LIST OF TABLES

TABLE PAGE
TITLE
NO. NO.
THE CALCULATED ELECTRONIC TRANSITION OF 2,3
2.1 (DICHLORO-BENZYLIDINE)-2- TRIFLUOROMETHYL- 28
PHENYL)-AMINE
 LIST OF FIGURES
FIGURE PAGE
TITLE
NO. NO.
1.1 UV-VISIBLE TRANSITIONS 7

SCHEMATIC DIAGRAM OF UV-VIS

1.2 10
SPECTROPHOTOMETER
THE OPTIMIZED MOLECULAR STRUCTURE OF THE
THEORETICAL ELECTRONIC TRANSITION OF 2,3
2.1 23
(DICHLORO- BENZYLIDINE)-2-TRIFLUOROMETHYL-
PHENYL)-AMINE

2.2 THE ENERGY LEVEL DIAGREM 24

2.3 ABSORPTION AND EMISSION PATHWAYS 24

2.4 ABSORPTION INTENSITY VS WAVELENGTH 25

UV-VIS ABSORPTION SHIFT WITH CHANGE IN

2.5
POLARITY OF SOLVENTS
THE CALCULATED UV-VISIBLE SPECTRA FOR 2,3
2.6 (DICHLORO-BENZYLIDINE)-2- TRIFLUOROMETHYL- 27
PHENYL)-AMINE IN DIFFERENT SOLVENTS
 CHAPTER-1

UV-VISIBLE SPECTROSCOPY THEORY

AND INSTRUMENTATION

ABSTRACT

The basic principle of UV-Vis spectroscopy is explained. The Working of

UV-Vis spectroscopy and its types of sources, monochromator, cuvettes and

detector are elaborated. Beer-Lambert's law is also outlined along with this.

1
 CHAPTER-1
UV-VISIBLE SPECTROSCOPY THEORY
AND INSTRUMENTATION

1.1 INTRODUCTION

Ultra-Violet Visible (UV-Vis) spectroscopy is type of absorption

spectroscopy in which light of UV-Vis region is absorbed by the molecule.

Absorption of the UV-Vis radiations results in the excitation of the electrons

from the ground state to higher energy state. The energy of the UV-Vis

radiation that is absorbed is equal to the energy difference between the ground

state and higher energy state. Generally the most favoured transition is from

the highest occupied molecular orbital (HOMO) to lowest unoccupied

molecular orbital (LUMO). For most of the molecules, the lowest energy

occupied molecular orbitals are "s orbital", which correspond to sigma bands.

The "p orbitals" are at somewhat higher energy levels, the (n) orbitals (non-

bonding orbitals) with unshared paired of electrons lie at higher energy levels.

The unoccupied or anti-bonding orbitals (pie* and sigma*) are the highest

energy occupied orbitals.

In all the compounds (other than alkanes), the electrons undergo

various transitions. Some of the important transitions with increasing energies

are non-bonding to pie, non-bonding to sigma*, pie to pie*, sigma to pie* and

sigma to sigma*.

2
1.2 PRINCIPLE

UV-V is spectroscopy obeys the Beer-Lamberts law, which states that

when a beam of monochromatic light is passed through a solution of an

absorbing substance, the rate of decrease of intensity of radiation with

thickness of the absorbing solution is proportional to the incident radiation as

well as the concentration of the solution. The expression of Beer- Lambert's

law is:

A=log(Io/I)= εcl

Where,

A = absorbance

Io = intensity of light incident up on sample cell

I = intensity of light leaving sample cell

C = molar concentration of solute

L = length of the sample

ε = molar absorptivity

From the Beer-Lambert's law it is clear that greater the number of

molecules capable of absorbing light of a given wavelength, the greater the

extent of light absorption. This is the basic principle of UV-Vis spectroscopy.

