPs, when they are irradiated with UV-A. Recently studied Gd-
doped TiO2 has been intended as a potential means of tracking and kill-
ing cancerous cells [6,7].
Apart from this, TiO2 NPs have many biomedical applications and
hence some authors have studied the interaction of TiO2 NPs with
Human serum albumin (HSA) and Bovine Serum Albumin (BSA)
[8–10]. TiO2 NPs are also used as food colorant, as additive in sun screen
and cosmetic creams [11,12]. (z)-2-cyano-3-(10-hetyl-10H-
phenothiazin-7-yl) acrylic acid (CPTA) dye attached to TiO2 NPs have
solar cell applications [13].
In the present study we have chosen two coumarin derivatives, 6-
methoxy-4-azido methyl coumarin (6MCA) and 7-methoxy-4-azido

https://doi.org/10.1016/j.molliq.2019.111266
0167-7322/© 2019 Elsevier B.V. All rights reserved.
2 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266
methyl coumarin (7MCA). These two azides are substituted with
methoxy group at position 6 and 7. The TiO2 NPs are photosensitive
and their interaction with coumarin derivatives will reflect the changes
in the optical properties. Our objective is to understand the influence of
stereo electronic factors of these coumarin derivatives during their in-
teraction with TiO2 NPs in different solvents and also the role of azido
group (-N3) of 7MCA and 6MCA.
2. Materials and Methods
Coumarin derivatives, 6- methoxy-4-azidomethyl coumarin
(6MCA), 7-methoxy-4-azidomethyl coumarin (7MCA) and 6-
methoxy coumarin (6MC) were synthesized in the Department of
Chemistry, Karnatak University, Dharwad [14]. The solvents, ethyl
acetate (EA), tetrahydrofuran (THF), methanol (MeOH), N, N di-
methyl formamide (DMF) and acetonitrile (MeCN) were purchased
from S.D. Fine chemicals Mumbai. The nano particle TiO2 and the
electrolyte, tetrabutylammonium perchlorates were procured from
Sigma Aldrich. As per the specification, TiO2 is anatase, b25 nm par-
ticle size, 99.7% trace metals basis. All the above mentioned solvents
were of HPLC grade and were used without any further purification.
The structures of 6MCA and 7MCA are shown in the Fig. 1a and 1b
respectively.
The solutions were prepared by keeping the concentration of
coumarin derivative fixed at 1 × 10 −4 M to avoid self-quenching.
The concentration of TiO 2 was varied from 0.166 mM to
0.835 mM. The solution containing TiO2 NPs was sonicated to get
uniform suspension. The absorption spectra of the coumarin deriv-
ative in the absence and presence of TiO2 NPs were recorded using
N3
MeO
O O
a DMF solvents, suggesting 1:1 interaction between coumarin derivative
N3
MeO O O
b tra of coumarin derivatives in which C_O stretching band appears at
Fig. 1. (a) The Structure of 6- methoxy-4-azidomethyl coumarin (6MCA). (b) The
Structure of 7- methoxy-4-azidomethyl coumarin (7MCA).
uv-visible absorption spectrophotometer model JASCO V-670. The
fluorescence spectra of coumarin derivatives in the absence and
presence of TiO 2 NPs were recorded using spectrofluorometer
model Hitachi F-7000 in all the five solvents. The life time data of
coumarin derivatives in the absence and presence of TiO 2 NPs
were measured using Time correlated single photon counting
model Chronos-BH (ISS-92001). The fluorescence decay profiles
were fitted to obtain χ2 value very close to unity. The cyclic Voltam-
