inorganic chemistry

Interestingly, this effect was inversely proportional to the energy
of the^3 MLCT state (E 00 in Tables III and IV). Therefore, the
energy gap between the ground state and the transition state of
the photochemical ligand substitution reaction (E 00 þDG6¼) is
not affected by the modification of the bipyridine ligand as much

1500

260

0.0

0.1

Quantum yield

0.2

0.3

0.4

0.5

280 300

te

Fe

Fr

320 340

0

500 Lifetime (ns)

1000

T (K)

FIG. 11. Temperature dependence of the emission yield (Fe), the life-
time (te), and the quantum yield of the photochemical ligand substitu-
tion reaction (Fr) of 3a in a degassed CH 3 CN solution. Copyright
2002 American Chemical Society.

3.2 3.4 3.6 3.8

T–1 (10^3 K–1)

2.8 3.0

8

10

In {(

fe

/te

) (s

–1

)}, In{(

fr

/t

) (se

–1

)}

12

In kr

In ke

14

16

FIG. 12. Arrhenius plots of the radiative decay rate (ke) and the reac-

tion rate of the photochemical ligand substitution reaction (kr) of3ain

a degassed CH 3 CN solution. Copyright 2002 American Chemical

Society.

156 HIROYUKI TAKEDAet al.