Spectrochimica Acta Part A 75 (2010) 13471353

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

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

Spectrophotometric and spectroscopic studies of charge transfer complexes of

p-toluidine as an electron donor with picric acid as an electron acceptor in
different solvents
Neeti Singh, Ishaat M. Khan, Afaq Ahmad
Department of Chemistry, Faculty of Science, Aligarh Muslim University, Aligarh 202002, U.P., India

a r t i c l e

i n f o

Article history:
Received 4 June 2009
Received in revised form
26 December 2009
Accepted 31 December 2009
Keywords:
Charge transfer complex
p-Toluidine (PTD)
Picric acid (PiOH)
Visible region
Formation constant
FT-IR spectroscopy

a b s t r a c t
The charge transfer complexes of the donor p-toluidine with -acceptor picric acid have been studied
spectrophotometrically in various solvents such as carbon tetrachloride, chloroform, dichloromethane
acetone, ethanol, and methanol at room temperature using absorption spectrophotometer. The results
indicate that formation of CTC in non-polar solvent is high. The stoichiometry of the complex was found
to be 1:1 ratio by straight-line method between donor and acceptor with maximum absorption bands.
The data are discussed in terms of formation constant (KCT ), molar extinction coefcient (CT ), standard
free energy (Go ), oscillator strength (f), transition dipole moment (EN ), resonance energy (RN ) and
ionization potential (ID ). The results indicate that the formation constant (KCT ) for the complex was shown
to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Charge transfer complexation is an important phenomenon in
biochemical and bioelectrochemical energy transfer process [1].
Charge transfer phenomenon was introduced rst by Mulliken.
The term charge transfer gives a certain type of complex resulting from interactions of donor and acceptor with the formation
of weak bands [2,3] and discussed widely by Foster [4]. Molecular
interactions between electron donors and acceptors are generally
associated with the formation of intensely colored charge transfer
complexes (CTCs) in which absorb radiation in the visible region
[5]. Molecular complexation and structural recognition are important processes in biological systems, for example, drug action,
enzyme catalysis and ion transfers through lipophilic membranes
all involve complexation [6]. Charge transfer complexes are currently of great importance since these materials can be utilized as
organic semiconductors [7], photo catalysts [8] and dendrimers [9].
They are also important in studying redox processes [10], second
order non-liner optical activity [11] and micro-emulsion [12].
In the present studies it was noted that the CT complex was
formed between picric acid (acceptor) and p-toluidine (donor).
Picric acid forms molecular complexes with aromatic hydrocarbons

such as anthracene [13], some aniline derivatives [14] and also with
aromatic amines [1517]. Mulliken suggested that the formation of
molecular complexes from two aromatic molecules can arise from
the transfer of an electron from a -molecular orbital of a Lewis
base to vacant -molecular orbital of a Lewis acid, with resonance
between this dative structure and the no-band structure stabilizing
the complex [2]. He also noted the possibility of complex formation
through the donation of an electron from a non-bonding molecular
orbital in a Lewis base to a vacant -orbital of an acceptor (n)
[18] with resonance stabilization of the combination. As part of such
studies picric acid is able to from CT complex with p-toluidine in
different polar solvents.
In this paper we investigated the interaction of PiOH (picric acid)
with PTD (p-toluidine) in solvents of different polarity at room temperature by visible spectra data of CT complex () of p-toluidine
with -acceptor, picric acid in said solvents, viz, carbon tetrachloride, chloroform, dichloromethane, acetone, ethanol, and methanol
and also studied the effect of solvents on the formation of CT complex. We have determined the formation constant and CT for the
CT complex of picric acid with p-toluidine in different solvents.
2. Materials and methods
2.1. Materials

Corresponding author. Tel.: +91 0571 2703515.