mogram of 6MCA, 7MCA and 6MC were recorded using electro-
chemical analyser model-600E series, USA. Cyclic Voltammetry
consists of three electrodes namely Ag/AgCl reference electrode,
glassy carbon working electrode and platinum counter electrode.
The Cyclic Voltammogram of 6MCA, 7MCA and 6MC were obtained
at 0.1 M tetrabutylammonium perchlorate (TBAP) as supporting
electrolyte with the scan rate of 100mVs−1.
3. Results and Discussion
3.1. UV-VIS absorption spectroscopy
Absorption spectra of 6-methoxy-4-azidomethyl coumarin (6MCA)
and 7-methoxy- 4-azidomethyl coumarin (7MCA) with the concentra-
tion 1 × 10−4M in the absence and presence of TiO2 NPs (0.166 mM–
0.835 mM) in ethyl acetate (EA), tetrahydrofuran (THF), methanol
(MeOH), N, N dimethylformamide (DMF) and acetonitrile (MeCN) sol-
vents were recorded separately at room temperature. Absorption spec-
tra of 6MCA and 7MCA in EA, THF, MeOH, DMF and MeCN solvents are
shown in Fig. 2a–e and in Fig. 3a–e respectively. Hyperchromic effect
was observed in all these spectra with the increasing TiO2 concentration
and there is no shift in the absorption peak. In order to verify the effect
of concentration of TiO2 and possible complex formation, Benesi-
Hildebrand (B-H) equation Eq. (1) was applied [15].
c 1 1
¼ þ ð1Þ
Δa Δε Δεka ½TiO2 
where c is concentration of the coumarin derivative, Δa is difference in
the absorbance of coumarin derivative in the absence and presence of
TiO2 NPs. Δε is change in the molar extinction coefficient, ka is associa-
tion constant and [TiO2] is the concentration of TiO2 NPs. The plots of
c/Δa against 1/[TiO2] for 6MCA and for 7MCA systems in all the above
mentioned solvents are shown in Fig. 4a and b respectively. For 6MCA,
plots are linear with correlation coefficient very close to unity in
MeOH, DMF and MeCN solvents only and for 7MCA, plots are linear
with correlation coefficient very close to unity in EA, THF, MeOH and
and TiO2 NPs. For 6MCA in EA and THF and for 7MCA in MeCN, plots
are nonlinear with negative intercept suggesting 1:2 interactions [16].
Association constants ka for linear plots of both the systems are shown
in Table 1. However for 6MCA system in lower dielectric constants
(EA, THF) and for 7MCA system in high dielectric constant (MeCN), B-
H plots are not linear which suggests that interaction between 6MCA
and TiO2 is stronger in solvents with low dielectric constant whereas
for 7MCA and TiO2 system, interaction is stronger in solvents with
high dielectric constant. This indicates that nature of interaction of
6MCA with TiO2 is different from that of 7MCA with TiO2. In order to ex-
plore this difference, 1H NMR spectra of coumarin derivative in DMSO d6
is obtained. The CH3O protons appear at 3.31 δ ppm and CH2 protons ap-
pear at 4.78 δ ppm for both the coumarin derivatives in the absence of
TiO2. But with the addition of TiO2 NPs, no changes in chemical shifts
were observed thus the interaction between azide and TiO2 cannot be
predicted. Hence FTIR study [17] was carried out by recording FTIR spec-
1704 cm−1 and 1698 cm−1 for 6MCA and 7MCA respectively (Supple-
mentary Fig. 1a and 1b), FTIR spectrum of TiO2 (Fig. 2), FTIR spectra of
6MCA and TiO2 in the ratio 1:1 and 1:3 (Supplementary Fig. 3a, 3b)
 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266 3

