Class : M.Sc.

IVth Semester
Course: : Photo inorganic Chemistry and Reaction
Mechanism of Coordination compounds
Course Code : CHM4011
Unit : III
 The Photochemistry of Transition-Metal Complexes

oWhat is the nature of the interaction of light with matter?

• For an effective electronic transition, there must be an interaction between the

electric field vector of the light and the electric dipole of the molecule.

• The probability of absorption is expressed by the well-known Beer-Lambert law.

o Electronic transitions for coordination compounds

• A large variety of electronic transitions are possible for coordination compounds.

Two of those which are encountered most frequently, d-d transitions and ligand-to-
metal charge transfer transitions (LMCT).
o Deactivation processes

• Electronically excited states of coordination compounds, as for any compound, can

be deactivated by many different pathways

Some possible deactivation processes for excited states

• The efficiency of a particular primary process is quantified by a quantum yield.

• Deactivation pathways of the excited state can be classified as either photophysical or

photochemical processes.

1. Photophyscial Deactivation Process

A selection of intramolecular photophysical processes. The full arrows correspond to radiative processes, the dashed arrows to non-
radiative processes. Internal conversion (i.e.), intersystem crossing (i.s.c.), and vibrational relaxation (v.r.) are abbreviated. S represents
a singlet state, and T a triplet state.
2. Photochemical Deactivation Processes

• Excited states have molecular structures and thermodynamic properties which may
differ markedly from the ground state. The excited state may be able to make use of
its excess energy to undergo reactions which are not available to the ground state
molecule. For instance, excitation can be associated with significant radial and
angular distortions which may promote bond cleavage.

2.1. Outer-sphere redox reactions

• Outer sphere redox reactions can take place between the excited state and a suitable
Quencher.

• The excited state is often both a more powerful reductant (since an electron has been
promoted to a high-energy orbital), and oxidant (because there is now a "hole" in a
low-energy orbital) than the ground state.

•For example, redox quenching of an excited state of [Ru(bpy)3]2+ by hydrated Fe3+ cations.
2.2. Photoredox elimination and addition processes

• The redox properties of the excited state can also activate the complex to photoredox
elimination and addition reactions.

• These result in a change in the oxidation state of the central metal ion along with a
change in the coordination number of the complexes.

• Often the products are transient species which react further in secondary (thermal)
reactions to give the observed products. Photoaddition reactions stem from an
increase in the Lewis acidity of the metal upon excitation.
2.3. Intramolecular redox processes

• Redox processes can also take place in an intramolecular fashion, whereby an electron
is (formally) exchanged between the central metal atom and a coordinated ligand.

• The primary products, a reduced metal centre and an oxidised ligand, are often quite
reactive and will undergo secondary thermal reactions.
2.4. Photochemical isomerisation reactions

• Many different classes of isomerisations have been reported, including transformations

between linkage isomers, optical isomers, geometrical isomers, and tautomers. The
processes are often mediated by transients formed via inner-sphere redox pathways. For
example, linkage isomerism,

2.5. Photosubstitution reactions

• The term photosubstitution refers to the ligand exchange between the primary and
secondary coordination spheres, with preservation of the oxidation state and coordination
number of the metal ion.

• Aquation is the most common in photosubstitution avenue, as most photochemical studies

have been performed on aqueous solutions
 PHOTO REACTIONS OF
COMPLEXES OF CHROMIUM(III)
 PHOTO REACTIONS OF COMPLEXES OF CHROMIUM(III)

• Chromium(III) complexes in an octahedral (Oh) ligand field have the ground state t2g3 a
4A term, and the excited state t 2e 1 has 4T and 4T (F) terms.
2g 2g g 2g 1g

• The photochemical reactions of Cr(III) include both ligand substitutions and isomerization
in solution and solids. Intramolecular redox reactions also are noted when charge-transfer
bands are excited as well as intermolecular ones in cases where a long-lived state is
quenched by bimolecular electron transfer to another species in solutions.
1. Photoaquation Reactions

• Ligand field irradiation of chromium(III) complexes leads primarily to substitution

reactions.

• The most common reaction in aqueous solution is photosubstitution of a ligand by water.