E-mail addresses: neetisingh72@gmail.com (N. Singh),
afaqahmad212@gmail.com (A. Ahmad).
1386-1425/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2009.12.085

p-Toluidine (CDH) and picric acid (Aldrich) were of the highest purity and used without further purication. Ethanol (Merck

1348

N. Singh et al. / Spectrochimica Acta Part A 75 (2010) 13471353

analytical grade), acetone (Merck), methanol (Merck) carbon

tetrachloride (Merck), chloroform (Merck) and dichloromethane
(Merck), were used without further purication.
2.2. Preparation of standard solutions
Solutions of donor of different concentrations, 0.01 M, 0.015 M,
0.02 M, 0.03 M, 0.05 M, 0.1 M, 0.2 M, 0.3 M, and 0.5 M were prepared
in different volumetric ask by dissolving p-toluidine accurately
weighed in different solvents such as carbon tetrachloride, chloroform, dichloromethane, acetone, ethanol and methanol.
A standard solution of acceptor, picric acid (0.01 M) concentration was prepared by dissolving accurate weight of acceptor in
above solvents in different volumetric asks.
3. Results and discussion
3.1. Observation of CT bands
The electronic absorption spectra of the donor p-toluidine,
acceptor picric acid and the resulting complex in carbon tetrachloride, chloroform, dichloromethane, acetone, ethanol and methanol
were recorded in the visible range 400600 nm using a spectrophotometer ELICO SL 177 scanning mini spectrophotometer with a
1 cm quartz cell path length. The electronic absorption spectra of
PiOH and PTD in CCl4 , CHCl3 and methanol are shown in Figs. 24.
A 3 ml volume of donor and acceptor was scanned separately
through a spectrophotometric titration [19] at room temperature with their wavelength of maximum absorption 385 nm for
picric acid, 440 nm for p-toluidine in acetone and for blank solvent (acetone) 340 nm shown in Fig. 1. For the reaction mixture of
donor (10 ml) and acceptor (10 ml) in different solvents, viz, carbon tetrachloride, chloroform, dichloromethane, acetone, ethanol
and methanol. A dark yellow color charge transfer complex was
formed (the complex for each of the reaction mixture standing
overnight at room temperature to form stable couple before analysis at the maximum absorbance (425 nm for carbon tetrachloride,
430 nm for chloroform, 435 nm for dichloromethane, 440 nm for
acetone, 445 nm for ethanol and 450 nm for methanol)). The concentration of the donor in the reaction mixture was kept greater
than acceptor, [D]o  [A]o [20,21] and changed over a wide range
of concentration from 0.01 M to 0.5 M while concentration of acceptor (picric acid) was kept xed [20] at 0.01 M in each solvents,
these produced solutions with donor:acceptor molar ratios varying

Fig. 1. Absorption spectra of (A) blank solvent (acetone), (B) picric acid 0.01 M, (C)
p-toluidine 0.01 M, and (D) CTC of PTD 0.01 M and PiOH 0.01 M in acetone.

Fig. 2. Absorption spectra of picric acid (1 102 M) in chloroform with addition of

p-toluidine concentrations ranging from 0.01 M to 0.5 M are shown with increasing
concentrations bottom to top.

from 1:1 to 50:1, these concentration ratios were used to straightline diagram for determination of the formation constants of CTC
are shown in Tables 3 and 4.
To obtain the CT bands, the spectrum of solution of 0.01 M PiOH,
and 0.01 M PTD in different solvents was recorded with solvents
used as a reference, it is observed that new absorption peak appear
in the visible region. In some cases multiple peaks were obtained,
the longest wavelength peak was considered as CT peak [22]. The
change of the absorption intensity to higher for all complexes in
this study when adding the donor was detected and invested is
shown in Tables 3 and 4. These measurements were based on
the CT absorption bands exhibited by the spectra of the systems
which were above mentioned and given in Figs. 24. In all systems studied the absorption spectra are of similar nature except
for the position of absorption maxima (CT ) of the complex. The
CTC absorption spectra
were analyzed by tting to the Gaussian
function y = y0 + [A/w (/2)]exp[2(x xc )2 /w2 ], where x and
y denote wavelength and absorbance, respectively. The results of
the Gaussian analysis for all systems under study are shown in
Table 1. The wavelengths at these new absorption maxima (CT = xc )
and the corresponding transition energies (h) are summarized in
Table 2.

Fig. 3. Absorption spectra of picric acid (1 102 M) in methanol with addition of

p-toluidine concentrations ranging from 0.01 M to 0.5 M are shown with increasing
concentrations bottom to top.