Fig. 2. Absorption Spectra of 6MCA in (a) ethyl acetate, (b) tetrahydrofuran (c) methanol, (d) N,N dimethylformamide and (e) acetonitrile.

and FTIR spectra of 7MCA and TiO2 in the ratio 1:1 and 1:3 (Supplemen-
tary Fig. 4a, 4b) were recorded. As we have not observed significant
changes in the stretching bonds of 6MCA and 7MCA with the addition
of TiO2 NP, interaction between coumarin derivative and TiO2 NPs can-
not be inferred.
3.2. Fluorescence quenching
Fluorescence spectra of 6MCA (1 × 10−4M) and 7MCA (1 × 10−4M)
in the absence and presence of TiO2 NPs (0.166 mM-0.835 mM) were
recorded separately at room temperature in EA, THF, MeOH, DMF and
4 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266

Fig. 3. Absorption Spectra of 7MCA in (a) ethyl acetate, (b) tetrahydrofuran, (c) methanol, (d) N,N dimethylformamide and (e) acetonitrile.

MeCN solvents and are shown in Figs. 5a–e and 6a–e respectively. The τ0
¼ 1 þ K 0SV ½TiO2  ð3Þ
excitation wavelength of 6MCA is 342 nm and that of 7MCA is τ
322 nm. Fluorescence spectra reveals quenching of fluorescence of cou-
marin derivatives with the increasing concentration of TiO2 NPs and
these spectra were analysed using steady state and time resolved where, I0 and I are fluorescence intensities in the absence and presence
Stern-Volmer equations Eqs. (2) and (3) respectively [18–22]. of TiO2. KSV is the steady state S-V constant, τ0 is lifetime of the coumarin
derivative in the absence of TiO2, τ is lifetime of the coumarin derivative
I0 in the presence of TiO2. The life time τ, decreases with the increase in
¼ 1 þ K SV ½TiO2  ð2Þ
I the concentration of the TiO2 NPs in all the solvents and for both the
 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266 5

Table 1
The values of association constant determined from Benesi-Hildebrand plots.

Solvent Coumarin derivative Association constant ka M−1

EA 6MCA –
7MCA 1.01×103
THF 6MCA –
7MCA 1.59×102
MeOH 6MCA 8.21×102
7MCA 1.01×102
DMF 6MCA 2.07×103
7MCA 8.37×102
MeCN 6MCA 6.31×102
7MCA –

overlapping of absorption spectra of TiO2 and fluorescence spectra of

coumarin derivatives.

3.3. Forster resonance energy transfer (FRET)

FRET is an electro dynamic phenomenon and is due to long range

dipole-dipole interaction between donor (coumarin derivative) and an
acceptor (TiO2). Overlapping spectra for 6MCA systems and for 7MCA
systems are shown in Fig. 9a–e and in Fig. 10a–e respectively in all the
solvents.
Rate of energy transfer depends on the quantum yield of donor, rel-
ative orientation of donor and acceptor transition dipoles and distance
between donor and acceptor [23–27]. Rate of energy transfer kT (r),
from donor to acceptor is determined from Eq. (6)


1 R0 6
kT ðr Þ ¼ ð6Þ
τ0 r

where R0 is Forster distance at which FRET is 50% efficient, τ0 is life time

of donor and r is distance between donor and acceptor. Forster distance
R0 is calculated using Eq. (7)
h i1=6
R0 ¼ 0:211 K 2 ∅n−4 J ðλÞ ð7Þ
Fig. 4. The plots of c/Δa against 1/[TiO2] for (a) 6MCA (b) 7MCA.

where K2 = 2/3 is relative orientation factor for donor and acceptor

coumarin derivatives (Supplementary Table 1a and 1b). K'SV is the time
resolved S\\V constant and [TiO2] is the concentration of TiO2 NPs. The
S-V plots according to Eqs. (2) and (3) are shown in Figs. 7a & b and 8a &
b for 6MCA and 7MCA systems respectively. These plots are linear with
the intercepts very close to unity in all the solvents. The slopes of the
steady state and time resolved S-V plots are KSV and K'SV respectively.
Respective quenching rate parameters (kq and k'q) are obtained using
Eqs. (4) and (5).
K SV
kq ¼
τ0
transition dipole in space, n = 1.3314 is the refractive index of metha-
nol, ϕ is a relative quantum yield of the coumarin derivatives (ϕ =
0.16 for 6MCA, ϕ = 0.045 for 7MCA) determined with respect to an-
thracene (ϕ = 0.27) in methanol solvent. J (λ) is overlap integral be-
tween emission spectra of coumarin derivative and absorption spectra
of TiO2. The distance between donor and acceptor r is calculated from
the Eq. (8) using the value of R0 and E obtained from Eq. (9)
1=6
1
r¼ −1Þ R0 ð8Þ
E
ð4Þ
where E is efficiency of energy transfer determined using Eq. (9)

