Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 148 (2015) 105113

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Studies of the photophysics of highly uorescent Red Mega 480 laser dye
in solutions: Steady state spectroscopy
V.B. Tangod a, B.M. Mastiholi a, Prasad Raikar b, S.G. Kulkarni a, U.S. Raikar a,
a
b

Department of Physics, Karnatak University, Dharwad, Karnataka, India

Visveswaraya Technological University, Belgaum, Karnataka, India

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Solvent effect on absorption and

uorescence spectra of highly

uorescent Red Mega 480 laser dye
studied.
 Bathochromic shift is observed with
increasing polarity.
 Excited state dipole moments are
larger than the ground state due to
high polarity in excited state.
 Dipole moments are calculated by
various methods.
 Linear solvation energy relationships
are studied on the dye in reference to
degree of solvation strength.

a r t i c l e

i n f o

Article history:
Received 8 August 2014
Received in revised form 25 March 2015
Accepted 27 March 2015
Available online 4 April 2015
Keywords:
Red Mega 480
Dipole moment
Absorption
Emission
Solvatochromic
Stokes shift

a b s t r a c t
The absorption and uorescence spectra of highly uorescent industrially useful medium sized Red Mega
480 dye have been studied in various solvents at 298 K. The solute photophysical behavior depends
strongly on the solutesolvent interactions. In order to understand the effect of inter molecular
interactions on spectral behaviors of the dye in different solvents extent of this behavior can be analyzed
by linear solvation energy relationships. In addition, ground and excited state dipole moments were
evaluated by various methods. It is observed that excited state dipole moment (le) is larger than the
ground state (lg), absorption spectra show a bathochromic shift with increasing polarity indicating that
transition involved is p ? p and Onsager cavity radius is determined by atomic increment method.
2015 Elsevier B.V. All rights reserved.

Introduction
The effects of solvent environment on absorption and uorescence spectra of highly uorescent organic compounds has been
the subject of several great motivating [1,2] investigations.
Effects are complex, and are due several factors that affect the
Corresponding author at: Department of Physics, Karnatak University, Pavate
Nagar 580003, Dharwad, Karnataka, India. Tel.: +91 9480480079.
E-mail address: usraykar_kud@yahoo.co.in (U.S. Raikar).
http://dx.doi.org/10.1016/j.saa.2015.03.119
1386-1425/ 2015 Elsevier B.V. All rights reserved.

absorption and uorescence emission spectra and quantum

yields like solvent polarity, rate of solvent relaxation, probe conformational changes, rigidity of the local environment, internal
charge transfer, intermolecular charge transfer, proton transfer
and excited state reactions, probeprobe interactions and changes
in radiative and non-radiative decay rates.
These multiple effects provide many opportunities to investigate the effect of local environment on a uorophore [1].
However, it is difcult to know which effect is dominant in a
particular experimental system, and predictably more than one

106

V.B. Tangod et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 148 (2015) 105113

effect will simultaneously affect the uorophore. Excitation of a

molecule by photon causes a redistribution of charges leading to
conformational changes in the excited state. This can lead to an
increase or decrease of dipole moment of the excited state as
compared to the ground state.
A dipole moment represents a direct measure of electron
distribution in a molecule of known geometry [3]. It is a physical
constant which can be obtained by many experimental and
theoretical techniques. A number of excellent texts, monographs,
and reviews devoted to dipole moments are available and contain
a detailed discussion on the theory of dipole moments. It seems
worthwhile to point out here that, dipole moments convey most
important sources of structural information about organic molecules in ground and excited states [2].
Knowledge of the dipole moment in the ground and excited
state reects the charge distribution in the molecule and helps to
assess the efciencies of the quantum chemical derivations, electronic and geometrical structure of the molecule in short-lived
state, course of photochemical transformation, electron correlation
treatments and for calculating the electron density distribution in
the singlet and triplet state. It has been useful in the extraction of
parameters like molecular polarizability in nonlinear optical materials using electro optic methods [5]. An excellent overview of the
solvatochromic method by Koutek [5] has shown to facilitate
satisfactory results. The statistical analysis performed using various expressions in the process of identifying the best parameters
were based on the bulk solvent properties such as refractive index
(n) and dielectric constant (e). Out of the various expressions
chosen a few have been identied which could afford satisfactory
results for our selected Red Mega 480 dye compound. The best
expression identied by Koutek [4] was used earlier by Kawski
[4,6], Bakshiev [7], ChammaViallet [8], Lippert [9] and Suppan
[10] several reports are available in the literature in which the
above methods have been used independently or with other
methods to evaluate the excited state dipole moments. Several
organic compounds such as coumarin 6, coumarin 7, coumarin
30 and coumarin 337 have been widely studied by U.S. Raikar
et al. [1116], apart from the above mentioned methods there have
been other authors who have used various solvent parameters in
order to relate the spectral shifts. One of the well used parameter
is the ET(30) scale put forward by Reichardt [2]. Other parameters
are also taken into consideration by Katritzky et al. [17] in our
present work.
We have newly developed Red Mega 480 laser dye, whose dipole
moments presented in the present work is of our great interest.
Photophysics of a dye is an active eld of research because of very
much importance as laser material, strong absorption cross section
and high orescence quantum yield makes it an excellent laser dye
for the greenred region. Its uorescence properties are dependent
on the surrounding environments. That is why; it is widely used as a
laser dye, daylight uorescent pigment, lithography, microlithography, biomolecular labelling, direct conversion of excitation light
into emission without using a FRET (Forster Resonance Energy
Transfer) mechanism, variety of possible applications including
DNA sequencing and FISH (Fluorescence InSitu Hybridization)
microscopy, also used for multiwavelength backward photo acoustic scanner for 3D imaging of soft tissues to depths of several millimetres with a spatial resolution [18], biosensors, printing
technology, imaging of biological tissues and lipophilic uorescent
probe for biochemical and medicinal investigations [16,17].
Solvent effects play a key role in many chemical and physical
processes in solutions [1,2], this effect is closely related to the
nature and the degree of the solute dipole moment changing in
the process of solutesolvent interactions, solvent polarity, internal charge transfer and therefore it has been of the highest interest
in developing quantitative measurement of the dipole moment and

