Notes on

Organic photochemistry

By
Dr. Gangutri Saikia
Photochemistry is the study of reactions that are brought about by the action of visible or ultraviolet light.

Chapman’s definition: It is the science arising from application of photochemical methods to organic chemistry and
organic chemical methods to photochemistry.

Basic Principles
In order to bring about a chemical transformation, a certain amount of energy is provided to molecules by irradiating
the molecule with certain wavelength of electromagnetic radiation when the molecule absorbs a photon and gets excited. The
wavelength of elctromagnetic region in general lies in the ultraviolet region or less frequently in the visible region of the spectrum. The
basic relationship of energy of radiation to frequency and wavelength are given by the expression-

Ɛ = hᴜ; Ɛ= energy per quantum, h= Planck’s constant= 6.63x10-34 Js, ᴜ= frequency of radiation

The energy absorbed per mole at a specific wavelength can be calculated by following the equation-

E= Nhᴜ=Nhc/λ; E= energy per mole, N= Avogadro’s number,

c= velocity of light, λ= wavelength of radiation

2
 Light in the visible and ultraviolet region has sufficient energy to cover the range of chemical bond energies. When a
molecule absorbs a photon of the appropriate energy, one of its electrons is raised to an orbital of higher energy i.e. an electron from
its highest occupied molecular orbital (HOMO) is excited to the lowest unoccupied molecular orbital (LUMO) of the molecule. The
resulting molecule may take part in a reaction in this excited state. The reaction so induced may be either intramolecular e.g.
rearrangement or dissociation, or intermolecular, for example-addition reactions. On the other hand, the excited molecule may also
transfer its energy to another molecule which in turn can undergo reaction. These variants open up a wide range of synthetic
possibilities.

Different types of electronic transition in organic molecules

The valence electrons of organic compounds in the ground state are accommodated in σ-MOs , π-MOs, and nonbonding
molecular orbitals . For each of the bonding σ or π-MO, there is a corresponding antibonding σ* or π* orbital.

Electronic transition due to photochemical excitation of molecules involve the promotion of an electron from σ or π-MO
or NBMO to one of the antibonding orbitals σ* or π*.
The order of energy required for various
electronic transition is given below-

σ → σ* > n → σ* > π → π* > n → π*

σ → σ* - Alkanes (no n or pi electrons)

n → σ* -Alcohols, amines, ethers etc.
π → π* - aldehydes, carboxylic esters, alkenes.
n → π* - aldehydes, ketones, carboxylic esters

In photochemical reactions, the most important type of electronic excitation in organic molecules are n→π* and π→π*
transitions. These transitions have lower energy requirements and occur at longer wavelengths, usually well within uv light. The
energies required for σ → σ* and n → σ* are usually very high, requiring a wavelength far below 200 nm. Therefore, photochemical
reactions are usually limited to those in which at least one of the reactants is unsaturated or aromatic.
Photophysical processes

In the ground state of the molecules, most of the organic compounds remain in spin paired state. This state is denoted by
S0 state. When a molecule absorbs a photon of a particular wavelength, an electron from the bonding level is promoted to an
antibonding level depending on the size of the quantum of energy provided by the photon.

 If an electronic transition takes place with the conservation

of spin state of the molecule, this means that the molecule is
photoexcited from S0 to Sn state, n= 1,2,3...etc. The excited
state is known as singlet excited state.

 In many cases, electronic excitation is followed by spin

inversion, thus giving rise to a new excited state. This state is
called triplet excited state or Tn.

Suppose, a molecule is photoexcited from S0 to Sn state, where n is the higher

electronic state of the molecule. There are many more photophysical processes which can cause
energy dissipation by the photoexcited molecule. Of these, the uni- and bi-molecular processes are
given below-

Unimolecular processes- Bimolecular processes-

Internal conversion (IC) Solvent quenching

 Fluorescence (hᴜf)  Self-quenching

 Intersystem crossing (ISC)  Impurity quenching

 Phosphorescence (hᴜp)  Electronic energy transfer (ET)

Jablonski diagram

VC Vibrational cascade
IC Internal conversion
ISC Intersystem crossing
hνf Fluoroscence
hνp Phosphorescence
Franck Condon principle

