ChemInform Abstract: Ru(II) Polypyridine Complexes: Photophysics, Photochemistry, Electrochemistry, and Chemiluminescence

Juris, Alberto; Balzani, Vincenzo; Barigelletti, F.; Campagna, Sebastiano; Belser, Peter; Zelewsky, Alex von

doi:10.1002/chin.198831377

Cited by 188 publications

(394 citation statements)

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“…The electrolyte used was an aqueous phosphate buffer solution (0.1 m,p H7.2) or triflic acid (0.1 m,p H1.0). All potentials are reported vs. NHE using the [Ru(bpy) 3 ] 3 + /[Ru(bpy) 3 ] 2 + couple (E 1/2 = 1.26 Vv s. NHE [19] )a sastandard.…”

Section: Electrochemistrymentioning

confidence: 99%

Chemical and Photochemical Water Oxidation Mediated by an Efficient Single‐Site Ruthenium Catalyst

et al. 2016

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Water oxidation is a fundamental step in artificial photosynthesis for solar fuels production. In this study, we report a single‐site Ru‐based water oxidation catalyst, housing a dicarboxylate‐benzimidazole ligand, that mediates both chemical and light‐driven oxidation of water efficiently under neutral conditions. The importance of the incorporation of the negatively charged ligand framework is manifested in the low redox potentials of the developed complex, which allows water oxidation to be driven by the mild one‐electron oxidant [Ru(bpy)3]3+ (bpy=2,2’‐bipyridine). Furthermore, combined experimental and DFT studies provide insight into the mechanistic details of the catalytic cycle.

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Section: Electrochemistrymentioning

confidence: 99%

Chemical and Photochemical Water Oxidation Mediated by an Efficient Single‐Site Ruthenium Catalyst

et al. 2016

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“…The complexes are water-soluble, coordinatively saturated, and inert to substitution. Polypyridyl complexes of ruthenium-(11) furthermore are intensely colored owing to a wellcharacterized, localized metal-to-ligand charge transfer (MLCT) transition (Juris et al, 1988). Importantly, this transition is perturbed on binding to DNA, providing a sensitive spectroscopic handle for interactions with nucleic acids (Pyle et al, 1989).…”

mentioning

confidence: 99%

Characterization of dipyridophenazine complexes of ruthenium(II): The light switch effect as a function of nucleic acid sequence and conformation

Jenkins¹,

Friedman²,

Turro³

et al. 1992

Biochemistry

440

368

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Spectroscopic parameters for two novel ruthenium complexes on binding to nucleic acids of varying sequences and conformations have been determined. These complexes, R~( b p y )~d p p z~+ and Ru(phen)zdppz2+ (bpy = 2,2'-bipyridine; phen = 1,lO-phenanthroline; dppz = dipyrido[3,2:a-2',3':~]-phenazine) serve as "molecular light switches" for DNA, displaying no photoluminescence in aqueous solution but luminescing intensely in the presence of DNA. The luminescent enhancement observed upon binding is attributed to the sensitivity of the excited state to quenching by water; in DNA, the metal complex, upon intercalation into the helix, is protected from the aqueous solvent, thereby preserving the luminescence. Correlations between the extent of protection (depending upon the DNA conformation) and the luminescence parameters are observed. Indeed, the strongest luminescent enhancement is observed for intercalation into DNA conformations which afford the greatest amount of overlap with access from the major groove, such as in triple helices. Differences are observed in the luminescent parameters between the two complexes which also correlate with the level of water protection. In the presence of nucleic acids, both complexes exhibit biexponential decays in emission. Quenching studies are consistent with two intercalative binding modes for the dppz ligand from the major groove: one in which the metal-phenazine axis lies along the DNA dyad axis and another where the metal-phenazine axis lies almost perpendicular to the DNA dyad axis. Ru(bpy)zdppz2+ and Ru(phen)2dppzz+ are shown here to be unique reporters of nucleic acid structures and may become valuable in the design of new diagnostics for DNA.Considerable attention has been given to the design of small molecules that bind to DNA with site selectivity so as to develop novel therapeutics and chemical probes for nucleic acid sites and structures, as well as novel diagnostic agents targeted to double-helical DNA (Pyle & Dervan, 1986;Moser & Dervan, 1987;Hecht, 1986;Tullius, 1988). Our laboratory has focused in part on the development of transitionmetal complexes as probes of nucleic acid structure (Chow & Barton, 1992;Mei & Barton, 1986;Kirshenbaum et al., 1988;Barton, 1986). We have found that ruthenium complexes serve as very sensitive luminescent reporters of DNA in aqueous solution and may become particularly useful in developing new diagnostics.Ruthenium complexes are ideally suited for application as sensitive noncovalent probes for polymer structure. The complexes are water-soluble, coordinatively saturated, and inert to substitution. Polypyridyl complexes of ruthenium-(11) furthermore are intensely colored owing to a wellcharacterized, localized metal-to-ligand charge transfer (MLCT) transition (Juris et al., 1988). Importantly, this transition is perturbed on binding to DNA, providing a sensitive spectroscopic handle for interactions with nucleic acids (Pyle et al., 1989). Tris( 1 ,IO-phenanthroline)ruthenium(II), Ru-(phen)j2+, has been established, primar...

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“…The complexes of the [Ru(bpy) 3 ] 2+ family (bpy= 2,2-bipyridine) show a unique combination of photophysical and redox properties (Juris et al 1988). These properties can be significantly modified by the functionalization of the bpy ligand with dendrimeric arms (Issberner et al 1997).…”

Section: Metal Complexes Containing Dendritic Bipyridine Ligandsmentioning

confidence: 99%

Supramolecular effects in dendritic systems containing photoactive groups

Azzellini

2000

An. Acad. Bras. Ciênc.

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In this article are described dendritic structures containing photoactive groups at the surface or in the core. The observed supramolecular effects can be attributed to the nature of the photoactive group and their location in the dendritic architecture. The peripheric azobenzene groups in these dendrimeric compounds can be regarded as single residues that retain the spectroscopic and photochemical properties of free azobenzene moiety. The E and Z forms of higher generation dendrimer, functionalized with azobenzene groups, show different host ability towards eosin dye, suggesting the possibility of using such dendrimer in photocontrolled host-guest systems. The photophysical properties of many dendritic-bipyridine ruthenium complexes have been investigated. Particularly in aerated medium more intense emission and a longer excited-state lifetime are observed as compared to the parent unsubstituted bipyridine ruthenium complexes. These differences can be attributed to a shielding effect towards dioxygen quenching originated by the dendritic branches.

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ChemInform Abstract: Ru(II) Polypyridine Complexes: Photophysics, Photochemistry, Electrochemistry, and Chemiluminescence

Cited by 188 publications

References 1 publication

Chemical and Photochemical Water Oxidation Mediated by an Efficient Single‐Site Ruthenium Catalyst

Chemical and Photochemical Water Oxidation Mediated by an Efficient Single‐Site Ruthenium Catalyst

Characterization of dipyridophenazine complexes of ruthenium(II): The light switch effect as a function of nucleic acid sequence and conformation

Supramolecular effects in dendritic systems containing photoactive groups

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