Anionic ruthenium complexes, luminescence

The luminescence spectra of all receptors in CH3CN were found to be dramatically affected by the addition of acetate or chloride. While compound 19 exhibits an emission decrease, the other receptors 17,18 and 20 show a remarkable intensity increase (up to 500%) with a slight concomitant blue shift of the emission maximum (660 nm for 17). The anion-induced enhancement of luminescence intensity in the case of 17 is clearly due to the decrease of the electron transfer between the ruthenium(II) bipyridyl centre and the quinone moieties. Alternatively, receptors bearing ruthenium or rhenium complexes on the upper rim were also described [20]. 

Table I shows examples of the steady-state and time-resolved emission characteristics of [Ru(phen)2(dppz)]2+ upon binding to various DNAs. The time-resolved luminescence of DNA-bound Ru(II) is characterized by a biexponential decay, consistent with the presence of at least two binding modes for the complex (47, 48). Previous photophysical studies conducted with tris(phenanthroline)ruthenium(II) also showed biexponential decays in emission and led to the proposal of two non-covalent binding modes for the complex (i) a surface-bound mode in which the ancillary ligands of the metal complex rest against the minor groove of DNA and (ii) an intercalative stacking mode in which one of the ligands inserts partially between adjacent base pairs in the double helix (36, 37). In contrast, quenching studies using both cationic quenchers such as [Ru(NH3)6]3+ and anionic quenchers such as [Fe(CN)6]4 have indicated that for the dppz complex both binding modes...

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