Organic Chemistry and Theory by Boschke F.L.

By Boschke F.L.

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Os(bpy)~ § Fig. 18. Oxidation and reduction potentials in aqueous solution of the lowest excited state of some polypyridine complexes. 84 V. 86 V. Thus the excited state of this complex is a moderately strong oxidant and at the same time a strong reductant. If we take another complex, we will have different excited state redox properties because of different ground state redox properties and different excited state energies. For example, *Cr(bpy) 3§ (Fig. 18) is a very strong oxidant but a poor reductant.

However, it is not clear 214) how much o f this proceeds from an intermolecular route, since UO~ + is known to complex, for example, with aromatic amines. 3. Quenching by Metal Cations Quenching of*UO22§ b y metal cations has been studied by several authors 214' 236, 237) Some o f the results obtained have been collected in Table 5. It is evident that the absolute magnitudes o f the quenching constants and also the order o f the efficiencies o f the various quenchers given b y the two authors differ greatly.

Macero, D. : lnorg. Chem. 15, 2040 (1976); acetonitrile vs. Ag/AgC1. 17) Hughes, M. , Macero, D. : lnorg. Chem. 13, 2739 (1974); in water-ethanol 50%. 5417 ) -r5) (us) E0_o(M-*M) 4) (eV) ,,max*abs3x (am) EO'(M/M-) 2) (V) 1) Room temperature, aqueous solution, unless otherwise noted. 2) El/2 ' vs. NHE, unless otherwise noted. 3) Absorption maximum of the lowest energy spin-allowed transition. 4) Energy of the 0 - 0 transition of the emitting excited state. S) Emission lifetime in de-aerated solution.

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