Fundamentals of UV Spectroscopy

Dr. Asit K. Chakraborti FRSC, FASc, FNA

Prof and Head
Department of Medicinal Chemistry
National Institute of Pharmaceutical Education and Research (NIPER)
S. A. S. Nagar, Punjab 160 062, INDIA
www.niper.gov.in
 Spectral Analysis:
Molecular Informatics
 The Oscillating electric and magnetic fields of a beam of ordinary light

Oscillating of the electrical field of ordinary light

occurs in all possible planes Perpendicular to
the direction of propagation

The plane of oscillation of the electrical field of

plane polarized light. In this example the plane of
polarization is vertical.
Various Regions of Electromagnetic Spectrum

Region Wavelength Wavenumber, Frequency,

 A c m-1 f

Far ultraviolet 0.01-0.2 100-2000 1,000,000-50,000 30,000-1500

Near ultraviolet 0.20-0.38 2000-3800 50,000-26.300 1500 -787
Visible 0.38-0.78 3800-7800 26,300-12,800 787-385
Near infrared 0.78-3 7800-30,000 12,800-3333 385-100
Middle infrared 3-30 30,000-300,000 3333-333 100-10
Far infrared 30-300 300,000-3,000,000 333-33.3 10-1
Microwave 300-1,000,000 3,000,000-10,000,000,000 33.3-0.01 1-0.0003
 VARIOUS REGIONS OF ELECTROMAGNETIC RADIATION:
CORRELATION OF ABSORPTION AND SPECTROSCOPIC/METRIC TECHNIQUES
 Molecular Level Changes:
Absorption of Electromagnetic Radiation
 Light Absorption and its Measurement:
Different Energy Levels

Energies of a diatomic molecule in (left to right) electronic, vibrational and rotational States.
(Reprinting by permission from G.W. Wheland, resonance in Organic Chemistry, John Wiley
andSons, New york, 1955, p. 246.)
VARIOUS SPECTROSCOPIC TERMINOLOGIES
SOME IMPORTANT PHYSICAL PARAMETERS

A) WAVELENGTH () : 
B) WAVENUMBER (v) : cm-1
C) FREQUENCY (v) : sec-1, f( 1012 oscillation per sec. )
D) MOLAR ABSORPTIVITY : 
E) CHROMOPHORE
F) AUXOCHROME

SOME IMPORTANT TERMINOLOGIES

A) BATHOCHROMIC EFFECT
B) HYPSOCHROMIC EFFECT
C) HYPERCHROMIC EFFECT
D) HYPOCHROMIC EFFECT
 FACTORS INFLUENCING  MAX AND  VALUES
A) EFFECT OF SUBSTITUENT:
a) SUBSTITUENT WITH LONE PAIR OF ELECTRONS
i) INDUCTIVE EFFECT
ii) RESONANCE EFFECT

b) ALKYL SUBSTITUENT
i) DIRECTLY ATTACHED TO THE CHROMOPHORE
ii) ATTACHED TO THE -CARBON

c) UNSATURATION IN CONJUGATION TO THE CHROMPHORE

d) HALOGEN

i) DIRECTLY ATTACHED TO THE CHROMOPHORE

ii) ATTACHED TO THE -CARBON

B ) STEREOCHEMICAL FACTORS:
a) STERIC INHIBITION TO RESONANCE
b) ANGULAR DISTORTION
c) INTRODUCTION OF EXTRA STRAIN

C) EFFECT OF SOLVENT

D) EFFECT OF RING SIZE

a) CHROMOPHORE IS IN THE RING
b) CHROMOPHORE MAKES A PART OF THE RING

E) NON-CONJUGATED INTERACTION
Essential Structural Requirement
to be UV Active: Chromophore!
 Effect of Substituent:
Rationalisation of
Bathochromic/Auxochromic Shift
Effect of Conjugation
Energy Level Diagram of Ethylene and Butadiene

C=C C=C-C=C C=C

Evolving Fingerprint of
Structure Elucidation
Validation of Emperical Rules
Implication of Emperical (!) Rules
Effect of Alkyl Group Substitution
Effect of Alkyl Groups on the Long-Wavelength
Absorption Band of Methyl Ketones CH3COCRR’R” in CHCl3

R R’ R”  max 

H H H 275 17.1

H H CH3 277 19.4

H H C2H5 279 21.2

H H C3H7 279 21.2

H CH3 CH3 281 21.2

CH3 CH3 CH3 285 21.2

Effect of Heteroatom Substitution
 Hypsochromic Effect of Lone Pair Auxochromes
on the n - π* Transition of a Carbonyl Group
Compound  max  max Solvent
_____________________________________________________
O
CH3 C H 293 nm 12 Hexane

O 235 53 Hexane
CH3 C Cl

O 214 - Water
CH3 C NH2

O 204 60 Water
CH3 C OCH2CH3

O
CH3 C OH 204 41 Ethanol

O
CH3 C CH3 279 15 Hexane
Effect of Solvent on UV Spectra
 EFFECT OF SOLVENT
EFFECT OF SOLVENT ON THE SPECTRUM OF (CH3)2C=CH – COCH3

 - * n- *
Solvent
------------------------
 (nm)  max
------------------------
 (nm)  max
max max

Hexane 229.5 12,600 327 97.5

Ether 230 12,600 326 96

Ethanol 237 12,600 315 78

Methanol 238 10,700 312 74

Water 244.5 10,000 305 60

 EFFECT OF SOLVENT :
DETERMINATION OF THE STRENGTH OF HYDROGEN BOND

EFFECT OF THE SOLVENT ON THE n - * TRANSITION OF CH3 –CO- CH3

Solvent  max (nm)

Water 264.5 (126 K. Cal./Mol)
Methanol 270
Ethanol 272
Chloroform 277
Hexane 279 (121 K. Cal./Mol.)

Strength of the H-bond = 5 K. Cal./Mol.

 STEREOCHEMICAL FACTORS

A) EFFECT OF STRAIN:

a) Increase of Ground State Energy

b) Stabilisation of the Excited State
c) Loss of Planarity

B) NON-CONJUGATIVE INTERACTION
Steric
Determination of Stereochemistry
Distinguish Between the Axial and Equotorial α-
Halogenated Cyclohexanones

O O- O
H H Vs X
X X+ H

O
O
X
X
H
The S-Cis Band in UV Spectra
 Wavelength, nm
The Spectra of (i) trans-trans, (ii) cis-trans, and (iii) cis-cis-1,4-diphenylbutadiene.
[Reprinted by permission from J.H. Pinckard, B. Willie, and L. Zechmeister, J. Am.
Chem. Soc., 70, 1938 (1948).]
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