Applications of CIDNP in Photochemistry

presentation by
Kiran Chillewad
Department Of Chemistry
IIT Kharagpur
Radical Pair Mechanism • Wigner's Rule : spin angular momentum
must be conserved in any elementary
chemical step

• Combination reactions depend on the

electronic spin state of the dynamic radical
pair, reaction from the singlet being
allowed and reaction from the triplet being
forbidden

• radical pairs can undergo intersystem

crossing, which provides a leakage
between the two vertical pathways
g values of the radicals=> Zeeman interactions
hyperfine coupling constants a => hyperfine interactions
J Am Chem Soc 91:4552–4554
Intersystem Crossing of Radical Pairs
• The mixing interaction M is not influenced by a
separation but the energy is influenced

• difference ∆E is a strong function of the

interradical distance because its origin is the
electrostatic interaction between the electrons.

• the energies of singlet and triplet converge at

sufficient interradical separations

• despite the smallness of the magnetic interactions,

intersystem crossing between Sand T0 states is
|∆E|>>|M| feasible for all interradical distance exceeding a
critical distance
P2(t)max =(2M/∆E)2
J Chem Phys 57:5107–5113
Origin of nuclear polarization :
• the nuclear spin indirectly determines the
rate of bond formation through hyperfine
coupling which influences the rate of
intersystem crossing.

• the rate of intersystem crossing of a

dynamic radical pair depends on the
orientations of the nuclear spins that are
hyperfine coupled to the electron spins in
the radical pair.

• β orientation of 13C nuclei lead to a faster

ISC than the α orientation of 13C nuclei.
α-cleavage of DBK
CIDNP Intensities and Signs :
• ∆g=g1-g2 ,with the g values of the two
radicals;

• β= Bohr magneton
B0= field of the magnet and the

• ak =hyperfine coupling constant

mk=z component of nuclear spin for
nucleus k

• the positive sign and index i refer to the

nuclei in radical 1 the negative sign and
index j to those in
radical 2
J Am Chem Soc 103:3217–3219
Kaptein's rule:
Kapteins rule says observation of emission (E) and enhanced absorption (A) in the
n.m.r. spectra of reacting systems is evidence for the fact that products showing
these effects are formed by a radical mechanism

• μ= precursor multiplicity
+1 for Triplet and -1 for Singlet

• ε= Exit channel
+1 for products of singlet exit channel
Γk = +1 denotes enhanced absorption
-1 for products of triplet exit channel
Γk = -1 denotes emission
• Zeeman interactions (g values of the radicals)
and hyperfine interactions (hyperfine coupling
constants a)
Chem Commun 1971,732–733
Determination of Precursor Multiplicity :
β-cleavage of (N-methylaniline)-acetone

• singlet cleavage is an activated process

, Ea =15–20 kJ/mol

• intersystem crossing to the much

longer-lived triplet state is temperature
independent

J Photochem Photobiol A 1992,65:371–382

Temperature dependence of the CIDNP signals :

• At low temperatures singlet cleavage is

slow, and formation of triplet pairs
prevails

• However, with increasing temperature

the participation of singlet pairs
becomes more and more important and
ultimately dominates

• CIDNP signals experience an inversion

when the temperature is raised, i.e. (μ=
+1 → μ= -1).
 Conclusion:

• Only radical pair and biradical intermediates cause CIDNP

• CIDNP effect arises only during the life of the

spin-correlated intermediates (nanoseconds to subnanoseconds)

• CIDNP is able to capture shorter-lived paramagnetic

intermediates than is EPR
Thank You!