➡Concept of Chromophore and Auxochrome

(Bathocromic,hypsochromic, hyperchromic and hypochromic

shifts):
CHROMOPHORE: These are groups (substituents carbon, bromo,
functional) which imparts colours to compound.

e.g NO2 gives yellow colour to compound.

Nowadays these groups are defined as those groups which exhibit

absorption of radiations in UV and visible region and undergoes transition.

These groups may or may not impart colours to compounds.

Chromophores types:

i) Chromophores such as etc. contain 'π' electrons and

undergo 'π' to 'π*' transition.

ii) Chromophores such as etc. contain both 'π' and non bonding
electrons and undergo 'π' to 'π*' and 'η' and 'π*' transition.

Compound having same Chromophore show λ max at same value and also show same ε max.

Application of chromophores:

It is applicable to identify functional in unknown group by comparing its UV spectrum

with data of known compound.

AUXOCHROMES: These grpups itself donot act as chromophore

but when they are attach to chromophores , they shift absorption
to longer wavelength with increasing intensity of absorption.

Alcohol, aloxy, amine, alkyl amine, di- alkyl amine e.g. OH, OR,
-NH2, NHR, NR2 etc.
Explanation:
When Auxochrome is attached with chromophore then it

leads to conjugation shown as:

Due to conjugation energy difference between bonding and
antibonding orbitals decreases and thus absorption shifted to
longer wavelength. e.g. when NH2 group is attached with benzene
then λ max increases from 255 to 280 nm or εmax increases

from 203 to 1430 shown as:

Change in position and intensity of absorption:

These changes can produce four effects:

1. Bathocromic effect (Red effect).

2. Hypsochromic effect(Blue effect).

3. Hyperchromic effect .

Hypochromic effect.

1. Bathocromic effect: This effect shift absorption to longer wavelength.

Cause of Bathocromic effect:

1. Attachment of axochrome to Chromophore.

e.g. when NH2 group is attached with benzene then λmax

increases from 250 nm to 280 nm.

2. Presence of conjugation: conjugation shift absorption to longer

wavelength. e.g. In ethylene λmax is 175 nm and in Buta-1,3 diene λmax is
217 nm.
 3. Use of lower polarity solvent: lower polarity solvent shift absorption to
longer wavelength.

e.g. acetone in water shows λmax at 264 nm and in hexane shows λmax
at 279 nm .

2. Hypsochromic effect: This effect shift absorption to shorter wavelength.

Causes:

i) removal of conjugation shifts absorption to shorter wavelength.

e.g. Buta- 1,3 diene= 217nm and Ethylene=175nm.

ii) use of high polarity solvent: It shifts absorption to shorter wavelength.

e.g. Absorption of acetone in water is 264 nm and in hexane =279nm.

3. Hyperchromic effect: This effect increases the intensity of the

absorption. This is due to the presence of Auxochrome to chromophore.

e.g. ε max for benzene is 203 and then NH2 group is introduced ε max
becomes 1430.

4. Hypochromic effect: This effect decreases the intensity of absorption.

This is due to distortion of geometry of molecule due to group introduction.

e.g. fancy CH3 group is introduced in diphenyl group then intensity

decreases.