A series of metal complexes having the general formula
[Ru(bpy)n(mebpq+)3-n] (5-n)+ (n = 0, 1,2,3)(2,2'-bipyridine
(bpy) and/or 2-(N-methylpyridyl)3-pyridyl quinoxaline (mebpq+) were synthesized and characterized by optical, elemental analysis, NMR and electrochemical methods. The absorption spectra of complexes have bands in the UV region (≤350 nm) consisting of an intense
p→
p* transition due to the ligands
(e ~
105 dm3 mol-1 cm-1) and in the visible region dominated by MLCT
(dp
→ p*). The emission intensity is the least when ruthenium is fully coordinated to
mebpq+ and it increased 50 fold on going to [Ru(bpy)3]Cl2. Electrochemical data revealed that the
Ru(II)/Ru(III) oxidation peaks are in the range 1.31 to 1.76 V and the sequential replacement of bpy by
mebpq+ resulted in the increase of the oxidation potential. The reactions of oxidizing and reducing radicals (×OH, O×-,
N3 ×,
Cl2 ×- and
e-aq ) with these complexes were studied by pulse radiolysis. The
×OH radical reacts with all complexes at diffusion controlled rates and the k values increased from 6.2 to 9.8
x 109 dm3 mol-1 s-1 on going from
[Ru(bpy)3]Cl2 to [Ru(mebpq+)3](PF6)5. The rates of reaction of
e-aq with Ru(II) complexes are high (k »
1010 dm3 mol-1s-1) and the reaction leads to the formation of the radical anion of the bipyridine in
[Ru(bpy)3]Cl2 and tertiary quinoxaline radical in mixed complexes containing
mebpq+. The underlying reaction mechanism is discussed.
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