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1. PHOTOCHEMICAL EXCITATION
1. Photochemical excitation is the process in which a reactant is elevated to a
higher energy state, or excited state.
2. This happens when a chromophore, absorbs light

2. EXPERIMENTAL TECHNIQUES
1. Light source
Quartz mercury –vapor arc lamp is used for photochemical investigation
2. Production of monochromatic light
3. Filters
A. Filters are used for restricting the radiation to a narrow range of
frequencies
B. Glass filters are used to isolate mercury, helium and hydrogen
C. Filter of chlorine and bromine gas in quartz is used for filtering longer
wavelength
4. Monochromators
5. Measurement of radiation
6. Calibration
7. Photoelectric cells
8. Reaction cell
9. Chemical analysis

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3. ELECTRONIC TRANSITIONS
Types of Electronic Transitions
The following electronic transitions exist:

1. σ – σ* Transitions:
1. These transitions involve promotion of an electron from a sigma (σ)
bonding orbital to an antibonding sigma (σ*) orbital.
2. These transitions require a larger amount of energy
3. so they occur in the far UV region.
4. Examples of compounds showing σ → σ* transition are saturated
hydrocarbons like methane, ethane,
2. π - π *Transitions:
1. Here, an electron transitions from a bonding π orbital to an antibonding π*
orbital takesplace
2. These are observed for compounds that have conjugated double bonds
(e.g., ethene).
3. Such transitions are observed in UV-Visible spectroscopy.
4. The absorbance due to the π – π* transition in 1,3,5-hexatriene
5. It occurs at 258 nm
3. n – σ* Transitions:
1. Here, an electron transitions from a non-bonding orbital to a sigma*
antibonding orbital.
2. Like σ - σ* transitions, these also typically occur in the deep UV region.

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 3. Examples of compounds showing n → σ* transition are organic compounds
like halides, alcohols, aldehydes, ketones, ethers, amines,
4. n – π* Transitions:
1. An electron from a non-bonding orbital transitions to an antibonding π*
orbital.
2. These are observed in molecules that have non-bonding electrons (n-
electrons) and a π* orbital.
3. This transition requires lesser energy than π - π* transitions
4. so these absorptions appear at longer wavelengths compared to π - π*
transitions.
5. Examples of compounds showing n → π* transition are carbonyl
compounds, nitrile compounds,

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 4
JABLONSKII DIAGRAMS
23
Based on spin multiplicity there are two types of states
1. Singlet state denoted by S
Singlet state is a molecular electronic state such that all electron spins are
paired.
.

2. Triplet state denoted by T

In a triplet state the excited electron is no longer paired
that is, they are parallel (same spin).

Jabalonski diagram explain the following processes

1. Absorption of light energy
2. Fluorescence
3. Internal conversion
4. Inter system crossing
5. Phosphorescence

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1. ABSORPTION OF LIGHT ENERGY
The absorption of light energy promotes the electron from ground state to
excited state
2. FLUORESCENCE
Fluorescence is the phenomenon of absorption of electromagnetic radiation,
from ultraviolet or visible light, by a molecule and the subsequent emission of a
photon of a lower energy (smaller frequency, longer wavelength).
3 INTERNAL CONVERSION (IC)
1. This is a non radiative transition
2. It occurs when a vibrational state of an electronically excited state, couple
to a vibrational state of a lower electronic state.
3. It is singlet state to singlet state

4. INTERSYSTEM CROSSING (ISC)

1. This is a transition to a state with a different spin multiplicity.
2. ISC can be followed by phosphorescence.

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 5.PHOSPHORESCENCE
When exposed to light (radiation) of a shorter wavelength, a phosphorescent
substance will glow, absorbing the light and reemitting it at a longer
wavelength.

It occurs when an atom absorbs a high-energy photon, and the energy

becomes locked in the spin multiplicity changing from "singlet state" to a
slower emitting "triplet state".

5
INTERSYSTEM CROSSINGS
23
Intersystem crossing (ISC), the non- radiative transition between two
electronic states of different multiplicity,

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 6
ENERGY TRANSFER PROCESSES
23

7
STERN VOLMER EQUATION.
23

The ratio of quantum yield of flouoresence in the absence of quencher ( φ 0f

)and in the presence of quencher (φ 0f )is given by

0
φf
= 1 + KSV[Q]
φf

This is known as Stern – Volmer equation.