solutesolvent interactions [3,4,6]. Excitation of a molecule by

photon causes a redistribution of charges leading to conformational changes [19] in the excited state.
A number of experimental methods like microwave conductivity [20], electric dichroism [21], electric polarization of uorescence and stark splitting [22] are available to determine the
dipoles moment more precisely, but application have been limited
to instrument intensive and restricted to small organic molecules.
Solvatochromic method offers the simplest technique to determine
the dipole moments and is based on the shift of absorption and
uorescence maxima in different solvents [23,24].
These studies have gained much importance due to the progress
in photo science of dyes in recent and past. The accurate dipole
moment values give the information about the optical aspects of
a material. The improved estimation of the dipole moments means
a better understanding of the electron charge distribution as these
estimated values give insight into photochemical reaction or
quantum yield of a highly applicative dye.
To establish the dipole moment in excited state (le) with the solvatochromic method and also to compare the values which are
obtained, several approaches have been used by Lippert [9,15],
Bakhshiev [7,15], KawskiChammaViallet [6,13], Suppan [10,13],
Ravi et al. [25] , McRae [26] and these will be employed in this study.
The solvent dependency of Stokes shift can originate from
dielectric constant and specic (hydrogen bonding) solutesolvent
interactions. Further solvent effect can be analyzed by solvatochromic parameters and solvent polarity [17,15,27,28]. Stokes shift can
be used to explain the multiparameter solvent polarity scales for
solutesolvent interactions. Effect of solvent polarity on the spectral features of the solute can be interpreted by means of linear solvation energy relationship (LSER), a concept that can be formulated
by KamletAbboudTaft (KAT) and Katritzky (KTZ) parameters
[17,27,28].
In this paper, detailed calculations of dipole moments both in
ground state and excited state of Red Mega 480 laser dye by various methods and in respect to solvent polarities are discussed in
depth.
Materials and methodology
Red Mega 480 was purchased from Sigma Aldrich and was used
without further purication. The Molecular structure for this highly
uorescent laser dye is given in Fig. 1. All the solvents viz., methanol, ethanol, propanol, butanol, nonanol, decanol, DMSO, and acetonitrile are of spectroscopic grade. Electronic absorption spectra
are recorded on Ocean Optics spectrophotometer at 298 K.
Theory: determination of dipole moments
The independent equations used for the estimation of ground
and excited state dipole moments of Red Mega 480 laser dye is
as follows:

Fig. 1. Molecular structure and IUPAC name of Red Mega 480. Molecular formula:
C26H30N2O7S (Red Mega 480). IUPAC Name: 1-(5-carboxypentyl)-6-{2-[7-(diethylamino)-2-oxo-2H-chromen-3-yl]ethenyl}pyridinium-3-sulfonate.

107

V.B. Tangod et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 148 (2015) 105113

Lipperts equation [9,15]:

ma  mf m1 Fe; n const

3:1

Bakhshievs equation [7,15]:

ma  mf m2 F 1 e; n const

3:2

KawskiChammaViallets equation [6,13]:

ma mf
2

lg

m3 F 2 e; n const

le

ma m4 F 3 e const

3:4

ma m5 F 4 e const

3:5

The expression Fe; n [Lipperts polarity parameter], F 1 e; n

[Bakhshievs polarity parameter], F 2 e; n [KawskiChamma
Viallets polarity parameter], F 3 e [McRaes polarity parameter]
and F 4 e [Suppans polarity parameter] are given below:

F 1 e; n

e  1 n2  1

2e 1 2n2 1

2n2 1
n2 2

"

e  1 n2  1

e 2 n2 2

2n2 1
F 2 e; n
2n2 2

2e  1
F 3 e
e2

"
#
3 1=2
m3 m2 hca
2
2m2

3:6

le


2e  1
2e 2

3:18

The validity of above equations is based on the following certain

assumptions [16] like lg and le dipole moments are collinear, the
Onsager cavity radius is same in ground and excited state,
polarizability of the molecule is ignored and hydrogen bonding
effect is also ignored.The above theoretical calculations correlate
much better with microscopic solvent polarity ENT rather than bulk
solvent polarity functions involving dielectric constant and


3:7


e  1 n2  1
3n4  1

 2
2
e2 n 2
2n2  1

refractive index (e,n). The spectral shift with ENT parameter proposed
by Reichardt [2], and improved by Ravi et al. [25] is given in
Eq. (3.19),

3:8

ma  mf 11307:6
3:9

3:10

ma and mf are absorption and uorescence maxima in wave numbers

(cm1) respectively. e and n are dielectric constant and refractive
index of the solvents respectively. Plotting the graphs of
Eqs. (3.1)(3.5) it follows that ma  mf versus Fe; n, ma  mf
versus F 1 e; n, 12 ma mf versus F 2 e; n, ma versus F 3 e and ma
versus F 4 e should give linear graphs with slopes m1, m2, m3, m4,
m5 respectively and are given below

m1

m2

m3

m4

2le  lg 2
3

hca

"

dl
d lB

3:11

hca

2l2e  l2g
3

lg le  lg
3

hca

lg le  lg
3

hca

3:19

where dlB = 9D and aB = 6.2 are dipole moment changes on excitation and Onsager cavity radius respectively of a betaine dye molecule [2,25], dl and a are corresponding quantities of Red Mega 480
laser dye of our present interest. The change in dipole moment can
be evaluated from the slope of Stokes shift versus ENT plot and is
given by the equation.