3
1.3 ABSORPTION AND INTENSITY SHIFTS IN THE UV-V is
SPECTROSCOPY

There are four types of shifts observed in the UV-Vis spectroscopy:

a) Bathochromic effect- This type of shift is also known as "red shift".

Bathochromic shift is an effect by virtue of which the absorption maximum

is shifted towards the longer wavelength due to the presence of an

auxochrome or change in solvents. The non-bonding to pie transition of

carbonyl compounds observes bathochromic or red shift.

b) Hypsochromic effect. This effect is also known as "blue shift".

Hypsochromic shift is an effect by virtue of which absorption maximum is

shifted towards the shorter wavelength. Generally it is caused due to the

removal of conjugation or by changing the polarity of the solvents.

c) Hyperchromic effect- Hyperchromic shift is an effect by virtue of which

absorption maximum increases. The introduction of an auxochrome in the

compound generally results in the hyperchromic effect

d) Hypochromic effect- Hypochromic effect is defined as the effect by

virtue of intensity of absorption maximum decreases Hypochromic effect

occurs due to the distortion of the geometry of the molecule with an

introduction of new group.

4
1.4 BEER-LAMBERT'S LAW

The Beer-Lambert's law states that the absorbance of a solution is

directly proportional to the concentration of the absorbing species in the

solution and the path length. Thus, for a fixed path length, UV-Vis

spectroscopy can be used to determine the concentration of the absorber in a

solution. It is necessary to know how quickly the absorbance changes with

concentration. This can be taken from references (tables of molar extinction

coefficients), or more accurately, determined from calibration curve.

A UV-Vis spectrophotometer may be used as a detector for high

performance liquid chromatography (HPLC). The presence of an analyte

gives a response assumed to be proportional to the concentration. For

accurate results, the instrument's response to the analyte in the unknown

should be compared with the response to a standard; this is very similar to

the use of calibration curves. The response (e.g., peak height) for a particular

concentration is known as the response factor.

The method is most often used in a quantitative way to determine

Concentrations of an absorbing species in solution, using the Beer-Lambert

law:

A=log(Io/I)= εcl

5
 where, A is the measured absorbance (in Absorbance Units (AU)), is

the intensity of the incident light at a given wavelength, I is the transmitted

intensity, L is the path length through the sample, and the concentration of

the absorbing species, For each species and wavelength, is a constant known

as the "molar absorptivity" or "extinction coefficient". This constant is a

fundamental molecular property in a given solvent, at a particular

temperature and pressure, and has units of mole-1 em-1. The absorbance and

extinction are sometimes defined in terms of the natural logarithm instead of

the base-10 logarithm.

The Beer-Lambert's Law is useful for characterizing many

compounds but does not hold as a universal relationship for the

concentration and absorption of all substances. A second order polynomial

relationship between absorption and concentration is sometimes encountered

for very large, complex molecules such as organic dyes (Xylenol Orange or

Neutral Red, for example).

UV-Vis spectroscopy is also used in the semiconductor industry to

measure the thickness and optical properties of thin films on a wafer. UV-Vis

spectrometers are used to measure the reflectance of light, and can be

analyzed via the Forouhi-Bloomer dispersion equations to determine the

Index of Refraction (n) and the Extinction Coefficient (k) of a given film

across the measured spectral range.

6
1.5 TYPES OF ELECTRONIC TRANSITIONS

According to the molecular orbital theory, when a molecule is excited

by the absorption of energy (UV or Visible light), its electrons are promoted

from a bonding to an anti-bonding orbital.

I. The anti-bonding orbital which is associated with excitation of σ electron

is called σ anti-bonding orbital. So σ to σ* transition takes place when

σ electron is promoted to anti-bonding (σ*) orbital. It is represented as

σ → σ* transition.

II. When a non-bonding electron (n) gets promoted to an anti-bonding sigma

orbital (σ*), then represents n → σ* transition.

III. Similarly π → π* transition represents the promotion of π electron to an

anti-bonding orbital i.e, π* orbital, given in Fig.1.1.