0 K 0SV I
kq ¼ ð5Þ E ¼ 1− ð9Þ
τ0 I0

The values of KSV, K'SV, kq, k'q and τ0 for 6MCA and 7MCA in all the
solvents are shown in Tables 2a and 2b respectively. From Table 2a for
6MCA, quenching rate parameters (kq and k'q) are in decreasing trend
with the increasing dielectric constant of the solvents except in MeOH
under time resolved state only. From Table 2b, for 7MCA, quenching
rate parameters (kq and k'q) are in increasing trend with the increasing
dielectric constant of the solvents except in MeOH and DMF in both
steady and time resolved states. Thus fluorescence quenching study re-
veals that the nature of interaction of 6MCA with TiO2 is different from
that of 7MCA with TiO2. Now, the magnitudes of rate of energy transfer
for these two systems can be determined using FRET as there is an
Here I and I0 have the usual meaning. The values of R0, distance be-
tween donor and acceptor r, energy transfer efficiency E, energy transfer
rate kT(r) for 6MCA and for 7MCA are shown in Tables 3a and 3b
respectively.
From Figs. 9a–e and 10a–e, extent of overlap is limited, how-
ever, only the tail of absorption spectrum of TiO2 extends over the
entire range of emission spectrum of coumarin derivative in all
the solvents and for both 6MCA and 7MCA systems. Further, FRET
can be used as a spectroscopic ruler in the range of 10– 100 Å. Ac-
cordingly, in order to avoid the effect of short range interactions,
the distance between donor and acceptor (r) should be N10 Å.
6 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266

Fig. 5. Fluorescence spectra of 6MCA in (a) ethyl acetate, (b) tetrahydrofuran, (c) methanol, (d) N,N dimethylformamide, (e) acetonitrile.

Thus, it is observed from the Tables 3a and 3b that for both 6MCA
and 7MCA in all the solvents, the value of r is N10 Å and also the
possible range of FRET is 0.5R 0 b r b 1.5R 0 [23,24]. For 6MCA and
7MCA, from the tables mentioned, probable range of FRET 0.5R 0
b r b 1.5R 0 is satisfied. Rate of energy transfer for 6MCA is in de-
creasing order with the increasing dielectric constant of the sol-
vents except in MeOH. Whereas for 7MCA, energy transfer rate is
in increasing order with the increasing dielectric constant of the
solvents except in EA and THF. Thus FRET study reveals that nature
of interaction of 6MCA with TiO 2 is different from that of 7MCA
with TiO2. As the nature of interactions for two systems are differ-
ing, electrochemical analysis is carried out to investigate the role
of electron transfer process [28–32].
3.4. Electrochemical analysis
The role of electron transfer in fluorescence quenching process is in-
vestigated using Rehm-Weller equation Eq. (11) [33]. The oxidation and
reduction potentials are obtained from cyclic Voltammogram of 6MCA
and 7MCA recorded in acetonitrile solvent and are shown in Fig. 11a
 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266 7

Fig. 6. Fluorescence spectra of 7MCA in (a) ethyl acetate, (b) tetrahydrofuran, (c) methanol, (d) N,N dimethylformamide, (e) acetonitrile.

and b respectively. The oxidation potential of the coumarin derivative is −2.83 eV and − 2.90 eV for 6MCA and 7MCA respectively. The reduc-
EHOMO (HOMO level) and E00 is the energy gap between HOMO and tion potential (conduction band edge) of TiO2 is −0.5 eV in acetonitrile
LUMO levels. E00 is estimated from the intersection of absorption and [34]. Here, ELUMO for 6MCA and 7MCA are more negative compared to
emission spectra of coumarin derivative. The value ELUMO (LUMO conduction band edge of TiO2 thus, there is a possibility of electron
level) is calculated using Eq. (10). transfer from coumarin derivative to TiO2.
Then, the standard free energy change ΔG0 for electron transfer can
ELUMO ¼ EHOMO −E00 ð10Þ be determined using Rehm-Weller equation Eq. (11)