Dl l e  l g

s
mNT  81

3:20

6:2=a3  11307:6

where mNT is the slope between Stokes shift and ENT parameter.
Reichardt [2] proposed relationship between ENT and ET(30) for a solvent is given by:

3:21

3:12

3:13

ET(30) values are based on negatively pyridinium N-phenolate

betaine dye [32].
1

ET 30 kcal mol hcmm NA

2:8591  103 mm ; cm1
28591=km nm

3:14

and

m5

2  3 #
aB
ENT const
a

ENT ET 30solv ent  30:7=32

2le  lg

hca

3:17



m2 m3
l
m3  m2 g

F 4 e

3:16

and

Suppans equation [25]:

"
#
3 1=2
m3  m2 hca

2
2m2

3:3

McRaes equation [26]:

Fe; n

volume is calculated based on the Bondi radii method [30] and this
value is also compared with atomic increment method by Edward JT
[31] with assuming the fact that ground and excited state dipole
moments are almost parallel to each other. The following
expressions are obtained on the basis of Eqs. (3.12) and (3.13).

3:15

where lg and le are the ground and excited state dipole moments
of the solute molecule respectively, h and c are planks constant and
velocity of light in vacuum respectively, a is the Onsager cavity
radius which is determined by Suppans equation [29] a = (3M/
4pdN)1/3, where M is the molecular weight, d is the density of the
solute molecule and N is Avogadros number. The ratio (M/d) molar

km is the wavelength of the absorption maxima.

Generally according to the McRae-Bayliss model of solvatochromism [2] which is directly evolved from Onsagers eld theory, the
angle between ground state and excited state dipoles are solute
dependent, and solute dipole is polarizable and therefore affected
by the onsagers reaction eld, the dipole moments lg and le are
not parallel to each other but have a very small angle U between
them and is given by [15,16]:

cos U

1
2lg le

l2g l2e 

m2 2
l  l2g
m3 e


3:22

108

V.B. Tangod et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 148 (2015) 105113
Table 2
Calculated values of F(e,n), F1(e,n), F2(e,n), F3(e), F4(e) for various solvents.

Results and discussion

Absorption and uorescence spectra of Red Mega 480 in various
solvent parameters like dielectric constant (e) and refractive index
(n) are recorded using Ocean Optics Spectrophotometer. Table 1
summarizes dielectric constant (e), refractive index (n), ET (30)
and ENT and other values of various solvents. The calculated values
of solvent polarity functions F(e,n), F1(e,n), F2(e,n), F3(e), F4(e) (Eqs.
(3.6)(3.10)) for various solvents employed in the present study is
depicted in Table 2.
The absorption spectra of Red Mega 480 in different solvents
show a maximum around 490507 nm (Table 3). The maximum
absorption wavelength band (Fig. 2) is sensitive to solvent polarity;
shifts with solvent have been reported [33]. The uorescence emission spectras are recorded by exciting the sample at its longest
absorption maximum. The excitation maximum coincides with
the longest wavelength absorption band has been assigned as the
intermolecular charge transfer (ICT) [27,28]. Increase in solvent
polarity shifts absorption and emission maximum to the longer
wavelength region.
Stokes shift values for all the solvents are given in Table 3. The
uorescence emission spectra show a maximum around 602
644 nm in different solvents, with a shift of the maximum depending upon the solvent we used. The uorescence emission spectra
show little larger shift as compared with the absorption spectra.
The absorption shift with solvent implies that the ground state
energy distribution is affected to greater extent, possibly due to
the polar nature of the dye in the ground state rather than the
excited state.
The magnitude of the Stokes shift varies between 3458.43 and
4392.37 cm1. The values of the Stokes shift is also an indicative
of the intramolecular charge transfer (ICT) [27,28]. The large magnitude of Stokes shift indicates the excited-state geometry could be
different from that of the ground state. The general observation is
that, there is an increase in the Stokes shift values with increasing
solvent polarity which shows an increase in the dipole moment on
excitation.
The solvatochromic data can be used to identify the spectra,
namely p ? p, n ? p. It can be noticed from Tables 1 and 3 that,
with increase in the polarity of the solvent, the uorescence emission peak undergoes bathochromic (red) shift, conrming p ? p
transition [33]. The shift of the uorescence wavelengths towards
longer wavelengths could be caused, if the excited state charge distribution in the solute is markedly different from the ground state
charge distribution, and it gives rise to a stronger interaction with
polar solvents in the excited state. Among the different methods of
determining excited-state dipole moment (le), solvatochromic
method [510] is the most extensively used. This method has been
based on a linear correlation between the wave numbers of the
absorption and uorescence maxima and a solvent polarity function. Such correlations have been derived from quantum mechanical second order perturbation and Onsagers reaction-eld theories

Table 1
Spectroscopic polarity parameters [16] and polarity functions are used in multiparameter analysis of Red Mega 480 laser dye.
Solvent