N. Singh et al. / Spectrochimica Acta Part A 75 (2010) 13471353

1349

approximation:
f = 4.32 109 CT 1/2

(3)

where CT is the maximum extinction coefcient of the band and

1/2 is the half-width, i.e., the width of the band at half the maximum extinction. The observed oscillator strengths of the CT bands
are summarized in Table 2.
The extinction coefcient is related to the transition dipole
by


EN = 0.0952 CT

1/2

1/2
(4)



r
where   at CT and EN is dened as e
ex
i i
for the complexes of PiOH with PTD is given in Table 2.
Fig. 4. BH plot between [A]o /[A] and 1/[D]o for CTC of PiOH/PTD in carbon tetrachloride.

g d.

EN

3.4. Determination of resonance energy (RN )

Briegleb and Czekalla [24] theoretically derived the relation:

3.2. Determination of ionization potentials of the donor

CT =

The ionization potentials of the donor (ID ) in the charge transfer

complexes are calculated using empirical equation derived by Aloisi
and Pignataro [23]:
ID (eV) = 5.76 + 1.53 104 CT

(1)

where CT is the wavenumber in cm1 of the complex, which was

determined in different solvents, viz, carbon tetrachloride, chloroform, dichloromethane, acetone, ethanol and methanol. The values
of ionization potentials thus determined are given in Table 6.
3.3. Determination of oscillator strength (f) and transition dipole
moment (EN )
From the CT absorption spectra, one can extract oscillator
strength. The oscillator strength f is estimated using the formula:


f = 4.32 109

CT d

(2)

where CT d is the area under the curve of the extinction coefcient of the absorption band in question vs. frequency. To a rst

7.7 104
hCT /[RN ] 3.5

(5)

where CT is the molar extinction coefcient of the complex at the

maximum of the CT absorption, CT is the frequency of the CT peak
and RN is the resonance energy of the complex in the ground state,
which, obviously is a contributing factor to the stability constant
of the complex (a ground state property). The values of RN for the
complexes under study have been given in Table 2.
3.5. Determination of standard free energy changes (Go ), and
transition energy (ECT ) of the * interaction between donor
and acceptor
The standard free energy changes of complexation (Go ) were
calculated from the association constants by the following equation
derived by Martin et al. [25]:
Go = 2.303RT log KCT

(6)
(kJ mol1 ),

Go

where
is the free energy change of the complexes
R is the gas constant (8.314 J mol1 K1 ), T is the temperature in
Kelvin degrees (273 + C) and KCT is the association constant of the
complexes (l mol1 ) in different solvents at room temperature. The
values thus calculated are represented in Table 5.

Table 1
Gaussion curve analysis for the CTC in spectrum of PiOH with PTD different solvents.
System

Area of the curve (A)

PiOH + PTD (carbon tetrachloride)

PiOH + PTD (chloroform)
PiOH + PTD (dichloromethane)
PiOH + PTD (acetone)
PiOH + PTD (ethanol)
PiOH + PTD (methanol)

79.78
131.76
123.10
96.83
144.13
171.58

Width of the curve (W)

4.43
4.03
10.40
9.18
18.56
10.94

38.022
60.16
56.91
47.95
78.62
99.93

2.23
1.91
4.74
4.84
9.10
5.20

Centre of the curve (xc )

416.65
421.10
423.62
423.881
431.08
438.15

0.930
0.8977
1.98
1.905
3.66
1.85

Y0
0.01143
0.00913
0.00019
0.00541
0.0233
0.0167

0.02389
0.0147
0.0433
0.0470
0.0646
0.0341

Table 2
CT absorption maxima (CT ), transition energies (hCT ) of the PiOH complexes, experimentally determined values of ionization potentials (ID ), oscillator strength (f), dipole
moments (EN ), and resonance energies (RN ) of complexes.
System

CT (nm)

hCT (eV)

ID (eV)

f 105

EN (Debyes)

RN (eV)

PiOH + PTD (carbon tetrachloride)

PiOH + PTD (chloroform)
PiOH + PTD (dichloromethane)
PiOH + PTD (acetone)
PiOH + PTD (ethanol)
PiOH + PTD (methanol)

