Enantioselective Luminescence Quenching of DNA Light-Switch [Ru(phen)_2dppz]~(2+) by Electron Transfer to Structural Homologue [Ru(phendione)_2dppz]~(2+)

摘要

The quenching of the luminescence of [Ru(phen)_2dppz]~(2+) by structural homologue [Ru(phendione)_2dppz]~(2+),when both complexes are bound to DNA,has been studied for all four combinations of A and A enantiomers.Flow linear dichroism spectroscopy (LD) indicates similar binding geometries for all the four compounds,with the dppz ligand fully intercalated between the DNA base pairs.A difference in the LD spectrum observed for the lowest-energy MLCT transition suggests that a transition,potentially related to the final localization of the excited electron to the dppz ligand in [Ru(phen)_2dppz]~(2+),is overlaid by an orthogonally polarized transition in [Ru(phendione)_2dppz]~(2+).This would be consistent with a low-lying LUMO of the phendione moiety of [Ru(phendione)_2dppz]~(2+) that can accept the excited electron from [Ru(phen)_2dppz]~(2+),thereby quenching the emission of the latter.The lifetime of excited A-[Ru(phen)_2dppz]~(2+) is decreased moderately,from 664 to 427 ns,when bound simultaneously with the phendione complex to DNA.The 108 ns lifetime of opposite enantiomer,A-[Ru(phen)_2dppz]~(2+),is only shortened to 94 ns.These results are consistent with an average rate constant for electron transfer of approximately 1-10~6 s~(-1) between the phenanthroline- and phendione-ruthenium complexes.At binding ratios close to saturation of DNA,the total emission of the two enantiomers is lowered equally much,but for the A enantiomer,this is not paralleled by a decrease in luminescence lifetime.A binding isotherm simulation based on a generalized McGhee-von Hippel approach shows that the A enantiomer binds approximately 3 times stronger to DNA both for [Ru(phendione)_2dppz]~(2+) and [Ru(phen)_2dppz]~(2+).This explains the similar decrease in total emission,without the parallel decrease in lifetime for the A enantiomer.The simulation also does not indicate any significant binding cooperativity,in contrast to the case when DELTA-[Rh(phi)_2bipy]~(3+) is used as quencher.The very slow electron transfer from [Ru-(phen)_2dppz]~(2+) to [Ru(phendione)_2dppz]~(2+),compared to the case when [Rh(phi)_2phen]~(3+) is the acceptor,can be explained by a much smaller driving free-energy difference.