ET(30)

EN
T

Methanol
Ethanol
2-Propanol
1-Butanol
Nonanol
Decanol
DMSO
Acetonitrile

33.7
24.3
20.2
17.4
8.83
8.0
47.2
38.8

1.329
1.361
1.377
1.399
1.427
1.437
1.479
1.344

55.4
51.9
48.4
49.7
47.8
47.7
45.1
45.6

0.98
0.86
0.76
0.84
0.13
0.70
0.00
0.19

0.66
0.75
0.84
0.84
0.1
0.82
0.76
0.4

0.60
0.54
0.48
0.47
0.73
0.45
1.00
0.66

0.762
0.654
0.546
0.593
0.528
0.525
0.444
0.460

Solvent

F(e,n)

F1(e,n)

F2(e,n)

F3(e)

F4(e)

Methanol
Ethanol
Propanol
Butanol
1-Nonanol
Decanol
DMSO
Acetonitrile

0.309
0.289
0.277
0.263
0.215
0.203
0.263
0.306

0.857
0.812
0.781
0.749
0.586
0.55
0.841
0.866

0.653
0.652
0.647
0.646
0.583
0.571
0.744
0.667

1.832
1.772
1.730
1.691
1.446
1.396
1.878
1.853

0.956
0.940
0.928
0.916
0.839
0.822
0.969
0.962

for development of solvent polarity functions. The most employed

solvent polarity functions are those obtained by Lippert [9],
Bakhshiev [7], KawskiChammaViallet [6], which use both dielectric constant (e) and refractive index (n) of the medium as empirical parameters. Moreover, the same experimental data can be used
for quantitative evaluation of the contribution of different types of
solutesolvent interactions using multi-parameter solvent polarity
scales [27,28]. It was shown that correlations of spectral properties
are signicantly improved by such multiparameter treatment. This
method allows various independent interactions to be characterized implicitly between solvent and solute ground, transition,
and excited states [15].
Table 3 summarizes Stokes shift and arithmetic mean of Stokes
values [34]. Figs. 38 shows the graphs of Stokes shift versus F(e,n)
i.e. Lipperts polarity parameter, Stokes shift versus F1(e,n) i.e.
Bakshievs polarity parameter, 12 ma mf versus F2(e,n) i.e.
KawskiChammaViallets polarity, ma versus F3(e) i.e. McRaes
polarity parameter, ma versus F4(e) i.e. Suppans polarity parameter,

ma versus ENT i.e. solvent polarity parameter (Eq. (3.19)) and the
slopes m1, m2, m3, m4, m5 and mNT (Eqs. (3.11)(3.15) and (3.20))
are obtained from these graphs, respectively. A linear progression
was done by employing Origin 6.0 software and the data was t
to a Straight line. The correlation coefcients, slopes, intercepts
of the linearly tted data are given in Table 4. Here in most of
the cases, correlation coefcients are found to be larger than 0.85
that indicates a good linearity with selected number of Stokes shift
data points. In few cases some of the solvents do not participate in
the correlation. Generally this deviation from linearity may be due
to specic solutesolvent interactions. The deviation from linearity
for some solvents might probably be due to hydrogen bonding nature of the molecule and at the same time charge transfer in the
excited state cannot be ruled out. For Red Mega 480 Onsager cavity
radius a = 4.53 is calculated by atomic increment method and the
various slopes are m1 = 5967.03, m2 = 2138.13, m3 = 3618.44,
m4 = 1321.5, m5 = 4735.43 and mNT = 685.80. Using the Eqs.
(3.11)(3.15), we get the dipole moment lg = 1.54 D, le = 5.99 D
(Solvatochromic method), le = 8.97 D (Lipperts method),
le = 17.42 D (McRae method), le = 58.43 D (Suppans method),

le = 2.95 D (ENT solvent polarity method). These differences

between the values of le may be in part, due to the various
assumptions and simplications made in the solvatochromic
method, so the solvatochromic method is considered the right
method to calculate the dipole moment of the molecule. The le
values obtained by Lipperts method are large, since it does not
considered the polarizability [3538]. The le values obtained by
Suppans method are large compared to any other methods, also
value of le is calculated by McRae and it is large. Both Suppan
and Mc Rae assumptions made during the equations which do
not involve the uorescence maxima and refractive index of the
solvents, without involvement of uorescence maxima and refractive index of the solvent, it is insufcient to calculate the exact
value of excited and ground state dipole moments, so the results
are not reliable compared with that calculated from emission

109

V.B. Tangod et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 148 (2015) 105113
Table 3
Absorption maxima, uorescence maxima, Stokes shift and arithmetic mean of Stoke values for Red Mega 480.
Solvent

Absorption maximum (nm)

Fluorescence maximum (nm)

ma (cm1)

mf (cm1)

Stokes shift (ma  mf ) (cm1)

1=2 ma  mf (cm1)

Methanol
Ethanol
Propanol
Butanol
Nonanol
Decanol
DMSO
Acetonitrile

502
503
503
507
501
490
499
501

644
630
622
621
606
602
637
635

19920.32
19880.72
19880.72
19723.87
19960.08
20408.16
20040.08
19960.08

15527.95
15873.02
16077.17
16103.06
16501.65
16611.3
15698.59
15748.03

4392.37
4007.70
3803.55
3620.81
3458.43
3796.87
4341.49
4212.05

17724.13
17876.87
17978.94
17913.46
18230.87
18509.73
17869.33
17854.06

0.3

4800

1800

Backshiev's
4600

1600

0.1

1
7
8

4200

a-f

1400

4400

Fluorescence

Absorption

0.2

4000

2
3

3800

1200

3600

5
3400

0.0

1000
400

500

600

3200
0.50

700

0.55

0.60

0.65

Wavelength (nm)

0.70

0.75

0.80

0.85

0.90

F 1 (, n)

Fig. 2. Absorption and emission spectra of Red Mega 480 in ethanol.

