Mixed-ligand complexes of ruthenium(II) containing new photoactive or electroactive ligands: synthesis, spectral characterization and DNA interactions

Ghosh, Tamal ; Maiya, Bhaskar G. ; Samanta, Anunay ; Shukla, Atindra D. ; Amilan Jose, D. ; Krishna Kumar, D. ; Das, Amitava (2005) Mixed-ligand complexes of ruthenium(II) containing new photoactive or electroactive ligands: synthesis, spectral characterization and DNA interactions Journal of Biological Inorganic Chemistry, 10 (5). pp. 496-508. ISSN 0949-8257

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Official URL: http://www.springerlink.com/content/q8256282x86736...

Related URL: http://dx.doi.org/10.1007/s00775-005-0660-6


Mixed-ligand ruthenium(II) complexes of three photoactive ligands, viz., (E)-1-[2-(4-methyl-2-pyridyl)-4-pyridyl]-2-(1-naphthyl)-1-ethene (mppne), (E)-1-(9-anthryl)-2-[2-(4-methyl-2-pyridyl)-4-pyridyl]-1-ethene (mppae) and (E)-1-[2-(4-methyl-2-pyridyl)-4-pyridyl]-2-(1-pyrenyl)-1-ethene (mpppe), in which a 2,2'-bipyridyl unit is linked via an ethylinic linkage to either a naphthalene, an anthracene or a pyrene chromophore and three electroactive ligands, viz., 4-(4-pyridyl)-1,2-benzenediol (catpy), 5,6-dihydroxy-1,10-phenanthroline (catphen) and 1,2-benzenediol (cat), were synthesized in good to moderate yields. Complexes [Ru(bpy)2(mppne)]2+ (bpy is 2, 2'-bipyridyl), [Ru(bpy)2(mppae)]2+, [Ru(bpy)2(mpppe)]2+, [Ru(bpy)2(sq-py)]+, [Ru(bpy)2(sq-phen)]+ and [Ru(phen)2(bsq)]+ (phen is 1,10-phenanthroline) were fully characterized by elemental analysis, IR, 1H NMR, fast-atom bombardment or electron-impact mass, UV-vis and cyclic voltammetric methods. In the latter three complexes, the ligands catpy, catphen and cat are actually bound to the metal center as the corresponding semiquinone species, viz., 4-(4-pyridyl)-1,2-benzenedioleto(+I) (sq-py), 1,10-phenanthroline-5,6-dioleto(+I) (sq-phen) and 1,2-benzenedioleto(+I) (bsq), thus making the overall charge of the complexes formally equal to + 1 in each case. These three complexes are electron paramagnetic resonance active and exhibit an intense absorption band between 941 and 958 nm owing to metal-to-ligand charge transfer (MLCT, dRusq) transitions. The other three ruthenium(II) complexes containing three photoactive ligands, mppne, mppae and mpppe, exhibit MLCT (dRubpy ) bands in the 454-461-nm region and are diamagnetic. These can be characterized by the 1H NMR method. [Ru(bpy)2(mppne)]2+, [Ru(bpy)2(mppae)]2+ and [Ru(bpy)2(mpppe)]2+ exhibit redox waves corresponding to the RuIII/RuII couple along with the expected ligand (bpy and substituted bpy) based ones in their cyclic and differential pulse voltammograms (CH3CN, 0.1 M tetrabutylammonium hexafluorophosphate)-corresponding voltammograms of [Ru(bpy)2(sq-py)]+, [Ru(bpy)2(sq-phen)]+ and [Ru(phen)2(bsq)]+ are mainly characterized by waves corresponding to the quinone/semiquinone (q/sq) and semiquinone/1,2-diol (sq/cat) redox processes. The results of absorption and fluorescence titration as well as thermal denaturation studies reveal that [Ru(bpy)2(mppne)]2+ and [Ru(bpy)2(mppae)]2+ are moderate-to-strong binders of calf thymus DNA with binding constants ranging from 105 to 106 M−1. Under the identical conditions of drug and light dose, the DNA (supercoiled pBR 322) photocleavage activities of these two complexes follow the order:[Ru(bpy)2(mppne)]2+>[Ru(bpy)2(mppae)]2+, although the emission quantum yields follow the reverse order. The other ruthenium(II) complexes containing the semiquinone-based ligands are found to be nonluminescent and inefficient photocleavage agents of DNA. However, experiments shows that [Ru(bpy)2(sq)]+-based complexes oxidize the sugar unit and could be used as mild oxidants for the sugar moiety of DNA. Possible explanations for these observations are presented.

Item Type:Article
Source:Copyright of this article belongs to Springer.
Keywords:Ru(II) Complexes; DNA Binding; DNA Photocleavage; Oxidation of Sugar Unit in DNA; Semiquinone
ID Code:51614
Deposited On:29 Jul 2011 04:03
Last Modified:17 Jul 2012 05:16

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