416.65
421.10
423.62
423.88
431.08
438.15

2.98
2.95
2.93
2.93
2.88
2.83

9.43
9.38
9.37
9.35
9.29
9.24

1.52
2.49
2.42
1.92
3.02
3.99

0.917
0.932
0.944
0.917
0.897
0.914

0.00713
0.00729
0.00742
0.00701
0.00660
0.00674

1350

N. Singh et al. / Spectrochimica Acta Part A 75 (2010) 13471353

Table 3
Data for spectrophotometric determination of stoichiometry, absorption maxima (CT ), and association constants (KCT ), molar absorptivities (CT ), of CTC of PiOH and PTD in
different polar solvents at 298 K.
System

Temperature (K)

Donor
concentration in
M

PiOH/PTD (carbon tetrachloride)

298

0.01
0.015
0.02
0.03
0.05
0.1
0.2
0.3
0.5
0.01

PiOH/PTD (chloroform)

298

PiOH/PTD (dichloromethane)

298

[A]o in M

0.01

0.015
0.02
0.03
0.05
0.1
0.2
0.3
0.5
0.01

0.01

0.015
0.02
0.03
0.05
0.1
0.2
0.3
0.5

0.01

The energy (ECT ) of the * interaction between donor (PTD),

and acceptor (PiOH), is calculated using the following equation
derived by Briegleb [26].
The calculated values of ECT are given in Table 6:
ECT =

1243.667
CT nm

(7)

where CT is the wavelength of the CT band.

3.6. Spectrophotometric study of formation constants of the
charge transfer complexes of PiOH/PTD in different solvents
Stoichiometries and the formation constants of the charge
transfer complex of p-toluidine with picric acid have been
determined in different solvents, viz, carbon tetrachloride, chloroform, dichloromethane, acetone, ethanol and methanol at room
temperature using BenesiHildebrand equation [27,28]. The spectrophotometric data were employed to calculate the values of
formation constants, KCT of the complex. The changes in the
absorbance upon addition of PTD to a solution of PiOH of xed concentration follow the BenesiHildebrand [27,28] equation in the
form:
[A]o
=
[A]

1
KCT CT

1
1
+
CT
[D]o

Absorbance at CT
(nm)
1.677
1.732
1.754
1.785
1.812
1.835
1.853
1.861
1.868
1.710
1.783
1.805
1.845
1.860
1.895
1.908
1.924
1.932
1.691
1.782
1.812
1.858
1.898
1.932
1.945
1.964
1.987

CT (nm)

KCT (l mol1 )

CT (l mol1 cm1 )

425

881

186

430

796

192

435

604

197

The BenesiHildebrand [27,28] method is an approximation that

has been used many times and gives decent results. But the extinction coefcient is really a different one between the complex and
free species that absorbs at the same wavelength. The intensity in
the visible region of the absorption bands, measured against the
solvent as reference, increases with increase in the polarity and
addition of PTD. The typical absorbance data for charge transfer
complexes of PTD with PiOH in different solvents at room temperature are reported in Tables 1, 3 and 4. In all systems very good
linear plots according to Eq. (7) [27,28] are obtained, the linear plot
of PiOH + PTD in carbon tetrachloride, chloroform, and methanol is
shown in Figs. 57. Formation constants for the complex in different polar solvents at room temperature determined from the BH
plots are summarized in Tables 3 and 4. The correlation coefcients
of all such plots were above 0.994. Plots of [A]o /[A] against 1/[D]o
were found to be linear in all systems in some example shown in

(8)

where [D]o and [A]o are the concentrations of the p-toluidine donor,
and picric acid acceptor, respectively, A is the absorbance of the
donoracceptor mixture at CT , against the solvents as reference,
KCT is the formation constant and CT is the molar extinction coefcient, which is not quite that of complex Eq. (8) [27,28] is valid
under the condition [D]o  [A]o [20,21] for 1:1 donoracceptor
complexes. The concentration of the donor (PTD) was changed
over a wide range from 0.01 M to 0.5 M while concentration of acceptor PiOH was kept xed at 0.01 M in each reaction mixture.
These produced solution with donor:acceptor molar ratio varying
from 1:1 to 50:1, experimental data are given in Tables 3 and 4.

Fig. 5. BH plot between [A]o /[A] and 1/[D]o for CTC of PiOH/PTD in chloroform.