Fig. 4. Plot of Stokes shift versus F1(e,n) i.e. Bakshievs polarity parameter of Red
Mega 480 in different solvents (1 methanol, 2 ethanol, 3 isopropanol, 4
butanol, 5 nonanol, 6 decanol, 7 DMSO, 8 acetonitrile) (
linear t).

4800

Lippert's
4600
19000

4400

Kawski-Chamma-Viallet's

18750

7
4200

a- f

18500

4000

18250

3
6
3600

1/2 (a+f)

3800

4
5

5
3

18000

4
17750

3400
17500

3200
0.20

0.22

0.24

0.26

0.28

0.30

0.32

F (, n)
Fig. 3. Plot of Stokes shift versus F(e,n) i.e. Lipperts polarity parameter of Red Mega
480 in different solvents (1 methanol, 2 ethanol, 3 isopropanol, 4 butanol, 5
nonanol, 6 decanol, 7 DMSO, 8 acetonitrile) (
linear t).

maxima and refractive index of the solvents. The value of le calculated by ENT almost agrees with solvatochromic method [15,33].
It is very interesting to note from the Table 5, small differences
are observed between the estimated values of le and by Lippert
method are large, since it does not take into account of polarizability. The le values obtained by solvatochromic method Eqs. (3.17)
and (3.18), almost agree with ENT solvent polarity method compared to any other methods, because, other methods includes only
absorption maxima and dielectric constant only. In literature one
may nd that large number of investigators has used solvatochromic shift method (Eqs. (3.17) and (3.18)) to estimate excited state

17250
17000
0.56

0.58

0.60

0.62

0.64

0.66

0.68

0.70

0.72

0.74

0.76

F2 (, n)
Fig. 5. Plot of 12 ma mf versus F2(e,n) i.e. KawskiChammaViallets polarity
parameter of Red Mega 480 in different solvents (1 methanol, 2 ethanol, 3
isopropanol, 4 butanol, 5 nonanol, 6 decanol, 7 DMSO, 8 acetonitrile)
(
linear t).

dipole moment. We believe that the excited state dipole moments

estimated from solvatochromic shift method are the most proper
values.
Zakerhamidi [27,28,34] also obtained the values of lg and le for
his chosen compounds and are also positive, further le is very
much larger than the lg which means that the excited state is more
polar than the ground state. It also indicates that the excited state
electronic charge distribution should be substantially different

110

V.B. Tangod et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 148 (2015) 105113
5000

21000

Mc Rae's

20800

4750

20600

N
T

4500

20400

4250

20000

19800

a-f

1
8

20200

4000

3750

3500

19600

3250

19400

3000
0.40

19200
1.4

1.5

1.6

1.7

1.8

1.9

0.45

0.50

F3 ( )

0.55

0.60

Fig. 6. Plot of ma versus F3(e) i.e. McRaes polarity parameter of Red Mega 480 in
different solvents (1 methanol, 2 ethanol, 3 isopropanol, 4 butanol, 5
nonanol, 6 decanol, 7 DMSO, 8 acetonitrile) (
linear t).

0.65

0.70

0.75

0.80

T
N

ENT

Fig. 8. Plot of ma versus

i.e. solvent polarity parameter of Red Mega 480 in
different solvents (1 methanol, 2 ethanol, 3 isopropanol, 4 butanol, 5
nonanol, 6 decanol, 7 DMSO, 8 acetonitrile) (
linear t).
Table 4
Slope, intercept and correlation coefcient data of Red Mega 480 laser dye by
different methods.

21000

Suppan's
20750

Method

Slope

Intercept

Correlation
coefcient

No of
data

Lipperts
Bakhshievs
KawskiChamma
Viallets
McRaes
Suppans

5967.03
2138.13
3618.44

2477.71
2496.65
20501.13

0.95
0.92
0.91

8
8
8

1321.5
4735.43
685.80

21014.42
21727.91
4347.19

0.89
0.85
0.91

8
8
8

20500

20250

20000

3
4

19750

8
2

EN
T

19500
19250
19000
0.82

0.84

0.86

0.88

0.90

0.92

0.94

0.96

0.98

F 4 ( )
Fig. 7. Plot of ma versus F4(e) i.e. Suppans polarity parameter of Red Mega 480 in
different solvents (1 methanol, 2 ethanol, 3 isopropanol, 4 butanol, 5
nonanol, 6 decanol, 7 DMSO, 8 acetonitrile) (
linear t).