Fig. 1.1 UV-Visible Transition

7
Similarly, when an n-electron (non-bonding) is promoted to anti bonding π*

orbital, it represents n→ π* transition. The energy required for various

transitions obey the following order.

σ → σ* > n → σ* > π → π* > n → π*

1.6 ULTRAVIOLET-VISIBLE SPECTROPHOTOMETER

The instrument used in UV-Vis spectroscopy is called a UV-Vis

spectrophotometer. It measures the intensity of light passing through a

sample (I), and compares it to the intensity of light before it passes through

the sample (I0). The ratio is called the transmittance, and is usually

expressed as a percentage (%T). The absorbance, A is based on the

transmittance:

T%
A = - log ( )
100%

The UV-Vis spectrophotometer can also be configured to measure

reflectance. In this case, the spectrophotometer measures the intensity of

light reflected from a sample (I), and compares it to intensity of light

reflected from a reference material (I0) (such as a white tile). The ratio I/ I0

is called the "reflectance", and is usually expressed as percentage (%R). The

basic parts of spectrophotometer are a light source, a holder for the sample,

diffraction grating in a monochromator or a prism to separate the different

wavelengths of light, and a detector.

The detector is typically a photomultiplier tube, a photodiode, a

photodiode array or a charge-coupled device (CCD). Single photodiode

8
detectors and photomultiplier tubes are used with scanning monochromators,

which filter the light so that only light of a single wavelength reaches the

detector at one time.

Simplified schematic diagram of a double beam UV-Vis

spectrophotometer is shown in Fig. 1.2. A spectrophotometer can be either

single beam or double beam. In a single beam instrument (such as the

Spectronic 20), all of the light passes through the sample cell. This was the

earliest design and is still in common use in both teaching and industrial

labs. In a double-beam instrument, the light is split into two beams before it

reaches the sample.

Samples are typically placed in a transparent cell known as cuvette.

Cuvettes are typically rectangular in shape, commonly with an internal

width of 1 cm. (This width becomes the path length, in the Beer-Lambert's

law). Test tubes can also be used as cuvettes in some instruments. The type

of sample container used must allow radiation to pass over the spectral

region of interest. The most widely applicable cuvettes are made of high

quality fused silica or quartz glass because these are transparent throughout

the UV, visible and near infrared regions. Glass and plastic cuvettes are also

common, although class and most plastics absorb in the UV, which limits

their usefulness to visible wavelengths.

Specialized instruments have also been made. These include attaching

spectrophotometers to telescopes to measure the spectra of astronomical

9
features. UV-Visible microspectrometers consist of a UV-Visible microscope

integrated with a UV-Visible spectrometer. A complete spectrum of the

absorption at all wavelengths of interest can often be produced directly by a

more sophisticated spectrophotometer. In simpler instruments the absorption

is determined one wavelength at time and then compiled into a spectrum by

the operator. By removing the concentration dependence, the extinction

coefficient (ε) can be determined as a function of wavelength.

Fig. 1.2 Schematic diagram of UV-Vis spectrophotometer

1.7 INSTRUMENTATION

The main components of UV-Vis spectrophotometer are shown in

Fig. 1.2. It is made up of the following components:

10
 1. Sources (UV and visible)

2. Wavelength selector (monochromator)

3. Sample containers

4. Detector

5. Signal processor and readout

Each of these components will be considered in turn

1.7.1 Sources of UV radiation

It is important that the power of the radiation source does not change

abruptly over its wavelength range. The electrical excitation of deuterium or

hydrogen at low pressure produces a continuous Ultra Violet (UV) spectrum.

The mechanism for this involves formation of an excited molecular species,

which breaks up to give two atomic species and an UV photon. Both

deuterium and hydrogen lamps emit radiation in the range 160 375 nm.