KSV is called Stern – Volmer constant.
USE:
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The Stern-Volmer (SV) equation is used to study the kinetics of intermolecular
deactivation processes, such as fluorescence and phosphorescence.
The equation correlates the lifetime and quantum yield of a chemical in an excited
state when a quencher is added.
8
REACTIONS OF ELECTRONICALLY EXCITED KETONES
23
1. Photolysis[Norish type -1reaction ]
2. Photocycloaddition[Paterno Buchi reaction]
3. Photo reduction

9
NORRISH TYPE-I REACTION
23
1. Norrish reactions are light initiated photochemical cleavage of carbon-
carbon bond in aldehydes and ketones
2. Reported by Renald George Wrefor Norrish
TYPE – 1
1. This includes the cleavage of C-C bond adjacent to carbonyl group[ α -
cleavage]
Primary process
2. It involves the C-C bond adjacent to carbonyl group to yield acyl radical
and alkyl radical

3. The acyl radical eliminates CO to give alkyl radical

4. This alkyl radical may undergo combination or intramolecular elimination

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 Secondary process
1. Depending upon the environment three secondary process may occur
2. Decarbonylation

3. Intramolecular hydrogen abstraction from alkyl radical

This leads to the formation of aldehyde and alkene

4. Intramolecular hydrogen abstraction from acyl radical

5. This leads to the formation of ketene and alkane

6.
Example -1

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Example -2

Example -3

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10
NORISH TYPE-II CLEAVAGE REACTIONS
23

It takes place in aldehydes and ketones containingγ - hydrogen

Primary process
It involves the intramolecular abstraction of γ - hydrogen to yield 1,4- biradaical

Secondary process
Depending upon the environment two secondary process may occur
1. Cyclisation

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In this process , the 1,4 diradical combines to form a cyclic product
2.Cleavage of β - bond
1. It forms an alkene and enol
2. The enol further undergoes tautomerisation to yield ketone
3. Thus the final products are ketone and an alkene

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11
PHOTO REDUCTIONS
23

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12
PATERNO-BUCHI REACTIONS
23

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 It is a 2+2 photocycloaddition,
which forms four-membered oxetane rings from an excited carbonyl and
reacting with an alkene.

13
UNSATURATED,
23

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14
PHOTOCHEMISTRY OF KETONES;
23
1. Photo reduction

2. Photocyclo addition

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3.Photolysis[Norrish type – 1 and II reactions]

15
23
CIS-TRANS ISOMERISATION.

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16
PHOTON ENERGY TRANSFER REACTIONS
23

17
PHOTO CYCLOADDITIONS
23

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18
PHOTOCHEMISTRY OF AROMATIC COMPOUNDS
23
Photochemical reactions of aromatic compounds are mainly of eight types,
1. Isomerization
2. [2+2]- And [4+2]- Cycloadditions
3. Hydrogen Abstraction And Addition,
4. Electrocyclization,
5. Dimerization,
6. Oxidation,
7. Substitution
8. Rearrangement Reactions

ISOMERIZATION

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 [2+2]- AND [4+2]- CYCLOADDITIONS

SUBSTITUTION

REARRANGEMENT REACTIONS

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 19
PHOTOCHEMICAL REARRANGEMENTS
23
20
PHOTO-STATIONERY STATE
23
1. The photostationary state is the equilibrium chemical composition under
a specific kind of electromagnetic irradiation
2. usually a single wavelength of visible or UV radiation
21
DI- Π-METHANE REARRANGEMENT[ ZIMMERMAN REACTION]
23

1. Di-π methane rearrangement is an intramolecular rearrangement in 1,4-

diene[two π-systems separated by a saturated carbon atom] by which the diene is
converted to vinyl cyclopropane
2. In this reaction, a three-membered cyclopropane ring is formed by 1,2 migration.

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22
REACTION OF CONJUGATED CYCLOHEXADIENONE TO 3,4
23
DIPHENYL PHENOLS
23
BARTON’S REACTIONS.[Barton nitrite ester reaction]
23

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 The Barton reaction, is a photochemical reaction that involves
the photolysis of an alkyl nitrite to form a δ-nitroso alcohol.

It involves
1. RO – NO cleavage
2. Conversion of organic nitrite in to nitrso alcohol
3. Formation of 6- membered transition state
4. δ - hydrogen abstraction
5. Free radical recombination
6. photolytic functionalization of an unactivated methylene moiety in a nitrite ester
to yield a γ-hydroxy oxime.
7. It introduces functional group at angular methyl group

8.

9.

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10. Both at angular methyl group and ONO should be in the same plane

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 UNIT-V: ORGANIC PHOTO CHEMISTRY
Class : II. MSc [ lll SEM] DATE : 13-07-2024

1. What do you mean by photochemical excitation?

2. Discuss the Experimental techniques in photo chemistry
3. Discuss the various types of electronic transitions
4. With neat sketch explain the Jablonskii diagram
5. What do you mean by intersystem crossing?
6. Discuss the various energy transfer processes in photo chemistry
7. Give Stern Volmer equation .Mention its use
8. List out the reactions of electronically excited ketones
9. Write note on Norrish type-I and type-II cleavage reactions
10.What is photo reduction?
11.Give a brief account of Paterno-Buchi reaction
12.Explain the Photochemistry of ketones
13.With an example explain cis-trans isomerisation in photo chemistry
14.List out the Photon energy transfer reactions
15.What is Photo cycloaddition? Explain with example
16.Discuss the Photochemistry of aromatic compounds
17.What do you mean by photochemical rearrangement?
18.Define photo-stationery state
19.Explain di- π-methane rearrangement
20.Explain the reaction of conjugated cyclohexadienone to 3,4 diphenyl
phenols
21.Discuss about Barton’s reactions.
**********

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