Photoaquation reactions involving light-induced exchange of water between [Cr(H2O)6]3+
and the solvent. The reaction is followed by using isotopically labeled H 2O18 as the
solvent, where sequential photosubstitution of the H2O molecules leads to the formation
of Cr(H2O18)6]3+

• The quantum yields at 261, 408, and 574 nm are rather low (ɸ= 0.02) and wavelength
independent. These low quantum yields for the aquation reaction correspond with a
mechanism involving labilization of a water ligand in the excited state.
• For other octahedral complexes such as [Cr(NH3)6]3+, the first step in the photoreaction in
aqueous solution involves photoaquation of one of the ammonia ligands to give
[Cr(NH3)5(H2O)]3+.

• For the corresponding hexacoordinated tris chelated complex [Cr(en)3]3+, the initial
photoreaction leads to substitution at one of the coordination positions to give
[Cr(en)2(enH)(H2O)]4+. This photoreaction involves dissociation of one end of a
coordinated ethylenediamine, followed by protonation of the nitrogen on the free "hinged"
ethylenediamine arm of the chelate.

• This "hinging" reaction is then followed by a second photoaquation step to give

[Cr(en)2(H2O)2]3+, a reaction that results in displacement of the monodentate enH ligand
by water.
• The quantum yields for the different complexes cover a relatively small numerical range,
which is indicative of a similar photoaquation mechanism for all of these different complexes.

Complexes Quantum Yield

[Cr(H2O)6]3+ 0.02
[Cr(NH3)6]3+ 0.3
[Cr(en)3]3+ 0.37
[Cr(CN)6]3- 0.12
[Cr(NCS)6]3- 0.26
[Cr(urea)6]3+ 0.10
[Cr(oxalate)3]3- 0.09
• Mixed-ligand complexes of chromium(III) also undergo photoaquation reactions.

• Under thermal conditions, aquation of the halide ion (X-) is the preferred pathway.

• Under the influence of light, photoaquation of an ammine ligand is the preferred pathway. A
classic example of a Cr(III) photosubstitution is the well-studied complex, [Cr(NH3)5CI]2+,
for which NH, photoaquation is the principal result of excitation of ligand-field bands, and
C1- aquation represents only about 2% of the overall total, The stereochemical origin of the
labilized NH, is trans to the coordinated C1- as shown by isotope-labeling experiments,
although the final reaction product has the cis configuration’:
• These data for [CrX(NH3)5]2+ (X = CI, Br, NCS) show that the quantum yields for ammine
photoaquation are approximately two orders of magnitude larger than are the corresponding
quantum yields for the photoaquation of the anion (X-).

Complex ɸ (NH3) ɸ (X-)

[CrCl(NH3)5]2+ 0.36 0.005
[CrBr(NH3)5]2+ 0.34 0.009
[Cr(NCS)(NH3)5]2+ 0.47 0.02
2. Photoracemization Reactions

Tris-chelate complexes of kinetically inert transition metal ions can be resolved into d and l
optical isomers. Under the influence of light, it is possible to cause racemization.

In this process the symmetry properties of the two enantiomers leads to an identical
quantum yield for the interconversion between the d and I forms The two mechanisms that
cause racemization of [Cr(en)3]3+ are (a) the "twist" mechanism in which a pseudorotation
causes racemization without changing the coordination sphere at chromium(III), and (b) the
"bond rupture" mechanism in which a bond breaks and racemization occurs either before or
during reformation of the bond.
3. Photosubstitution Reactions

• Chromium(III) complexes also undergo photoanation reactions. When aqueous solutions of

[Cr(H2O)6]3+ are photolyzed in the wavelength range of 400-575 nm in the presence of Cl- or
SCN- ion, replacement of a water molecule by the anionic ligand occurs.

• A comparative study of the photoaquation and photoanation reactions has been carried out by
photolyzing [Cr(NH3)6]3+" in an aqueous solution containing added chloride ion. Aquation
and anation therefore only compete with each other for the vacant coordination position in
[Cr(NH3)5]3+ that is formed by the photodissociation of an ammonia molecule. Since the
lowest excited quartet state that leads to photodissociation is very short-lived (τ < 10-10 s),
only those molecules present in the vicinity of the first coordination sphere of the complex
will effectively compete with the re-entry of the photodissociated ammonia molecule.