Quartz windows must be used in these lamps, and quartz cuvettes must be

used, because glass absorbs radiation of wavelengths less than 350 nm.

1.7.2 Wavelength Selector (Monochromator)

All monochromators contain the following component parts:

 An entrance slit

 A collimating lens

 A dispersing device (usually a prism or a grating)

11
  A focusing lens

 An exit slit

Polychromatic radiation (radiation of more than one wavelength)

enters the monochromator through the entrance slit. The beam is collimated.

and then strikes the dispersing element at an angle. The beam is split into its

component wavelengths by the grating or prism. By moving the dispersing

element or the exit slit, radiation of only particular wavelength leaves the

monochromator through the exit slit.

1.7.3 Sample Container (Cuvettes)

The containers for the sample and reference solution must be

transparent to the radiation which will pass through them Quartz or fused

silica cuvettes are required for spectroscopy in the UV region. These cells

are also transparent in the visible region. Silicate glasses can be used for the

manufacture of cuvettes for use between 350 and 2000 nm.

1.8 APPLICATIONS

UV-V is spectroscopy is routinely used in analytic chemistry for the

quantitative determination of different analysis, such as transition metal

icons, highly conjugated organic compounds, and biological macromolecules.

Spectroscopic analysis is commonly carried out in solutions but gases may

also be studied. Generally the following are often come across in UV-Vis

spectroscopy. Solutions of transition metal ions can be coloured (ie, absorb

12
visible light) because the electrons within the metal atoms can be excited

from one electronic state to another. The colour of metal ion solutions is

strongly affected by the presence of other species, such as certain anions or

ligands. For instance, the colour of a dilute solution of copper sulphate is very

light blue; adding ammonia intensity the colour and changes the wavelength

of maximum absorption.

13
 CHAPTER-2

A STUDY OF THE SOLVENT EFFECTS ON 2,3

(DICHLORO-BENZYLIDINE)-(2-TRIFLUOROMETHYL-
PHENYL)-AMINE BY EMPLOYING UV-VISBLE
SPECTROSCOPY

ABSTRACT

The theoretical UV-Vis analysis was done on the molecule 2,3

(dichloro-benzylidine)-(2-trifluoromethyl-phenyl)-amine (here after

abbreviated as 2,3DB2T). To obtain the electronic transition details of

2,3DB2T, theoretical absorption maxima values were calculated by

considering both gaseous and solvent phase using DFT/6-311++G(d,p) basis

set.

14
 CHAPTER-2
A STUDY OF THE SOLVENT EFFECTS ON 2, 3
(DICHLORO-BENZYLIDINE)-(2-TRIFLUOROMETHYL-
PHENYL)-AMINE BY EMPLOYING UV-VISBLE
SPECTROSCOPY
2.1 INTRODUCTION

Ultraviolet-visible (UV-Vis) absorption and emission in particular

circumstances, such as in solution, has been extremely important due to its

significant potential applications for the design of new dyes, light emitting

diodes and phototrophic materials, in the fields of photodynamic therapy and

molecular imaging, herein solvent effects have attracted great attention for a

long time, As a major part, solvatochromism, the shift of transition energies

by a solvent, is an important consideration in such research. Since

solvatochromism is commonly used in many fields of chemical and

biological research to study bulk and local polarity in macrosystems

(membranes, etc.) or even conformation and finding of proteins. It is known

the accurate theoretical description of solvatochromism requires a proper

account of non equilibrium state is a great challenge in theory.

In the past some researchers performed reversible electric work

integration along the path linking initial equilibrium state and mediated non

equilibrium state, to derive the non equilibrium salvation energy. Recently it

has been achieved to find a rational formula of electrostatic solvation energy

15
of nonequilibrium polarization by introducing the constrained equilibrium

approach in continuum model. This formula has been successfully applied to

evaluate reorganization energy of electron transfer reactions

solvatochromism of absorption spectrum and vertical ionization energy of

hydrated electron.