from the ground state charge distribution. It also depicts that the
observed transition is p ? p transition. The dipole moment of
Red Mega 480 molecule in excited state is higher than the ground
state. This is explained in terms of possible resonance structure as
shown in Fig. 9. The dipole moment of a probe molecule increases
almost four times on excitation can be explained in terms of nature
of intramolecular charge transfer (ICT). Further a large change in
the dipole moment on excitation suggests that, strong solvent
polarity and hydrogen bonding effects possibly makes the excited
state to be twisted and intramolecular charge transfer (TICT) in
nature. Thus the presence of a large TICT and increase in planarity
on excitation render the molecule more polar as compared to
ground state giving rise to a large change in the dipole moment.
The charge transfer band shows a shift of about 17 nm in the
absorption spectra on changing the solvent from decanol to butanol, while 42 nm shift in uorescence spectra from decanol to
methanol. The absorption shift with solvent implies that the
ground state energy distribution is lesser to excited state because
of polar nature of the dipole molecule Red Mega 480.
Assuming that the symmetry of the investigated solute molecule changes upon electronic transitions, the ground and excited

state dipole moments are not exactly parallel [14]. One more notable point is the large difference in the le and lg values, clearly
indicative of charge in the molecular structure of a dye on excitation. Of course the large solvatochromic shifts in the present study
are consistent with this observation. This indicates that on excitation the orientation of the dipole moment has considerably changed. This change in the orientation in the dipole moment (h) can
be measured using the Eq. (3.22) and it is 1.82.
The polarity of a molecule depends on electron density. With
supply of additional energy there will be transition of electron
from ground state to excited state. Which leads to the delocalization of the excited state, it may be solutesolvent interactions or
intramolecular hydrogen bonding via solvent. Because of the
movement of electron from ground state orbital to excited state
orbital, there will be increase of dipole moment with reference to
ground state dipole moment. The linear ET(30) dependence of
Stokes shift indicates the existence of general type of solutesolvent interaction.
It is observed that there is bathochromic shift in absorption
maximum in most of the solvents provides the strong evidence
of excited state dipole for the Red Mega 480 laser dye is larger than
the ground state dipole moment. The calculated dipole moments
indicate the excited-state dipole moments (le) are greater than
those in ground-state (lg). Increase in the singlet excited states
dipole moments is about Dl = 4.45 D that demonstrates the dye
is more polar in excited states as compared with ground states.
Additionally, large change in dipole moments on excitation suggests that excited states are twisted intramolecular charge transfer
(TICT) in the solvent environment. TICT process increases planarity
of dyes molecular structure on excitation and increases the change
in dipole moment.

111

V.B. Tangod et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 148 (2015) 105113
Table 5
Ground-state, excited state dipole moment of ADS680HO, ADS740WS and Red Mega 480 dyes.
Molecule

Onsager cavity radius a ()

lga (D)

leb (D)

lec (D)

led (D)

lef (D)

leh (D)

le/lgi

Uj

Red Mega 480

4.53

1.54

5.99

8.97

17.42

58.43

2.95

3.89

1.82

1 Debye = 3.33564  1030 cm = 1018 esu cm.

a
Ground state dipole moment calculated from Eq. (3.16).
b
Excited state dipole moment calculated from Eq. (3.17) Solvatochromic method.
c
Excited state dipole moment calculated from Lipperts Eq. (3.11).
d
Excited state dipole moment calculated from Mc Raes Eq. (3.14).
f
Excited state dipole moment calculated from Suppans Eq. (3.15).
h
Excited state dipole moment calculated from microscopic solvent polarity function EN
T.
i
Ratio of excited to ground state dipole moments calculated from Eq. (3.18).
j
Angle between excited state to ground state dipole moment with solvatochromic data.

Fig. 9. Possible resonance structures of Red Mega 480 laser dye.

Correlation with multiparameter solvent polarity scale

One of the most ambitious, and very successful, quantitative
treatments of solvent effects by means of a multiparameter equation is that introduced by Kamlet and Taft [39] in 1976 and called
Linear Solvation Energy Relationship (LSER). Using the UV/Vis/near
IR spectroscopically derived solvatochromic parameters. The solvent
dependent spectral shifts originate from [28,34], specic solutesolvent interactions (e.g. hydrogen-bonding, Intramolecular charge
transfer (ICT), proton transfer) and non-specic interactions
(dielectric enrichment) of the solvent.
In fact, there is a strong competition between the solutesolute,
solutesolvent and solventsolute interactions that determines the
nature of Solvatochromic behavior of the solute molecules. The solvent effect can be further evaluated by means of solvent polarity
scale and solvatochromic parameters. However, to explain multiparameter solvent polarity scale for quantitative and qualitative
assessment of the solvent/solute interactions, the spectroscopic
shifts can be used. Effect of solvent polarity on the spectral features
of the solute can be interpreted by means of linear solvation energy
relationship (LSER) concept that can be formulated as Kamlet
AbboudTaft (KAT) (Eq. (4.1)) and Katritzky (KTZ) (Eq. (4.2)).

ma  mf ma  mf

ma  mf ma  mf

a  a b  b s  p

a

4:1


e1
n2  1
b
s  ET 30
2e 1
2n2 1
4:2

where p is a measure of the solvent dipolarity/polarizability [40], b

is the scale of the solvent hydrogen bond acceptor (HBA) basicities
[39], a is the scale of the solvent hydrogen bond donor (HBD)