• An associative mechanism involving a heptacoordinate has also been proposed to explain the
stereochemical specificity in the photoaquation of substituted ammine complexes, and an
alternative suggestion has been made that an interchange mechanism is involved, which is
characterized by a hexacoordinate activated complex that is reached after the labilized ligand
has been expelled.
• Photoaquation can also be accompanied by isomerization of the metal complex. An example
is found in the photochemistry of cis-[Cr(en)2(OH)2]+ where both photoisomerization to
trans-[Cr(en)2(OH)2]+ and photoaquation to [Cr(en)2(OH)2(H2O)]+ are observed.
 PHOTOREACTIONS OF
COMPLEXES OF COBALT(III)
 PHOTOREACTIONS OF COMPLEXES OF COBALT(III)

• In cobalt(III) complexes, the lAlg ground state comes from the t26g electronic configuration,
while the low-lying ligand field excited states 3Tlg, 3T2g, 1T1g, and 1T2g result from the t25geg1
configuration. In addition, there is a 5T2g state that arises from the t24geg2 configuration. This
quintet state lies above the 3Tlg state for cobalt(III) complexes in a strong ligand field. For
complexes such as [Co(NH3)6]3+ that have a smaller ligand field strength, this ordering of
states may, however, be reversed. Some support for this premise that the ordering of states
may be ligand-dependent comes from the observation that whereas [Co(CN)6]3- shows a
phosphorescence due to the 3Tlg to lAlg transition, CO(NH3)~+ is non-emissive
1. Photosubstitution and Photoredox Reactions

• The major photochemical pathway for cobalt(Ill) complexes in solution is substitution.

• This difference can be explained on the basis of the excited states of the two sets of
complexes. Thus, while the lowest excited state of the hexacyano complexes have triplet
character, that of the hexaammine complex has quintet character. This difference results
from the relative ligand field strengths of the ammine and the cyanide ligands. The
independence of the quantum yield with incident wavelength for [Co(CN)6]3- in the ligand
field region can be explained on the basis of an intersystem crossing to the lowest
wavelength triplet occurring with a quantum yield of near unity. This premise has been
tested by showing that the quantum yields for photoaquation at 365 nm and 405 nm are
unchanged. In the former case the pathway involves excitation to a singlet state, followed
by intersystem crossing to a triplet, whereas in the latter case the mechanism involves
direct excitation to the triplet.
• Irradiation at 254 run into the charge transfer band of the cobalt(III) complex [Co(NH3)6]3+
results in photoredox reactions to give cobalt(II) complexes. The quantum yield for
irradiation into the charge transfer band at 254 nm is 0.16, which is considerably larger
than the corresponding photosubstitution quantum yield for irradiation into the ligand field
band. This quantum yield at 254 nm is independent of the pH of the solution, and it does not
depend on the concentration of either the complex or a non-coordinating ion such as
perchlorate. The quantum yield increases slightly with temperature, and also increases when
chloride ion is added to the solution. The overall reaction is

• Photolysis of the mixed-ligand complex ions Co(CN)5X]n- [where, X is CN-. N3-, Br-, OH-
(n = 3) and H2O (n = 2)] in the presence of thiocyanate ion gives primarily the aquation
product [Co(CN)5(H2O)]2-, along with the linkage isomers of the thiocyanate
substitution product.
• The favoring of S-coordination by the photochemical intermediate supports the view that a
species of greater polarizability is involved in the photochemical reaction. Such a situation
can arise with a 5-coordinate intermediate. If the photochemical intermediate reacts with
thiocyanate ion while still in the triplet excited state, this t2get state can be expected to
show some selectivity for sulfur coordination. Such a situation arises from the fact that the
excited state will be more polarizable than the ground state, and also that the frontier
orbitals of the excited state can extend further to react with the sulfur lone pair at longer
range than the equivalent lone pair on nitrogen
2. Photoisomerization Reactions

• Irradiation of cis-[CoCl2(en)2]+ in methanol solution into the first charge transfer band
results in isomerization to trans-CoCl2(en)2+.

• Isomerization of cobalt(III) complexes has been explained on the basis of the angular
overlap model. This model is based on the assumption that the photosubstitution in the
complex [MA4XY] occurs by loss of Y in the lowest triplet state. This loss of Y leads to
the formation of an intermediate 5-coordinated structure where the inter conversions
\ between apical and equatorial positions are separated by a low-activation barrier via the
trigonal bipyramidal structure.