The titled molecule is a schiff base derivative which is the

combination of benzene ring with fluorine atoms. Schiff bases known as

azomethinesor imines are also a crucial class of organic compounds because

of their applications in many fields including biological, inorganic and

physical applications. Titled molecule is structurally similar to

Benzimidazoles which are the members of heterocyclic compounds consist

of the combination of benzene ring and the imidazole ring having

heteroatom. The benzimidazoles also have special significance due to their

molecular arrangement with heteroaromatic and homoaromatic parts. The

different substitutions on rings and their derivatives provide additional

features such as functionality and enable easy modification of the electronic

characteristics. Benzimidazole and its derivatives have an important

functions with many pharmacological and biological, activities such as anti-

viral, anti-diabetic and anti-tubercular, anti-cancer, anti-microbial, anti-

oxcidant, anti-hepatitis-C- virus, anti-histaminic and anti-allergic.

16
2.2 REVIEW OF LITERATURE

A systematic approach has been adopted for structural analysis of, 2-

[(acetyloxy) methyl]-4-(2-amino-9H-purin-9-yl)butyl acetate by FT-IR, FT-

Raman, UV and NMR spectroscopic techniques. The optimized molecular

geometry, the vibrational assignments, the IR and the Raman scattering

activities were calculated by using density functional theory (DFT) B3LYP

method with 6-311++G(d,p) basis set. The calculated HOMO and LUMO

energies show the charge transfer within the molecule. Stability of the

molecule arising from hyperconjugative interactions, charge delocalization

have been analyzed using natural bond orbital analysis (NBO). Molecular

electrostatic potential (MEP) and Fukui functions calculation were also

performed. The thermodynamic properties (heat capacity, entropy, and

enthalpy) of the title compound at different temperatures have been

calculated. Antiviral activity was examined based on molecular docking

analysis and it has been identified that the title compound can act as a good

inhibitor against Herpes Simplex Virus. [Fathima Rizwana, B.et al.,2017].

The molecular structure of 3-[2-(4-chloro-phenyl)-2-oxo-ethyl]-5-(

agent 2,4-dichloro-thiazole-5-yl- methylenyl)thiazolidine-2,4-dione as an

antifungal against Candida albicans in the ground state was optimized by

density functional using Becke's three-parameter hybrid method with the

Lee, Yang, and Parr correlation functional method with 3-21G(d,p) basis

17
sets. The calculated geometric parameters were compared with obtained

experimental result. [Llkay yildiz,et al., 2016].

N-(2,4-dichlorobenzylidene)-3-methylbenzenamine (L6) was

synthesized as single crystal and characterized by FT-IR, Raman, 1H NMR,

13C NMR and UV-VIS spectroscopy. The thermal stability of the title

compound was also studied by thermogravimetric analysis (TGA) and

differential thermal analysis (DTA) analyses. The optimized geometric

parameters, conformational analysis, normal mode frequencies and

corresponding vibrational assignments of L6 was theoretically examined by

means of density functional theory (DFT) method using the Becke-3-Lee-

Yang-Parr (B3LYP) exchange- correlation functional and the 6-311G++(d, p)

basis sets. The DFT based nuclear magnetic resonance (NMR) calculations

were also performed to be used for assigning the 1H and 13C NMR chemical

shifts of L6. Reliable vibrational assignments were investigated by the

potential energy distribution analysis and the highest occupied and the lowest

unoccupied molecular orbitals (HOMO and LUMO) of L6 was predicted. A

good consistency were obtained between the theoretically predicted structural

parameters, vibrational frequencies and those obtained

experimentally.[Turkay Aytekin,et al., 2016].