N. Singh et al. / Spectrochimica Acta Part A 75 (2010) 13471353

1351

Table 4
Data for spectrophotometric determination of stoichiometry, absorption maxima (CT ), and association constants (KCT ), molar absorptivities (CT ) of CTC of PiOH and PTD in
different non-polar solvents at 298 K.
System

Temperature (K)

Donor concentration in M

PiOH/PTD (acetone)

298

0.01
0.015
0.02
0.03
0.05
0.1
0.2
0.3
0.5
0.01

PiOH/PTD (ethanol)

PiOH/PTD (methanol)

298

298

0.015
0.02
0.03
0.05
0.1
0.2
0.3
0.5
0.01
0.015
0.02
0.03
0.05
0.1
0.2
0.3
0.5

[A]o in M

0.01

0.01

0.01

Figs. 57 showing 1:1 charge transfer complex, i.e., the straight lines
are obtained with the slopes 1/KCT CT , these results prove the formation of the 1:1 CTC. From slope 1/KCT CT and intercept, 1/CT , KCT
and CT of the complex were calculated.

Absorbance at CT (nm)

1.558
1.635
1.698
1.740
1.787
1.829
1.840
1.852
1.870
1.454
1.542
1.595
1.650
1.710
1.744
1.762
1.779
1.795
1.440
1.540
1.610
1.677
1.740
1.788
1.812
1.842
1.871

CT (nm)

KCT (l mol1 )

CT (l mol1 cm1 )

440

502

186

445

432

178

450

360

185

The experimental results of the CT interaction between PiOH

with PTD in different solvents show the values of association constants KCT , 881 l mol1 in carbon tetrachloride, 796 l mol1 in chloroform, 604 l mol1 in dichloromethane, 502 l mol1 in acetone,
432 l mol1 in ethanol, and 360 l mol1 in methanol and the values of molar extinction coefcient CT , 186 l mol1 cm1 in carbon
tetrachloride, 192 l mol1 cm1 in chloroform, 197 l mol1 cm1 in
dichloromethane, 186 l mol1 cm1 in acetone, 178 l mol1 cm1 in
ethanol, and 185 l mol1 cm1 in methanol and spectroscopic prop-

erties were markedly affected by the variation in solvent polarity in

which measurements were carried out. In the present investigation
the KCT values increase signicantly from methanol to carbon tetrachloride with decreasing solvents polarity. Moreover, the increase
in KCT values with decreasing solvents polarity, may also be due
to the fact that, CTC should be stabilized in non-polar solvent [29].
Dissociation of the complexes into D+ A radicals have been found
to occur in the ground state [30]. It means the CTC should be strong
in non-polar solvent than polar solvent. The red shift occurred in
CTC complex caused by polarity change on going from carbon tetrachloride to methanol.
However the data given in Tables 3 and 4 show that PiOH
interacts more strongly with PTD in carbon tetrachloride than
other solvents. The experimentally determined values of oscillator strength (f), 1.52 105 in carbon tetrachloride, 2.49 105
in chloroform, and 2.42 105 in dichloromethane, 1.92 105 in

Fig. 6. BH plot between [A]o /[A] and 1/[D]o for CTC of PiOH/PTD in methanol.

Fig. 7. FT-IR spectra of (A) p-toluidine (donor), (B) picric acid (acceptor) and (C) CT
complex.

3.7. Effect of solvents on the formation of CT complexes

1352

N. Singh et al. / Spectrochimica Acta Part A 75 (2010) 13471353

Table 5
Association constant (KCT ), correlation coefcients (r) and standard free energy
changes (Go ) of PiOH/PTD complexes obtained from BenesiHildebrand plots.
System
PiOH/PTD (carbon tetrachloride)
PiOH/PTD (chloroform)
PiOH/PTD (dichloromethane)
PiOH/PTD (acetone)
PiOH/PTD (ethanol)
PiOH/PTD (methanol)

KCT (l mol1 )
881
796
604
502
432
360

Go (298 K)
(kJ mol1 )