Franck-Condon principle provides a useful guiding principle for investigating the vibrational structure of electronic
spectra. It states that an electronic transition takes place so rapidly that a vibrating molecule does not change its internuclear distance
appreciably during the transition. The principle is true in the sense that since the electrons move so much faster than the nuclei that
during the electronic transition the nuclei do not change their position. Hence an electronic transition may be represented by a vertical
line on a plot of potential energy versus internuclear distance.
Internal conversion:
This is a non-radiative unimolecular energy dissipation process. When a molecule absorbs a photon of a particular
wavelength, the molecule is raised to ground electronic state to higher electronic states depending on the amount of energy provided
by the photon, i.e. the molecule is photoexcited from S0 to Sn state where n=1,2,3....etc. The life time of upper excited singlet states
(n=2,3,4....) is usually less than 10-11 s and they rapidly decay to the lowest level S1 by successive release of energy. These energy
cascades of the electron involve overlapping vibrational states of each electronic state of the molecule. So, these energy cascades are
called vibrational cascades (VC) in which excess electronic energy is dissipated in the form of heat called nonradiative path. Such VC
from one electronic state to the other is called internal conversion (IC). IC from Sn, Sn-1,.....to S2 are quite common but IC from S1→S0 is
not so fast due to the high energy gap between S0 and S1 levels. Most of the higher electronic states S2, S3,.....etc. cannot lead to
chemical transformation due to their short life time compared with the collision frequency (~10-8 s) required for any chemical
transformation. Of all the excited singlet states, S1 has the longest life (10-8 s) and is very important in photochemistry.

S1 may undergo one of the following four energy degrading processes- (i) It
may emit the energy as photon and drop to S0. This process is called fluorescence and
generally occurs within 10-9 to 10-6 s. (ii) It may return to S0 by nonradiative process in
which excess energy of the excited state is shuffled into vibrational modes. (iii) S1 may
undergo chemical reactions and finally (iv) its decay to triplet state may occur before any
of the above processes take place.
Fluorescence:
It is the process where a material absorbs light at a higher energy, short wavelength and emits light at a lower energy,
usually visible, wavelength. In other words, it is a radiative unimolecular energy dissipation process and is caused due to S1→S0
transition. The emitted radiation is of lower frequency than the absorbed radiation due to the vibrational relaxation of the primary
excited state S1(V=Vn) to S1 (V=V0) state.

Organic molecules that possess more or less rigid structure and cannot lose their energy
through many vibrational levels generally fluoresce. Certain groups that are part of such molecules are
called fluorophores. The following groups are the examples of fluorophores:

Intersystem crossing:

If the singlet state S1 is sufficiently long-lived, as in aromatic and carbonyl compounds, and if S1 and the corresponding
triplet state T1 are close in energy, then the S1(v0) state may crossover to the T1(vn) state in a slow process. The crossover is slow in
accordance with the spectroscopic rule that change in multiplicity is a formally forbidden process. The T1(vn) state then vibrationally
cascades down to T1(v0) state. Therefore this process can be looked upon as S1(v0)→T1(v0) transition with loss of heat energy. This non-
radiative unimolecular energy dissipation by the S1(v0) state is called intersystem crossing (ISC).
 This process is very important for photochemical reactions
as T1 exists for a much longer period of time (10-3 to 1 s). This implies that
molecules in the T1 state may undergo many effective collisions leading to
chemical reactions. So, photochemical reactions are favored by the long
life of T1 state. Many aromatic ketones and other aromatic compounds
have high intersystem crossing efficiencies while due to the rather high
energy gap between two states of olefin, the latter have a lower tendency
to intersystem crossing.

Intersystem crossing leads to several interesting routes back to the ground electronic state. T1 state may either undergo a
chemical reaction or may return to the ground state (S0) by emission of a photon, a process known as phosphorescence. The third
alternative for the triplet state is to return to S0 by radiationless decay.

Phosphorescence:

The photoexcited molecules in the T1(v0) state is most likely to undergo photochemical changes. But this may also lose or
dissipate energy through a unimolecular radiative path called phosphorescence. The lifetime of phosphorescence is usually in the
range of 10-3 to 10 s. It is a slow process due to the spin forbiddenness and is caused due to T1(v0) → S0 transition. When a molecule has
both fluorescence and phosphorescence, the wavelength of phosphorescent light is always longer than that of fluorescent light (since
the energy gap of S1→S0 is higher than the energy gap of T1→S0). It is always a delayed process.
Energy transfer:
T1 state cannot be directly populated from S0 state by irradiation due to spin forbiddenness and also due to the fact that
in most cases the energy gap between S1(v0) and T1 (vn) states is too large for any crossover from S1(v0) to T1(vn) state. Energy transfer is
a means to populate T1 state. Some photoexcited molecules called donors, where the T1 state can be easily populated via ISC from S1
state, can transfer their T1 energy to the S0 state of some other molecules called acceptor molecules, where populating the T1 state is
not possible by ISC and thereby can directly populate the T1 state of the acceptor molecule and themselves return to the ground state.
This process is called energy transfer (ET) and plays a very important role in bringing about photochemical reactions. The phenomenon
is called photosensitization. It is a process of initiating a reaction through the use of a substance capable of absorbing light and
transferring the energy to the desired reactants.

