ON THE NATURE OF EXCITED STATES IN RUTHENIUM COMPLEXES:TOWARDS RENEWABLE ENERGYbyRYAN ANTONIO THOMASAugust 2015 Advisors: Prof. John F. Endicott and Prof. Cláudio N. Verani Major: Chemistry (Analytical) Degree: Doctor of Philosophy The 77 K radiative properties (spectra, quantum yields and lifetimes) of ruthenium-polypyridyl complexes are investigated to better understand th...

Transition metal complexes provide a promising avenue for designing new therapeutic and diagnostic agents. In particular, ruthenium(II) polypyridyl complexes are useful for studying cellular uptake, due to their easy synthesis and unique photophysical properties. Dyes are frequently combined with material substrates to modulate their properties, enhance stability, reduce toxicity, and improve d...

We describe a crystal structure, at atomic resolution (1.1 Å, 100 K), of a ruthenium polypyridyl complex bound to duplex DNA, in which one ligand acts as a wedge in the minor groove, resulting in the 51° kinking of the double helix. The complex cation Λ-[Ru(1,4,5,8-tetraazaphenanthrene)(2)(dipyridophenazine)](2+) crystallizes in a 11 ratio with the oligonucleotide d(TCGGCGCCGA) in the presence ...

There has been a recent surge of interest in the use of transition metal polypyridyl complexes as visible light-absorbing photocatalysts for synthetic applications. Among the most attractive features of this approach is the availability of many known complexes with well-characterized photophysical and electrochemical properties. In particular, Ru(bpz)3 (2+) is a powerful photooxidant that has p...

(R)-4-(alkylthiomethyl)-5,5-dimethyl-2-(2'-hydroxyphenyl)-2-oxazolines are demonstrated to be highly suitable chiral auxiliaries for the two-step conversion of the half-sandwich complex [Ru(η(6)-C6H6)(bpy)Cl]Cl, bpy = 2,2'-bipyridine, into Δ-configured ruthenium polypyridyl complexes. The tailored thioether substituent at the oxazoline ring is essential for this conversion and not only promotes...

A first investigation into the application of a luminescent osmium(ii) bipyridine complex to live cell imaging is presented. Osmium(ii) (bis-2,2-bipyridyl)-2(4-carboxylphenyl) imidazo[4,5f][1,10]phenanthroline was prepared and conjugated to octaarginine, a cell penetrating peptide. The photophysics, cell uptake and cytotoxicity of this osmium complex conjugate were performed and compared with i...