BARC/PUB/09/0305

 
  Synthesis, characterization and redox chemistry of Ru(II) complexes of N-methyl pyridyl quinoxaline  
     
 
Author(s)

Kulkarni, M. S.; Kumbhar, A. S.; Mohan, H.; Rao, B. S. M.

ABSTRACT

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 pp* 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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