The basic requirement for energy transfer is that the donor molecule should have at least 5 kcal/mole more energy than
the energy required to excite the acceptor molecule to its lowest excited state. Under these conditions, energy transfer does take place
on every collision between the excited donor molecule and the ground state acceptor molecule. Ketones and aldehydes are good
examples of donor molecules and alkenes are examples of acceptors. A typical mechanism for triplet energy transfer involves the
excitation to S1 of donor molecule on irradiation, and the subsequent decay of S1 to T1. Collision of the T1 donor with the ground state
acceptor molecule produces a T1 acceptor and ground state donor molecules. This photosensitization phenomenon can be represented
as follows with symbols D for donor and A for acceptor.
Laws of photochemistry
Photochemical processes are governed by two laws, namely

First law of Grotthus-Draper law: It is an empirical law, which states that when a substance is irradiated, only that fraction of the
radiation that is absorbed by the substance can bring about photochemical changes. The reflected or scattered or transmitted portions
of the incident light play no role in the chemical changes.

Second law of Stark-Einstein’s law of photochemical equivalence: It states that each quantum or photon absorbed by a substance
can activate only one molecule of it in the primary step of a photochemical equivalence.
But this rule does not imply that each excited or activated molecule will take part in the chemical change. Only in ideal
cases, such things happen, i.e., every activated molecule undergoes chemical transformation. But in most cases, it is not so. Many
activated molecules undergo deactivation by various quenching and photophysical processes.

Quantum yield
The efficiency of a photochemical process is usually expressed in terms of quantum efficiency or quantum yield (Φ), which is defined as-

Only in ideal cases, Φ = 1. In practice, however, Φ has been found to have a very low value (as low as 0.01) and also a very high value (as
high as 106). The low Φ values are very common for those reactions where the activated molecules are readily deactivated by different
quenching processes, or where the primary products formed recombine to give back the parent compound.

The high Φ values found in some chain reactions, where the primary products formed as free radicals can trigger a chain
reaction involving the parent molecules.
Types of photochemical reactions
1. Photodissociation: Since the electrons are weakly held in the excited state, the molecule may be more easily dissociated.

2. Because of Franck-Condon principle, unusual vibraional and rotational levels may be achieved that can bring about chemical
changes not normally possible in the ground state as in valence isomerization of benzene.

3. The photoexcited electron is more likely to be easily removed by an electrophile as in photooxidation.

4. The photoexcited state may interact with any other odd electron species to form a bond.

5. For systems with a variable valency as in the case of coordination compounds, a redox reaction may be set up either
intramolecularly or intermolecularly.

The reaction of excited states including both singlet and triplet can be classified under the following headings: reduction,
addition, rearrangement, oxidation, aromatic substitution and fragmentation.

Photolytic reactions of carbonyl compounds:

 Two readily accessible transition in a carbonyl group are n → π* and π → π* transitions. These transitions take place at around 285 nm
(n → π*) and 180 nm (π → π*).

 Since NBMO and antibonding π* MO are perpendicular to each other, the n → π* transition in carbonyl compound is overlap
forbidden. But due to unsymmetrical molecular vibrations, this transaction takes place slowly. The π → π* transition is an allowed
process.

 Due to the small energy gap between S1 and T1 states, ketones undergo intersystem crossing with high degree of efficiency. As a result,
most of the photochemistry of ketones arises from their triplet states. The nature of products of such reactions, very frequently depends
on the structure of ketone and medium of irradiation.
Photoreduction: Carbonyl compounds can be converted into 1,2-diols (pinacol) and alcohols by irradiation in presence of a hydrogen
donating compound such as alcohols, amines or hydrocarbons. Reaction occurs through triplet state of the carbonyl compound which
abstracts a hydrogen atom from the second reactant. The lowest singlet excited state of ketones is S1(nπ*) state.

The resulting radicals either combine,

Or abstract hydrogen from the solvent,

The latter reaction is favoured when R’· is a stabilized radical (e.g. tertiary) and the coupling reaction is favoured when R is a radical
stabilizing group (e.g. aryl). The coupling reaction is usually most efficient when the hydrogen donor is itself the alcoholic reduction
product of carbonyl compound. For example, in case of benzophenone
α,β-unsaturated ketones under similar condition often form saturated ketones.

The hydrogen abstraction reaction is much more efficient in the n,π* state of ketones than in the π,π* state, because of the high electron
density on O-atom in 3(ππ*) ketones , such oxygen atom cannot abstract a hydrogen atom but shows a tendency to abstract a proton
instead.
Photocycloaddition of ketones with C=C and C≡C (Paterno-Buchi reaction): Carbonyl compounds yield oxetanes on irradiation in
presence of olefins. This photocycloaddition is usually referred to as Paterno-Buchi reaction. This photoaddition normally occurs by
reaction of the triplet state of the carbonyl compound with the ground state of the alkene. As in photoreduction, it is more efficient when
the triplet is of (n,π*) type rather than (π,π*) type.