acidities [34]. e, n and ET(30) [25,27,28] are relative permittivity,

refractive index and empirical polarity parameter of the solvent,
respectively. ma  mf 0 is regression value of solute property in the
reference solvent. The Katritzky equation estimates independent
contributions of solvent dipolarity, polarizability, and other specic
interactions (e.g. hydrogen bonding, extra pp interaction). In order
to have a comparable a, b and s values for Katritzky equation, all the
parameters should be re-normalized and rescaled. The regression
coefcients a, b and s in these equations measure the relative susceptibilities of the solute property (such as absorption, uorescence
and other spectroscopic parameters) to the indicated solvent
parameters.
Scales of dipolarity/polarizability concept is that the solute
solvent interactions can be dissected into general, which have
electrostatic and dispersive origins and can be related conceptually
to reaction eld theories and specic interactions which include
hydrogen bonding donor/acceptor interactions. p dened by
KamletAbboudTaft (KAT) is intended to provide the information
about the non specic part of van deer Waals interactions between
solute and solvents. The scale was based on the treatment of the
solvatochromic shifts undergone by selected absorption bands of
a variety of aromatic molecules.
KAT (KamletAbboudTaft) equation comprises spectroscopic
polarity scales including hydrogen bonding donor ability (a),
hydrogen bonding accepting ability (b) and dipolarity/polarizability (p) is a multiparameter scale. The KAT equation originally
evaluates specic hydrogen bonding interactions between solute
and solvent, while the KTZ (Katritzky) equation basically evaluates
dipolarity/polarizability interactions.
The results for both KAT and KTZ scales were calculated using
the multi-linear regression analysis in Microsoft Excel by means
of Data Analysis tool pack.

112

V.B. Tangod et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 148 (2015) 105113

Table 6
Multiparameter regression ts to solvatochromic polarity scales for Stokes shift of Red Mega 480 laser dye.
Multiparameter scale

ma  mf 0 (103 cm1)

A (103 cm1)

b (103 cm1)

s (103 cm1)

Ra

SDb

Fc

Katritzky
KamletAbboudTaft

1.543 (0.045)
2.223 (0.009)

9.813 (0.044)
0.621 (0.007)

2.150 (0.087)
0.251 (0.006)

0.0119 (0.0004)
1.981 (0.012)

0.89
0.97

186
129

1.9
1.2

Number of the solvents: 8.

a
R-square.
b
SD-standard error.
c
F-statistic.

Table 7
Percentage contribution of solvatochromic parameters of Red Mega 480 laser dye.
Multiparameter scale

Katritzky
KamletAbboudTaft

Per (%) + Pn (%)

P ET 30 (%)

P p (%)

Pa (%)

Pb (%)

51.8
13.6

48.2
31.2

55.2

In order to estimate the comparable coefcient values a, b and s

for Red Mega 480 laser dye solute molecule, we have re normalized
and rescaled the parameters for all the used solvents
(Tables 1, 6 and 7), this scale can provide information about the
excitation process, the results for both KAT and KTZ scales, we calculated using multi-linear regression analysis and results are listed
in Tables 6 and 7. The obtained result were transformed into percentage contributions and summarized in Tables 6 and 7.
The sign of s coefcient, for KamletAbboudTaft parameter
and Katritzky is positive; it indicates overall contribution of dipolarity and polarizability increases stabilization of excited state of
Red Mega 480 dye in all solvents. However, the coefcients a is
positive (KAT), hydrogen bond establishes between the dye and
solvent molecules (a is the scale of the solvent hydrogen bond
donor (HBD) acidities) because of two @O groups, one OH group
makes the excited state to be more stable than the ground state.
b is positive (KAT) and this contribution, suggests the stabilization of excited state with inactive chain SO
3 , so b is the scale of
the solvent hydrogen bond acceptor (HBA) basicities. Two @O
groups, one OH group in the dye helps to increase in the HBD
and HBA, the dye makes the a and b positive in Katritzky
parameter (KTZ).
The KAT percentage contribution of solvatochromic parameters
for Red Mega 480 dye with different solvents is Pp 13:6%,
Pa = 31.2%, Pb = 55.2%, because of presence of two @O groups, one
OH group makes the hydrogen bond acceptor Pb (HBA) contribution is maximum. The KTZ percentage contribution of solvatochromic parameters for Red Mega 480 dye with different solvents
is PET 30 = 48.2% , while Pe + Pn = 51.8%. It witnesses, major contribution due to solvent basicity and dipolarity/ polarizability than
ET(30) parameter.
In case of Red Mega 480 dye the nonbonding electrons on carbonyl group, tertiary amino group and ring oxygen contribute
towards the mobility of electrons on the aromatic ring. The nitrogen atom of tertiary amino group being sp3 hybridized has more
electron donating tendency. Upon excitation, the carbonyl group
becomes highly electrophilic and tertiary amino group becomes
strong electron donor. Also there is possibility of electron mobility between ring oxygen and carbonyl group. These observed
variations in the dipole moments of the three dipolar laser dyes
which can be explained by the resonance structures (or hybrid)
that, generally it predicts the location of positive and negative
electrostatic potentials in the molecule. Resonance (Fig. 9) contributors are more in Red Mega 480, and hence the charge separation is larger.

