By Boschke F.L.
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Extra resources for Organic Chemistry and Theory
The quenchers used were pentaamine Co(III) complexes which are known to decompose upon one electron reduction: *Ru(bpy)] + + Co(NHa)sBr 2+ Co(NHs) s Br+ , Ru(bpy) 3+ + Co(NHa)sBr + 9 Co 2+ + 5 NH s + Br- (54) (55) The interpretation given by Gafney and Adamson was questioned by Natarajan and Endicott I IS, 116), who had previously suggested an energy transfer mechanism for the Ru(bpy)~ + sensitized photodecomposition of Co(HEDTA)X- complexes 4, i 17-119). However, definite experimental evidence of the reducing properties of *Ru(bpy) 2+ was obtained in several laboratories before the end of 197412o-123).
22. Plot of log kq vs. &G~ for the electron transfer quenching of *Cr(bpy)3+ (A, zx), , . Ru(bpy)32 + (m) and , lr(5,6-Me2phen)2Cl+2 (o, o) by aromatic quenchers (full points), and aliphatic amines (empty points) 54). The insert reports the data for the quenching of *Ru(bpy)32+ and *Ru(4,4'-Me2bpy)2§ Cr(bpy)33+,Ru(bpy)]+, Os(bpy)33+and Ru(a,4'-Me2bpy)33+87). Note the expanded ordinate scale in the insert oxidized quencher could have been obtained (Fig. 11), which would imply a high rate constant even according to the Marcus theory.
7 V Fig. 20. Plots of log k, vs the excited state energy (a) and the reduction potential (b) of *M in the quenching of *M I~y Fe(CN)46 - *Cr(bpy) 3§ 3 , ,, *Ru(bpy) 2+ 3 , 9, *Os(bpy) 2+, 3 9 1601 Energy v s electron transfer quenching of *Ru(bpy) 2+ and *Ru(phen) 2+ by a number of inorganic species is discussed in Ref. 161. Oxygen quenching of excited Ru(bpy) 2+ and other polypyridine complexes yields singlet oxygen In' 16s), but the reaction mechanism presents some complicated aspects in acid medium 169) and an electron transfer quenching mechanism (producing 0~-), followed by a back electron transfer reaction leading to 102 is also plausible 13, xs4, 1s61 Usually the existence, and thus the quenching, of an excited state is proved by means of luminescence measurements.
Organic Chemistry and Theory by Boschke F.L.