18
 Synthesis and characterization (IR, IH NMR, 13C NMR, molar

conductance, mass spectra, UV-Visible, thermal analysis, EPR, and Powder

XRD) of chemotherapeutic sulfa- drug, Schiff base namely 4- ((3, 5-

dichloro-2-hydroxy benzylidene) amino) benzene sulphonamide and its

dipositive complexes. The bidentate coordination of ligand through phenolic

oxygen and imine nitrogen (-CH-N-) was confirmed using spectral analysis

data. Also, number of water molecules in coordination sphere of complexes

was predicted with the help of thermograms. EPR spectra was used to

propose the geometry of complexes. The molecular structure of ligand was

optimized using DFT calculations. In-vitro antimicrobial activity of

compounds L, L-Cd, L-Cu, L-Ni, and L-Hg was evolved with bacterial and

fungal strains, In-vitro anticancer activity toward HeLa (human cervical

cancer cell) was carried out for compounds L, L-Cd, L-Cu, L-Ni and L-Mn.

Our results indicate, particularly L-Cd as a potent inhibitory agent, against

HeLa cell line.[Anandakumaran, J, et al., 2016].

A new series of Schiff bases were synthesized for the first time by the

condensation of substituted aldehyde and 3,5-dichloropyridin-4-amine in

ethanol (1:1). The structure of Schiff bases were experimentally

characterized by using IR and IH NMR spectroscopic methods. The

structural and vibrational properties of the studied molecules were

investigated theoretically by performing density functional theory (DFT) to

19
access reliable results to the experimental values and the calculation results

showed good agreement with the experimental ones. The calculated HOMO

and LUMO energies showed that charge transfer occurs within the molecule.

Atomic charges and molecular electrostatic potential (MEP) have been

calculated at the B3LYP method and standard 6-31G(d,p) basis set starting

from optimized geometry.[Prabhakaran, N. R, et al., 2016]

The synthesis of 2,6-bis(hydroxyphenyl)methyl)cyclohexanone 1 is

described. The molecular structure of the title compound 1 was confirmed

by NMR, FT-IR, MS, CHN microanalysis, and X-ray crystallography. The

molecular structure was also investigated by a set of computational studies

and found to be in good agreement with the experimental data obtained from

the various spectrophotometric techniques. The antimicrobial activity and

molecular docking of the synthesized compound was investigated. [Assem

barakat, et al,. 2015].

Quantum chemical calculation was correlated with geometrical structure and

total energy of fluoxetine and its five derivatives. Theoretical vibrational fre-

quencies and geometric parameters (bond lengths and bond angles) have

been calculated using ab initio (HF), density functional theory (B3LYP),

semi-empirical (AMI, PM3) methods with different basis sets to design the

fluoxetine drugs and its derivatives by a Gaussian 09 W program.

Theoretical optimized geometric parameters and vibrational frequencies of

20
fluoxetine have been compared with the corresponding five derivatives data.

The highest occupied molecular orbital (HOMO) and lowest unoccupied

molecular orbit- al (LUMO) energies have been determined. The theoretical

study includes the calculation of the thermodynamic properties of the drugs

and its derivatives like zero-point energy, enthalpy, entropy, ionization

energy, electron affinity to make a correlation between the gained results.

The results of the four me- thods were not very clear, but an correlation

between the dipole moment (potential character), static distribution (an

active site character) and HOMO-LUMO energies (energy for electron

transfer) shows that the patent 1.5 was important derivatives as a

recommended drug relative to fluoxetine drug.[Qabas M.Abdul Al-

Makhzumi,et al,.2018].

The Vibrational and electronic properties of phenyl substituted

compounds 1-(2-methoxyphenyl)piperazine and 1-(2-chlorophenyl)

piperazine have been investigated by FT-IR, FT-Raman, NMR and UV-Vis

spectral measurements. Density functional theory (DFT) method, using

B3LYP functional, with 6-311++G (d,p) basis set, has been performed for

assigning vibrational frequencies of the title compounds, which also helps to

derive useful information about the structure of the chosen compounds. A

detailed interpretation of the Infrared and Raman spectra of the two

molecules were reported based on potential energy distribution (PED). 13C

21
and 1H NMR chemical shifts of the molecules were calculated using the

gauge independent atomic orbital (GIAO) method. These studies

satisfactorily agree the experimental data. Charge density distribution and

site of chemical reactivity of the molecule have been studied by mapping

electron density isosurface with molecular electrostatic potential (MEP).