• When X is a poorer a donor than A, and the metal-to-ligand n-bonding is minimal, the
trans structure is favored, and the barrier to cis-to-trans isomerization is low as compared
to the triplet to singlet deactivation rate constant. Thus, trans-cis isomerization is expected
when X is a better a donor than A in trans-M~Y.
• Confirmation of this approach is shown in the photochemistry of trans-[Co(en)2(CN)Cl)]+
and trans-[Co(en)2(CN)H2O]2+. Loss of chloride ion (¢J = 10-2) from Co(en)2(CN)Cl]+ or
water from trans-[Co(en)2(CN)H2O]2+ leads to the same square pyramidal intermediate
[Co(en)2(CN)]+, where the cyanide ligand is trans to the vacant site. In each case the
photolysis product is cis-[Co(en)2(CN)H2O]2+, which supports the angular overlap model
of excited state reactivity.

• Photo induced linkage isomerization of cobalt(III) ammine complexes has also been
observed when one of the ligands is ambidentate.

• These photoisomerization reactions are believed to proceed via a pathway where

irradiation leads to a thermally equilibrated LMCT excited state. In this excited state, the
complex dissociates to give the radical pair.
• For the thiocyanate complex the photoisomerization reaction of [Co(NH3)5SCN]2+ to
[Co(NH3)5NCS]2+ is not reversible, and [Co(NH3)5NCS]2+ does not photoisomerize to
[Co(NH3)5SCN]2+.

• A plausible explanation for this observation is that radical recombination proceeds in

two steps. In the first step a precursor complex is formed between [Co(NH3)5]2+ and
the thiocyanate radical, and in the second step electron transfer occurs within the precursor
complex. The stability of this inner-sphere precursor complex is related to the bonding in
the thermally equilibrated LMCT excited state of the parent complex. Since, the LMCT
excited state formed from Co(NH3)5NCS2+ is more strongly bound than the LMCT excited
state formed from Co(NH3)5SCN2+, the electron transfer precursor complexes formed from
identical radical pairs will favor the more strongly bound N-bonded isomer rather than the
more weakly bound S-bonded precursor complex.
 ADAMSON’S RULE

 From observations of photoreactions of chromium(III) it has been generally found that

the selectivity of the substitution pathways leading to the replacement of different
ligands can be explained on the basis of two rules. These rules, which are commonly
called Adamson's rules, can be expressed as follows:

1. For six ligands lying in pairs along three mutually perpendicular axes, the axis having
the weakest average ligand field strength will be the one labilized, and the total quantum
yield will approximate that for an Oh complex of the same average ligand field.

2. When the labilized axis has different ligands, the one that preferentially aquates is the
one that has the greater field strength.

 For other octahedral complexes such as Cr(NH3)63+, the first step in the photoreaction
in aqueous solution involves photoaquation of one of the ammonia ligands to give
Cr(NH3)5(H2O)3+
 Mixed-ligand complexes of chromium(III) also undergo photoaquation reactions. In
general, two or more photoreactions occur simultaneously, and the predominant product
from the photochemical reaction may be different from the product that is obtained under
thermal conditions.

 A similar regioselective reaction, but with the reverse selectivity, is found for the analogous
chromium(III) ammine complexes CrX2(NH3)4. As an example it is found that, whereas the
quantum yield for ammine photoaquation in the chloro complex trans-CrCl2(NH3)4 is
0.003, the quantum yield for photoaquation of the chloride ion in this complex is 0.44. This
photoreaction provides a good example of Adamson's rules because the lowest ligand field
in trans-CrCl2(NH3)4 is along the CI-Cr-CI axis, and the preferred mode of photoaquation
is replacement of a chloride ion.

 Exceptions can occur when other factors become dominant. Such is the case for the
photoaquation of trans-Cr(1,3-diaminopropane)2(CN)2+ where both cyanide ion and the
chelating diamine are photoaquated. Although the loss of CN- is not predicted by
photochemical theory, its photoaquation is possibly due to the ligand interactions
becoming an important factor.
References:

1. J.J. Zuckerman Inorganic Reactions and Methods, Volume 15, Electron-Transfer and
Electrochemical Reactions; Photochemical and Other Energized Reaction.

2. E. Zinato, P. Riccieri, A. W. Adamson, J. Am. Chem. Soc., 96 375 (1974).

3. M. F. Manfrin, L. Moggi, V. Balzani, Inorg. Chem., 10, 207 (1971).

4. W. Adamson, Photochemistry of Transition Metal Coordination Compounds,

5. D. M. Roundhill, Photochemistry of Complexes of First-Row Transition Metals

(Photochemistry and Photophysics of Metal Complexes) © Springer Science + Business
Media New York 1994.

6. W. Adamson, Photosubstitution Reactions of Some Cr(III) complexes.