Conclusions
Solvent effect on absorption and emission spectra of investigated Red Mega 480 laser dye is complex and strongly depend
on the nature of solvents and the substituent groups.
Investigated solutesolvent interactions are generally controlled
by dipolarity/polarizability and basicity of the solvents.
The obtained excited-state dipole moment from Lippert,
Bakhashiev, KawskiChammaViallet, McRae, Suppan and solvent
polarity methods. Dye possesses greater dipole moment in excited
state than the ground state. Moreover, this large change in the
excited state dipole moment as compared to ground state is due
to intramolecular charge transfer (ICT); a large change in dipole
moment on excitation suggests that excited state is twisted
intramolecular charge transfer (TICT). Also, excited state is more
polar than the ground state.
The obtained values of dipole moments in the ground and
excited states with percentage contributions of solvatochromic
parameters for investigated dye demonstrates relative resonance
structures and quanties the interactions between solvent and
the dyes molecules.
Acknowledgement
This work is supported by Vision Group on Science and
Technology, Government of Karnataka (VGST, K-FIST-level II) at
Karnatak University, Dharwad.
References
[1] J.R. Lackowicz, Principles of Fluorescence Spectroscopy, Plenum, New York,
1983.
[2] C. Reichardt, Solvents and Solvents Effects in Organic Chemistry, Verlag
Chemie Weinheim, New York, 1988.
[3] R.J.W. Le Fevre, Dipole Moments, Methuen, London, 1953.
[4] A. Kawski, Progress in Photochemistry and Photophysics, vol. V, CRC Press,
Boca Raton, FL, 1994.
[5] B. Koutek, Collect. Czech. Chem. Commun. 43 (1978) 2368.
[6] A. Kawski, J.F. Rabek, Progress in Photochemistry and Photophysics, vol. V, CRC
Press, Boca Raton, 1992.
[7] N.G. Bakshiev, Opt. Spectrosc. 13 (1962) 507.
[8] A. Chamma, P. Viallet, Acad. Sci. Ser C 270 (1901) 1970.
[9] E. Lippert, Z. Naturforsch. 10A (1955) 541.
[10] P. Suppan, Chem. Phys. Lett. 94 (1983) 272275.
[11] U.S. Raikar, C.G. Renuka, Y.F. Nadaf, B.G. Mulimani, A.M. Karguppikar, J.
Fluoresc. 16 (6) (2006) 847854.
[12] U.S. Raikar, C.G. Renuka, Y.F. Nadaf, B.G. Mulimani, J. Mol. Struct. 787 (2006)
127130.
[13] U.S. Raikar, V.B. Tangod, C.G. Renuka, B.M. Mastiholi, Afr. J. Pure Appl. Chem. 4
(4) (2010) 5157.
[14] U.S. Raikar, V.B. Tangod, B.M. Mastiholi, V.J. Fulari, Opt. Commun. 284 (2011)
47614765.
[15] V.B. Tangod, P. Raikar, B.M. Mastiholi, U.S. Raikar, Can. J. Phys. 92 (2) (2014)
116123.
[16] U.S. Raikar, V.B. Tangod, B.M. Mastiholi, S. Sreenivasa, Afr. J. Pure Appl. Chem. 4
(9) (2010) 188197.
[17] A.R. Katritzky, D.C. Fara, H. Yang, K. Tmm, T. Tamm, M. Karelson, Chem. Rev.
104 (1) (2004) 175198.
[18] E. Zhang, J. Laufer, P. Beard, Appl. Opt. 47 (2008).
[19] A. Kumar Satpati, M. Kumbhakar, D. Kumar Maity, H. Pal, Chem. Phys. Lett. 407
(2005) 114118.
[20] W. Liptay, E.C. Lim, Excited States, vol. 1, Acad. Press, New York, 1974.

V.B. Tangod et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 148 (2015) 105113
[21] A. Kawski, J.F. Rabek, Progress in Photochemistry and Photophysics, vol. 207,
CRC Press, Boca Raton, 1992.
[22] J. Czekella, Z. Chim. 15 (1961) 26.
[23] C. Vijila, A. Ramalingam, P.K. Palanisamy, V. Masilamani, Spectrochim. Acta A
57 (2001) 491497.
[24] V. Karunakaran, P. Ramamurthy, T. Josephrajan, V.T. Ramakrishnan,
Spectrochim. Acta A Chem. 58 (2002) 14431451.
[25] M. Ravi, A. Samantha, T.P.R. Krishnan, J. Phys. Chem. 98 (1994) 9133.
[26] N.S. Baylis, E.G. McRae, J. Am. Chem. Soc. 58 (1954) 1002.
[27] M.S. Zakerhamidi, A. Ghanadzadeh, M. Moghadam, Spectrochim. Acta A 78
(2011) 961966.
[28] M.S. Zakerhamidi, M. Moghadam, A. Ghanadzadeh, S. Hosseini, J. Lumin. 132
(2012) 931937.
[29] P. Suppan, Chem. Phys. Lett. 94 (1983) 272275.

113

[30] Y.H. Zhao, M.H. Abraham, A.M. Zissimos, J. Org. Chem. 68 (2003) 7368.
[31] J.T. Edward, Chem. Ind. 4 (1956) 774.
[32] V. Sasirekha, M. Umadevi, V. Ramakrishnan, Spectrochim. Acta 69A (2008)
148.
[33] J. Thipperudrappa, D.S. Biradar, S.R. Manohara, S.M. Hanagodimath,
Spectrochim. Acta A 69 (2008) 991997.
[34] M.S. Zakerhamidi, S. Ahmadi-kandjani, M. Moghadam, E. Ortyl, S. Kucharski,
Spectrochim. Acta A 85 (2012) 105110.
[35] E. Lippert, B. Bunsenges, Phys. Chem. 61 (1957) 962.
[36] A. Kawski, Z. Naturforsch. 57 (2002) 255.
[37] A. Kawski, P. Bojarski, B. Kuklinski, Chem. Phys. Lett. 463 (2008) 410.
[38] A. Kawski, B. Kuklinski, P. Bojarski, Chem. Phys. 359 (2009) 58.
[39] M.J. Kamlet, R.W. Taft, J. Am. Chem. Soc. 98 (1976) 377383.
[40] J.M. Abboud, M.J. Kamlet, R.W. Taft, J. Am. Chem. Soc. 99 (1977) 83258327.