16.775
16.546
15.862
15.405
15.006
14.549

0.996
0.995
0.994
0.997
0.998
0.998

acetone, 3.02 105 in ethanol and 3.99 105 in methanol and

the values of transition dipole moment (EN ), 0.917 Debyes in carbon tetrachloride, 0.932 Debyes in chloroform, and 0.944 Debyes in
dichloromethane, 0.917 Debyes in acetone, 0.897 Debyes in ethanol
and 0.914 Debyes in methanol, values of resonance energy (RN ),
0.00713 in carbon tetrachloride, 0.00729 in chloroform, 0.00742
in dichloromethane, 0.00701 in acetone, 0.0066 in ethanol, and
0.00674 methanol, given in Table 2, indicate that complex should
be stable in non-polar solvent (carbon tetrachloride) than other
solvents. The very low values of f indicate that CT complex studied
here has almost neutral character in their ground state.
The parameters thus obtained are represented in Table 5
and these values show that complexation is thermodynamically favored. The free energy change of the complexation also
reveals that the CTC formation between used donor (PTD) and
acceptor (PiOH) is of exothermic in nature. The values of Go ,
16.775 kJ mol1 in carbon tetrachloride, 16.546 kJ mol1 in chloroform, 15.862 kJ mol1 in dichloromethane, 15.405 kJ mol1
in acetone, 15.006 kJ mol1 in ethanol, and 14.549 kJ mol1 in
methanol, given in Table 5, generally become more negative as the
association constants for molecular complex increase. As the bond
between the components becomes stronger and thus the components are subjected to more physical strain or loss of freedom, the
values of Go more negative.
The ionization potentials ID (eV) of the donor can be calculated using the experimentally determined CT of the CTC from Eq.
(1) [23]. The calculated values of ID 9.35 eV in carbon tetrachloride, 9.30 eV in chloroform, 9.26 eV in dichloromethane, 9.23 eV in
acetone, 9.19 eV in ethanol, and 9.15 eV in methanol of PiOH/PTD
system are shown in Table 6. The approximate constancy of ID values, indicates that the ionization potential shows a negligibly small
effect on KCT values.
3.8. Comparative study of FT-IR spectra of CT complex and
reactants
FT-IR spectra of picric acid, p-toluidine and the reaction
product obtained from solid state reaction between acceptor
and donor were recorded with the help of FT-IR spectrometer
INTERSPEC2020 (Spectra Lab, U.K.) measured in KBr pellets. FTIR spectra of the free acceptor and donor as well as the formed CT
complex are shown in Fig. 7 and their band assignments reported in
Table 7. However the appearance of a group of FT-IR spectral bands
Table 6
The CTC transition energies (ECT ), CTC absorption maxima (CT ), and ionization
potential (ID ) of donor in different solvents.
System

ECT (eV)

CT (nm)

ID (eV)

PiOH/PTD (carbon tetrachloride)

PiOH/PTD (chloroform)
PiOH/PTD (dichloromethane)
PiOH/PTD (acetone)
PiOH/PTD (ethanol)
PiOH/PTD (methanol)

2.92
2.89
2.85
2.82
2.79
2.76

425
430
435
440
445
450

9.35
9.30
9.26
9.23
9.19
9.15

Table 7
Characteristic infrared frequencies (cm1 ) and tentative assignments for PiOH, PTD
and their complex.
PiOH

PTD

Complex

Assignments

3108 s, br

3410 sharp
3338 br
3211 br
3013 br
2909 br
2855 w
2357 sharp

3235 sh
3083 sharp

2890 br
2589 br
2362 w

(OH), H bonded
(NH)

1618 vs
1515 vs

1628 ms

1561 ms

1340 sh

1509 ms
1437 vs

1370 br

1267 br

(CC), s NO2
(CN)
(CO)

1163 ms

(CH) in plane bending

1081 ms
936 sharp
812 sharp

rock, +NH2

2875 w
1630 vs
1606 ms
1529 br

1437 ms

1341 vs
1275 vs
1154 ms
1083 ms
916 ms
830 w
779 sharp
734 ms
703 ms
663 w
546 w
521 w
419 sharp

1267 vs
1174 w
1117 w
1040 br

812 sharp
735 vs
678 vs

507 ms
480 ms

404 sharp

(CH)
as (CH)
s (NO2 )
S (C N)
(C C)
def (NH), +NH2 ring
breathing bands
CH deformation

