Excited States of Ru(bipy)32+

Kasha’s rule: Photon emission (fluorescence or phosphorescence) occurs in

appreciable yield only from the lowest excited state of a given multiplicity.

3MLCT: phosphorescence, bimolecular or delayed reaction (photoredox reaction)

3MC: radiationless decay, ligand dissociation (photosubstitution/photorearrangement)
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 Excited States of Ru(bipy)32+

§ The MC excited states of d6 octahedral complexes are strongly displaced with respect
to the ground-state geometry along metal-ligand vibration coordinates.

§ When the lowest excited state is 3MC, it undergoes fast radiationless deactivation
to the ground state and/or ligand dissociation reactions. As a result, at room
temperature the excited-state lifetime is very short, no luminescence emission can
be observed, and very rarely bimolecular reactions can take place.

§ LC and MLCT excited states are usually not strongly displaced compared to the
ground-state geometry.

§ Thus, when the lowest excited state is LC or MLCT, it does not undergo fast
radiationless decay to the ground state and luminescence can usually be observed.

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 Photosubstitution and Photoracemization Processes

§ Although [Ru(bpy)3]2+ is normally considered as photochemically inert toward

ligand substitution, this is not strictly true.

§ In aqueous solution, photoaquation leads to formation of cis- and trans-

[Ru(bpy)2(OH2)2]2+. The quantum yields are in the range 10–5–10–3.

§ In chlorinated solvents such as CH2Cl2, photoexcitation of [Ru(bpy)3]X2

(X = Cl–, Br–, NCS–) gives rise to [Ru(bpy)2X2] as the final product. The quantum yields
are in the range 10–1–10–2.

§ The PF6- salt is photoinert.

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Mechanism of Photosubstitution

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 Mechanism of Photosubstitution

§ Mechanism: Thermally activated formation of a 3MC excited state leads to the

cleavage of a Ru–N bond, with formation of a five-coordinate square pyramidal
species.

§ In the absence of coordinating ions, as with the PF6- salt, this square pyramidal
species returns to [Ru(bpy)3]2+. When coordinating anions are present, as in the Cl–
salt, a hexacoordinated monodentate bpy intermediate is formed. Once formed, this
monodentate bpy species can undergo loss of bpy and formation of [Ru(bpy)2X2], or a
“self-annealing” process (chelate ring closure), with re-formation of [Ru(bpy)3]2+.

§ The “selfannealing” protective step is favored in aqueous solution, presumably

because of stabilization of the cationic [Ru(bpy)3]2+ species, whereas formation of
neutral [Ru(bpy)2X2] complexes is favored in low-polarity solvents.

§ Photoracemization of [Ru(bpy)3]2+ occurs by a rearrangement of the square

pyramidal primary photoproduct into a trigonal bipyramidal intermediate which can
lead back to either the Δ or the Λ isomer.

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 Photosubstitution and Photoracemization Processes

§ Ligand photodissociation is a drawback for the use of [Ru(bpy)3]2+ in practical

applications. To avoid ligand photodissociation one should prevent population of
3MC and/or ligand dissociation from 3MC.

§ Population of 3MC can be prevented or at least reduced by:

1) addition of sufficient quencher to capture 3MLCT before surface crossing to 3MC
can occur,
2) increasing the energy gap between 3MLCT and 3MC,
3) working at low temperature,
4) increasing pressure.

§ Ligand dissociation from 3MC can also be reduced by:

5) avoiding coordinating anions in solvent of low dielectric constant,
6) linking together the three bpy ligands so as to form a single caging ligand which
encapsulates the metal ion.

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 Quenching of Excited State by an Energy Transfer Reaction

§ Example: Energy transfer from (3CT) [Ru(bpy)3]2+ to [Cr(CN)6]3– was able to sensitize
the emission of the lowest excited state, 2Eg, of the Cr complex, but not the
photoaquation reaction.

§ Both reductive and oxidative ∗ [Ru(bpy)3]2+ electron transfer quenchings by

[Cr(CN)6]3– are thermodynamically forbidden because it is very difficult to reduce or
oxidize [Cr(CN)6]3–.

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 Quenching of Excited State by an Energy Transfer Reaction

[Cr(CN)6]3– Vs. [Cr(bpy)3]3+

§ In contrast to [Cr(CN)6]3–, [Cr(bpy)3]3+ can be very easily reduced and with this
quencher oxidative electron transfer predominates over energy transfer.

§ The converted energy cannot be stored but is immediately dissipated into heat
by the back electron transfer reaction.

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 Quenching of Excited State by an Electron Transfer Reaction

Oxidative Quenching
1)

2)

3) Methyl viologen (MV)

(N,N-dimethyl-4,4’-
bipyridinium cation

4)

Reductive Quenching

§ Back reactions lead to original products!