3(nπ*) undergo cycloaddition with C≡C to form unstable oxetenes that quickly isomerize to α,β-unsaturated ketones.
Photolysis of carbonyl compounds: Carbonyl compounds on irradiation alone generally undergo a cleavage of C-C bond giving a
number of products. The n → π* excitation of aldehydes and ketones can bring about two types of fragmentation.

First, fragmentation can occur of the C-C bond adjacent to carbonyl-

Thus, when cleavage of the C-C bond α to the carbonyl group takes place, it is called Norrish type I reaction. This cleavage
takes place by the 3(nπ*) state of the ketones. The half vacant NBMO of 3(nπ*) state overlaps the σ-BMO of the α-C-C bond. This
facilitates the cleavage of the α-C-C bond.

The cleavage is generally followed by one or more of three reactions depending on the reaction conditions:
disproportionation to give a ketene,

Decarbonylation and then dimerization and/or disproportionation or intermolecular H atom abstraction by acyl radical.
 For example,

Intermolecular H atom abstraction by acyl radical

 Benzophenone on α-cleavage at room temperature gives benzil and biphenyl as main products but above 100 °C, practically no benzil is
formed. The benzoyl radical decarbonylates to form biphenyl as the main product.

In case of cyclic ketones, it forms diradicals in the primary reaction. The diradical may decarbonylate, and the resulting new diradical
may cyclize if a strainless ring formation is possible.

The diradical formed in the primary reaction may also abstract a δ-H atom to form an unsaturated aldehyde.
 If the carbonyl compound contains a γ-H atom, intramolecular H-atom abstraction can occur. This β-cleavage is known as Norrish type
II reaction. The reaction proceeds by the initial γ-H abstraction by the oxygen atom yielding a 1,4-biradical which subsequently cleaves
to an olefin and an enol. In some cases, ring closure also occurs.

Both n,π* singlet and n,π* triplet participate in the intramolecular hydrogen abstraction reactions while ketones with a low lying π,π*
state do not undergo this reaction.
If alkyl or aryl group is present in the γ-C atom of the ketone, then cyclization reaction of the primary diradical competes with β-cleavage.

In case of smaller cyclic ketones, type I process predominates, while for larger rings type II process can occur. In case of some cyclic
ketones, H abstraction may take place from a C atom beyond the δ-position and the formation of cyclized product may compete with β-
cleavage if conformation allows.
Photochemistry of alkenes: In the phtoexcitation of a C=C bond in alkenes, only (ππ*) state is involved. But since ISC of S1 → T1 is
inefficient, the 3(ππ*) can only be populated via photosensitization.

The products formed in the photoreaction of alkenes depend on the following factors:

1. Nature of the olefin

2. The number of C=C present in the molecule and their relationship with one another

3. The excited state

Cis-trans isomerization of alkenes (Photostereomutation): Olefins usually undergo cis-trans isomerization upon irradiation with
ultraviolet light. The usefulness of the reaction lies in the fact that in photostereomutation, the thermodynamically less stable cis isomer
may be obtained as the major component of the product mixture.

The transformation can be effected by direct irradiation of the olefins or by irradiation in the presence of a sensitizer. It may either take
place through a singlet or triplet excited species. It is however known that isomerization in the triplet state possess a lower barrier to
rotation around the carbon-carbon bond.

Here, mercury photosensitized isomerisation takes place through T1 state of the alkenes. Isomerization can occur because π bond which
normally prevents it, is lost in passage to the excited state. In the excited state, the structure around the C-C σ-bond is twisted by
approximately 90 °. This distorted configuration of the excited state is called phantom state in which the distinction between cis and
trans form is lost. The phantom state then collapses to the ground state by conventional deactivation process. In doing so, C-C σ bond
can be twisted in either of the two directions to give both cis and trans isomers. Since more of the trans isomers are preferentially excited
to the phantom state, therefore the photostationary state obtained by the deactivation of the phantom state will contain a higher
percentage of the thermodynamically less stable cis form.
This process of obtaining the less stable stereoisomer by photostereomutation is called optical pumping.

Dimerization of alkene: Olefins may also undergo dimerization reaction. The process involves generation of an excited triplet molecule
which subsequently reacts with a ground state olefin molecule. It occurs through 3(ππ*) state. For example- acetone sensitized
photodimerization of norbornene.

Similar dimerization may also take place intramolecularly.

Alkenes can also be photodimerized by direct irradiation in [2 + 2] cycloaddition reaction giving stereospecific products..