CH2 rock skeletal vibrations

745 vs

699 vs
541 sh
482 sharp
409 ms

CH out of plane bending

(ONO), PiOH
CNC deformation

s, strong; w, weak; m, medium; sh, shoulder; v, very; vs, very strong; br, broad; ,
stretching; s , symmetrical stretching; as , asymmetrical stretching.

in the spectra of CT complex support the conclusion that a deformation of the electronic environment of p-toluidine has occurred
by accepting a proton from PiOH. The shift of the FT-IR bands of
the acceptor to lower wavenumbers and those of the donor part to
higher values reects a donor to acceptor charge transfer of *
interaction and DHOMO ALUMO transition [31].
The FT-IR spectrum of the complex of PiOH and PTD in Fig. 7
shows the presence of characteristic absorption bands due to the
varied forced constants in the donor and the acceptor species on
account of the prevalent charge transfer mechanism. This makes
the crystals of this type more ionic than other organic crystals. In the
FT-IR spectra of the complex the OH and NH stretching vibrations
are observed at 3235.17 cm1 and 3085.39 cm1 , respectively. The
band at 2925.27 cm1 is due to the aromatic CH stretching vibration. The NH2 deformation mode is observed by the absorption at
1628.79 cm1 . This band overlaps with the aromatic C C stretching
vibrations. The asymmetric and symmetric stretching vibrations of
the NO2 group are observed at 1561.64 cm1 and 1370.53 cm1 ,
respectively. Normally the asymmetric stretching vibration of the
NO2 group is sensitive to polar inuences and the electronic states
of the species. Therefore, it has been realized that the shift to lower
frequency of asym (NO2 ) vibration (1561.64 cm1 ) in the spectrum
of the complex compared with free picric acid (1606 cm1 ) is due
to the increased electron density on the picric acid moiety owing to
the charge transfer interaction in the complex [32]. The absorption
at 1628.79 cm1 , 1561.64 cm1 , 1509.99 cm1 and 1437.68 cm1
is due to the aromatic C C absorption stretching vibrations. The
absorption at 1267.22 cm1 is due to the CN stretching vibration. The CO stretching vibration is observed as a band of medium
intensity at 1163.92 cm1 . The CH in plane bending vibration is
observed at 1081.28 cm1 and the CH out of plane bending is
evidenced by the presence of a band at 789.95 cm1 . The CNO2

N. Singh et al. / Spectrochimica Acta Part A 75 (2010) 13471353

stretching is observed at 936.65 cm1 . The NO2 wagging vibrations are observed at 734.26 cm1 and 789.95 cm1 . The band at
699.05 cm1 is due to the ring bending vibration. The assignments
of various absorption frequencies of the compound are given in
Table 7. In the spectra of CT complex of p-toluidine and picric acid,
PTD almost completely consumed evidence of H bonding and OH
intensity decreased and position of the peak also shifted.
4. Conclusions
The UVvis spectrophotometric method for the study of CTC
of picric acid with p-toluidine reveals that it forms 1:1 (A:D)
complex in all solvents, viz, carbon tetrachloride, chloroform,
dichloromethane, acetone, ethanol and methanol. In all systems the
stoichiometry is unaltered by changing the solvent. The association
constants, KCT and molar extinction coefcients, CT , of all systems
were evaluated by the BenesiHildebrand method. The values of
association constant of the CTC decrease with increasing solvent
polarity, due to the destabilization of CTC in polar solvents and
then the dissociation of the complex into D+ A . The interaction
between the donor and acceptor was found to be * transitions
by the formation of radical ion pairs. The spectroscopic and thermodynamic parameters of the complexes were found to be solvent
dependent. The values of oscillator strengths (f) transition dipole
moments (EN ) resonance energies (RN ) and standard free energies
(Go ) have been estimated for the PiOH/PTD systems in different
solvents. The results show that the investigated complex is stable,
exothermic and spontaneous. From the trends in the CT absorption
bands, the ionization potentials of the donor molecules have been
estimated. The FT-IR spectrum shows that the complex formed
between donor and acceptor by transferring a proton from acceptor
(PiOH) to donor (PTD).
Acknowledgements
Authors thank Dr. Arunima Lal chairperson of Chemistry Department of Aligarh Muslim University, India, for providing the facilities
of instruments of FT-IR spectrometer and UVvisible spectropho-