Stability of the molecules arising from hyperconjugative interactions, charge

delocalization have been analyzed using natural bond orbital (NBO)

analysis. The compounds have similar HOMO (Highest Occupied Molecular

Orbitals) LUMO (Lowest Unoccupied Molecular Orbitals) gap due to

similarity in their structures. The compounds show (*) transitions in

the UV-Visible range.[Prabavath, N. et al., 2015].

2.3 COMPUTATIONAL DETAILS

The molecular structure of the title compound in the ground state is

computed using DFT/6-311++G (d, p) basis set. The theoretical UV-Vis

absorption were calculated in the gas phase and in three solvents CHCL,

DMSO, & Methanol using TD-DFT/6-311++G (d, p) basis set. The entire

calculations were performed on Pentium IV/3.02 GHz personal computer

using Gaussian 03 program, involving gradient geometry optimization

[Schlegel, J. 1982].

22
2.4 RESULTS AND DISCUSSION

UV-Vis spectrum is a graphical representation of wavelength (λ)

versus absorbance. UV radiation stimulates molecular vibrations and

electronic transitions. The UV-Vis spectroscopy ranges covering from 200-

800 nm. The absorption spectroscopy provides information about the

presence of unsaturated functional groups. The absorption spectroscopy

arises a transition from a lower level to a higher level with transfer of energy

from the radiation field to an absorber, atom, molecule or solid etc. The

molecular structure of 2,3DB2T is illustrated in Fig. 2.1. The absorption and

emission energy level diagram is shown in Fig. 2.2. In this Project Work 2,3

(dichloro-benzylidine)-(2-trifluoromethyl-phenyl)-amine is selected as a

representative compound to carry out the UV-Visible studies using three

different solvent system and the observed results are suitably interpreted

as follows.

Fig.2.1 The optimized molecular structure of 2,3-dichloro-

benzylidine- (2-trifluromethyl-phenyl)-amine

23
ABSORPTION SPECTROSCOPY EMISSION SPECTROSCOPY

Fig. 2.2 The Energy Level Diagram

The atom or a molecule goes to the excited states (S1, S2, S3 etc..)

due to the absorption of energy and the extent of absorption is appeared in the

form of UV spectrum. The absorption and emission pathways are shown in

Fig. 2.3.

Fig. 2.3 Absorption and emission pathways

24
The possibility of shift of absorption maxima ( λ max) is shown in Fig. 2.4.

Fig. 2.4 Absorption intensity Vs Wavelength

2.4.1 Solvent Effects in a, ẞ-unsaturated Compounds

The position of π→ π* and n→ π * transitions in carbonyl compounds

vary with the nature of the solvents used. As the polarity of the solvent

increases, the π →π* bands undergo "Bathochromic shift" whereas, the n→

π* bands undergo a gradual “Hypsochromic shift”. These shifts are due to the

solvent stabilization of the excited or ground electronic states, thus resulting

in the change in the energy gap between the levels involved in the transition.

The UV-Vis absorption shift with change in the polarity of solvent is shown

in Fig. 2.5.

