Experimental and theoretical study on DNA-binding and photocleavage properties of chiral complexes Δ- and Λ-[Ru(bpy)2L] (L = o-hpip, m-hpip and p-hpip)Electronic supplementary information (ESI) available: electronic spectra and photocleavage diagrams. See http://www.rsc.org/suppdata/dt/b2/b212443b/

Citations Over TimeTop 10% of 2003 papers

Abstract

In order to systematically perform an experimental and theoretical study on DNA-binding and photocleavage properties of chiral complexes Δ- and Λ-[Ru(bpy)2L] (L = o-hpip, m-hpip and p-hpip) on the basis of reported Δ- and Λ-[Ru(bpy)2(o-hpip)] (Δ-1 and Λ-1), a series of novel enantiomerically pure polypyridyl ruthenium(II) complexes, Δ- and Λ-[Ru(bpy)2(m-hpip)](PF6)2 (Δ-2 and Λ-2; bpy = 2,2′-bipyridine, m-hpip = 2-(3-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline), and Δ- and Λ-[Ru(bpy)2(p-hpip)](PF6)2 (Δ-3 and Λ-3, p-hpip = 2-(4-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline), have been synthesized and characterized by elemental analysis, 1H NMR, ESI-MS and CD spectra. The DNA-binding properties of these complexes have been investigated with UV-Vis, emission spectra, CD spectra and viscosity measurements. It is experimentally found that (1) both complexes [Ru(bpy)2(m-hpip)]2+2 and [Ru(bpy)2(p-hpip)]2+3 can bind to DNA with intercalation; (2) for complexes 2 and 3, a subtle but detectable difference was observed in the interaction of these isomers with CT-DNA. The DNA-binding of the Δ-isomer is stronger than that of Λ-isomer, whereas that of Λ-isomer is swifter. (3) Under irradiation with UV light, Ru(II) complexes 2 and 3 can promote almost complete conversion of pBR322 DNA from form I to form II at concentrations of 0.5, 1.0, 0.5, 1.0 (× 10−4M) for Δ-2, Λ-2, Δ-3 and Λ-3, respectively. On the other hand, theoretical calculations for these three isomer complexes have been carried out applying the density functional theory (DFT) method on the level of the B3LYP/LanL2DZ basis set. Some frontier molecular orbital energies and stereographs, as well as a schematic diagram of the energies and related 1MLCT transitions of [Ru(bpy)2L]2+ are presented, and applied to reasonably explain the obtained experimental regularities or trends in the DNA-binding strength or binding constants (Kb) and some spectral properties of the complexes.

Related Papers

• → Ligand control of metal oxidation states. Synthesis, characterization and cyclic voltammetric studies of a group of ruthenium phenolates(1996)18 cited
• THE FEATURES OF PROTEIN BINDING BY RUTHENIUM COMPLEXES: DOCKING, FORCE FIELD AND QM/MM STUDIES(2013)
• → ChemInform Abstract: Synthesis, Reactivities, and Structural Studies on High‐Valent Ruthenium Oxo Complexes. Ruthenium(IV), Ruthenium(V), and Ruthenium(VI) Oxo Complexes of Tertiary Amine Ligands.(1987)
• → Well-Defined Surface-Bonded Ruthenium Complexes with Molecular Nitrogen(1998)
• → ANALYSIS BY THE RFES METHOD OF CATALYTIC SYSTEMS BASED ON RUTHENIUM(2023)