The values of oxidation potential (EHOMO) and E00 for 6MCA and D A
ΔG0 ¼ E þ −E −E00 þ c ð11Þ
7MCA are shown in Table 4. The ELUMO estimated from Eq. (10) are D A−
8 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266
Fig. 7. Steady state S-V plots of (a) 6MCA (b) 7MCA.
+
where E(D/D ) is the oxidation potential of coumarin derivative, E
(A/A−) is the reduction potential of TiO2 NPs. E00 is the energy gap
between LUMO and HOMO levels, c is the coulombic energy term
and is equal to 0.1 eV for acetonitrile solvent. The values of free en-
ergy change for electron transfer ΔG0 are estimated from Eq. (11).
Free energy change for electron transfer ΔG0 can be correlated with
the quenching efficiencies of 7MCA and 6MCA systems. The free en-
ergy change for electron transfer ΔG0 and quenching rate parameter
determined in acetonitrile for 6MCA and 7MCA systems are shown in
Table 4. It is observed from table that ΔG0 value of 7MCA is more neg-
ative compared to 6MCA system. As the magnitude of free energy
change for electron transfer becomes more negative, quenching effi-
ciency increases [23,24]. Hence quenching is more efficient for 7MCA
system compared to 6MCA system. The higher values of quenching
rate parameter kq in the case 7MCA system are due to its stable and
polar structure shown in Fig. 12. Structure of 6MCA shown in this fig-
ure is different from that of 7MCA. In case of 7MCA, electrons
circumpass to pyrone ring which is not possible in case of 6MCA.
Thus it is concluded that, the stereo electronic factors of coumarin
derivatives are certainly playing a role.
3.5. Effect of azido group (-N3) of 6-methoxy-4-azido methyl coumarin and
7methoxy-4-azido methyl coumarin
In order to ascertain the effect of azido group (-N3) of 6-methoxy-4-
azido methyl coumarin and 7-methoxy-4-azido methyl coumarin dur-
ing their interaction with the TiO2 NPs, absorption, fluorescence and
Fig. 8. Time resolved S-V plots of (a) 6MCA (b) 7MCA.
electrochemical analysis of 6-methoxy coumarin (6MC) is carried out
for which -N3 group is absent at the position 4 (Supplementary Fig. 5)
Absorption spectra of 6-methoxy coumarin with the concentration 1
× 10−4 M in the absence and presence of TiO2 NPs (0.166 mM–
0.835 mM) in acetonitrile solvent were recorded at room temperature
(Supplementary Fig. 6). With the increasing TiO2 concentration, absorp-
tion of 6MC shows hyperchromic effect without shift in the absorption
peak. Benesi-Hildebrand plot is linear with positive intercept, indicating
1:1 interaction (Supplementary Fig. 7) and the association constant ka is
41.67 M−1. The quenching of fluorescence of 6MC (Supplementary
Fig. 8) with the increasing concentration of TiO2 NPs was analysed
using steady state Stern-Volmer plot (Supplementary Fig. 9) which is
linear with the intercept equal to unity. The steady state S-V constant
KSV and quenching rate parameter kq are 1667.12 and
5768.58×109M−1 s−1 respectively. Since there is an overlapping of ab-
sorption spectra of TiO2 on the fluorescence spectra of 6MC, FRET
study was carried out (Supplementary Fig. 10). Accordingly, Forster dis-
tance R0, r and E are 1.02 nm, 0.97 nm and 0.58 respectively are ob-
tained. Here it is seen that the values R0 and r are closer to 10 Å, thus
short range interaction is dominant than FRET [25]. Further, electro
chemical analysis reveals the absence of electron transfer process as ox-
idation and reduction potential peaks are absent in cyclic voltammo-
gram (Supplementary Fig. 11). Thus, the study of 6-methoxy
coumarin, suggest that -N3 group of 6MCA and 7MCA are responsible
for electron transfer process.
 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266 9

Table 2a
The values of dielectric constant of solvents, steady state Ksv, kq, life time τ0 of 6MCA in different solvents, time resolved K'sv and k'q.

Solvent Dielectric constant of solvent Steady state Steady state Life time τ0 in ns Time resolved Time resolved
Ksv M−1 kq×109 K'sv M−1 k'q×109
M−1 s−1 M−1 s−1

EA 6.02 946.05 1508.85 0.627 310.64 495.44

THF 7.58 692.46 996.34 0.695 246.91 355.27
MeOH 32.7 681.73 577.74 1.180 36.85 31.22
DMF 36.7 412.57 575.41 0.717 140.53 195.99
MeCN 37.5 374.91 422.67 0.887 139.72 157.52

4. Conclusion
Table 2b
The values of dielectric constant of solvents, steady state Ksv, kq, life time τ0 of 7MCA in dif-
ferent solvents, time resolved K'sv, and k'q. Following conclusions can be drawn from the present investigation:

Solvent Dielectric Steady Steady state Life Time Time 1. Benesi-Hildebrand plots indicate that interaction is stronger for
constant of state kq×109M−1 time resolved resolved 6MCA and TiO2 system in solvents with low dielectric constants.
solvent KSV M−1 s−1 τ0 in K'SV k'q×109M−1 But for 7MCA and TiO2 system, it is stronger in solvent with high di-
ns M−1 s−1
electric constant.
EA 6.02 276.78 2179.37 0.127 220.56 1736.69 2. The steady state and time resolved S-V plots are linear for both the
THF 7.58 408.84 4088.40 0.10 235.75 2405.61
systems in all the solvents. The magnitude of quenching rate param-
MeOH 32.7 673.19 2065.00 0.326 137.82 422.76
DMF 36.7 1081.089 3151.86 0.343 297.12 866.24 eter for 6MCA system is in decreasing order with increasing dielectric
MeCN 37.5 583.88 4170.57 0.14 670.58 4789.86 constant of the solvent except in methanol under time resolved state.

Fig. 9. Overlapping of absorption spectra (A) of TiO2 with emission spectra (E) of 6MCA.
10 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266

Fig. 10. Overlapping of absorption spectra (A) of TiO2 with emission spectra (E) of 7MCA.

Table 3a Table 3b
The values of Forster critical distance R0, energy transfer efficiency E, distance between do- The values of Forster critical distance R0, energy transfer efficiency E, distance between do-
nor and acceptor r, range of FRET and energy transfer rate of 6MCA. nor and acceptor r, range of FRET and energy transfer rate of 7MCA.

Solvent Forster Energy transfer r in Probable Energy transfer Solvent Forster Energy transfer r in Probable Energy transfer
distance R0 in efficiency E nm range for rate ×109s−1 distance R0 in efficiency E nm range for rate ×109s−1
nm FRET nm FRET

EA 1.58 0.44 1.64 0.79–2.37 1.28 EA 1.15 0.20 1.45 0.58–1.73 1.95
THF 1.55 0.35 1.72 0.78–2.33 0.77 THF 1.14 0.29 1.32 0.57–1.71 4.15
MeOH 1.62 0.35 1.80 0.81–2.43 0.45 MeOH 1.21 0.37 1.32 0.61–1.82 1.82
DMF 1.54 0.28 1.80 0.77–2.31 0.55 DMF 1.14 0.47 1.16 0.57–1.71 2.75
MeCN 1.61 0.24 1.95 0.81–2.42 0.36 MeCN 1.20 0.35 1.33 0.60–1.80 3.85
 J.M. Nirupama- et al. / Journal of Molecular Liquids 291 (2019) 111266 11

N N N

O
CH3

O O

6MCA

N N N

CH3
O O O

7MCA
Fig. 12. Polar and more stable structure of 7MCA compared to 6MCA.
Fig. 11. Cyclic Voltammogram of (a) 6MCA (b) 7MCA.

Acknowledgements

But for 7MCA system, quenching rate parameter is in increasing
order with increasing dielectric constant of the solvent except in
methanol and dimethylformamide.
3. From the FRET study, it is confirmed that, energy transfer rate for
6MCA and TiO2 system is decreasing with increasing dielectric con-
stant of the solvent. But for 7MCA system, energy transfer rate is in
increasing order with the increasing dielectric constant except in
ethyl acetate and tetrahydrofuran.
4. The electrochemical analysis reveals the role of electron transfer
from coumarin derivative to TiO2 NPs and also the involvement of
azido group (-N3) of 6MCA and 7MCA in electron transfer process.
The magnitude of free energy change for electron transfer confirms
that quenching is more efficient for 7MCA system compared to
6MCA.
5. The higher magnitude of quenching rate parameter of 7MCA com-
pared to 6MCA is due to its stable and polar structure. Further in
case of 7MCA, electrons circumpass to pyrone ring which is not pos-
sible in case of 6MCA.
One of the authors, Nirupama J.M. is grateful to the staff and Director
of USIC, Karnatak University, Dharwad, for providing instrument
facilities.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.molliq.2019.111266.
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Table 4
The values of reduction potential of TiO2, oxidation potential of coumarin derivatives, energy gap between HOMO and LUMO of coumarin derivative, quenching rate parameter and free
energy change for electron transfer in acetonitrile solvent.

Acceptor E(A/A−) Donor E(D/D+) E00 of coumarin kqx109 ΔG° in eV

In eV (coumarin derivative) in eV derivative M−1 s−1
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7MCA 0.62 3.52 4170.57 −2.30
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