1353

tometer. Financial assistance by the UGC, New Delhi, extended

through the scholarship, is also gratefully acknowledged. The
authors also thank the learned referee for making valuable comments.
References
[1] D.K. Roy, A. Saha, A.K. Mukherjee, Spectrochim. Acta A 61 (2005) 2017.
[2] R.S. Mulliken, J. Am. Chem. Soc. 72 (1950) 600.
[3] R.S. Mulliken, W.B. Pearson, Molecular Complexes, Wiley Publishers, New York,
1969.
[4] R. Foster, Charge Transfer Complexes, Academic Press, London, 1969.
[5] M.M.A. Hamed, M.I. Abdel-Hamid, M.R. Mahmoud, Monatsh. Chem. 129 (1998)
121.
[6] A. Dozal, H. Keyzer, H.K. Kim, W.W. Way, Int. J. Antimicrob. Agents 14 (2000)
261.
[7] A. Eychmuller, A.L. Rogach, Pure Appl. Chem. 72 (2000) 179.
[8] R. Dabestani, K.J. Reszka, M.E. Sigman, J. Photochem. Photobiol. A 117 (1998)
223.
[9] R. Jakubiak, Z. Bao, L. Rothberg, Synth. Met. 114 (2000) 61.
[10] K. Brueggermann, R.S. Czernuszewicz, J.K. Kochi, J. Phys. Chem. 96 (1992) 4405.
[11] M. Krishnamurthy, K. Surendrababu, U. Muralikrishna, Indian J. Chem. 27A
(1988) 669.
[12] S.M. Andrade, S.M.B. Costa, R. Pansu, J. Colloid Interface Sci. 226 (2000) 260.
[13] A. Bhal, B.S. Bhal, Text Book of Advanced Organic Chemistry, 1st ed., 1977, p.
1069.
[14] N. Singh, A. Ahmad, Canadian J. Anal. Sci. Spectrom. 54 (1) (2009) 292.
[15] G. Saito, Y. Matsunuga, Bull. Chem. Soc. Jpn. 45 (1972) 963.
[16] G. Saito, Y. Matsunuga, Bull. Chem. Soc. Jpn. 44 (1971) 3328.
[17] G. Saito, Y. Matsunuga, Bull. Chem. Soc. Jpn. 46 (1973) 714.
[18] N. Singh, I.M. Khan, A. Ahmad, Asian J. Chem. Res. 2 (2009) 476.
[19] D.A. Skoog, Principle of International Analysis, 3rd ed., Sannder College Publishing, New York, 1985 (chapter 7).
[20] M. Hasani, R. Alireza, Spectrochim. Acta A 65 (2006) 10931097.
[21] S. Bhattacharya, K. Gosh, C. Subrata, B. Momas, Spectrochim. Acta A 65 (2006)
659.
[22] R.K. Gupta, R.A. Sig, J. Appl. Sci. 5 (1) (2005) 28.
[23] G. Aloisi, S. Pignataro, J. Chem. Soc., Faraday Trans. 69 (1972) 534.
[24] G. Briegleb, J. Czekalla, Z. Physikchem. (Frankfurt) 24 (1960) 237.
[25] A.N. Martin, J. Swarbrick, A. Cammarata, in: Lee, Febiger (Eds.), Physical Pharmacy, 3rd ed., 1969, p. 344, Philadelphia, PA.
[26] G. Briegleb, Z. Angew. Chem. 76 (1964) 326.
[27] H.A. Benesi, J.H. Hildebrand, J. Am. Chem. Soc. 71 (1949) 2703.
[28] P. Douglas, G. Waechter, A. Mills, Photochem. Photobiol. 52 (1990) 473.
[29] M.E. El-Zaria, Spectrochim. Acta A 69 (2008) 216.
[30] R. Foster, T.J. Thomson, Trans. Faraday Soc. 58 (1962) 860.
[31] R.D. Kross, V.A. Fassel, J. Am. Chem. Soc. 79 (1957) 38.
[32] S.M. Teleb, A.S. Gaballa, Spectrochim. Acta A 62 (2005) 140.