25
Scheme-1

Fig. 2.5 UV-Vis Absorption shift with change in polarity of the solvents

The Theoretical UV-Vis spectra of the compound 2,3DB2T were

calculated in the chloroform, DMSO & methanol solvents and are shown in

Fig.2.6. The calculated UV-Vis absorption maxima of the title molecule are

given in Table 2.1. The calculated results have three excited states namely

ES1, ES2 and ES3. The ES1, ES2 and ES3 calculated in gaseous phase

appeared at 1276, 801 and 632 nm. The excited states ES1, ES2 and ES3

calculated in chloroform solvent appeared at 1333, 843 and 669 nm. The

excited states ES1, ES2 and ES3 calculated in methanol solvent appeared at

26
1343, 864 and 683. Similarly for DMSO solvent ES1, ES2 and ES3

appeared at 1351, 867 and 685 nm. The calculated λmax values indicated that

the "Bathochromic shift" is observed when we increase the polarity of the

solvents. Here the excited state is more polar as compared to the ground

state so the polar solvents stabilize excited state more than ground state. So

overall there is decrease in energy gap between excited and ground state

resulting in red shift.

Fig. 2.6 The Calculated UV-Visible spectra of 2, 3 (dichloro-

benzylidine)-(2-trifluoromethyl-phenyl)-amine in different solvents.

27
 Table 2.1:- The Calculated electronic transition of 2, 3 (dichloro-
benzylidine)-(2-trifluoromethyl-phenyl)-amine

Calculated at B3LYP/6- Calculated

Oscillator strength Туре
311++G(d,p) Band gap(nm)
Gas Phase
Excited State-1 Singlet-A (f 0.0126) 1276 nm
75->81 -0.1179
80->81 0.5983
Excited State-2 Singlet-A (f 0.0087) 801 nm π-π*
79->81 0.6539
Excited State-3 Singlet-A (f 0.0068) 632 nm
77->81 0.6393
78->81 0.1652
79->81 0.1419
Chloroform
Excited State-1 Singlet-A (f=0.0018) 1333 nm
75->81 -0.1009
80->81 0.6012
Excited State-2 Singlet-A (f 0.0150) 843 nm π-π*
79->81 0.65460
Excited State-3 Singlet-A (f=0.0082) 669 nm
77->81 0.6143
78->81 0.2463
79->81 0.1360
Methanol
Excited State-1 Singlet-A (f=0.0149) 1343 nm
80->81 0.5977
Excited State-2 Singlet-A (f=0.0156) 864 nm π-π*
79->81 0.6526
Excited State-3 Singlet-A (f=0.0074) 683 nm
77->81 0.5809
78->81 0.3166
79->81 -0.1325
DMSO
Excited State-1 Singlet-A (f-0.0161) 1351 nm
80->81 0.5994
Excited State-2 Singlet-A (f-0.0167) 867 nm π-π*
79->81 0.6536
Excited State-3 Singlet-A (f-0.0079) 685 nm
77->81 0.5802
78->81 0.3184
79->81 -0.1324

28
2.5 CONCLUSION AND FURTHER STUDY

The UV-Vis absorption spectra of titled molecule was examined in

chloroform, methanol and DMSO as well as in gaseous phase by using
TD-B3LYP/6-311++G (d, p) basis set.

 The UV-Vis spectrum of the compound 2, 3 (dichloro-benzylidine)- (2-

trifluoromethyl-phenyl)-amine was recorded with chloroform, DMSO and

methanol and their λmax values are 843, 867 and 864 nm, respectively.

 The calculated λmax revealed that the red shift i.e. bathochromic shift was

observed by virtue of which maximum absorption is shifted towards the

longer wavelength.

 Here the maximum absorption is shifted to longer wavelength when the

solvent polarity is increased. In π → π* transition the dipole interactions

with the solvent molecules lower the energy of the excited state more than

that of the ground state. Thus the value of λmax shifts to longer

wavelength when we increase the solvent polarity. Hence we concluded

that π* orbitals are more stabilized by hydrogen bonding with the polar

solvents.

 The molecular parameters and vibrational frequencies are going to be

calculated with higher basis set DFT/6-311++G (2d, 2p) in order to

complete the vibrational analysis. The HOMO-LUMO, NBO and

Mulliken charges are also to be calculated to bring out more scientific

information related to the title molecule.

29
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