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A senes of RU2(II,III) complexes containing the bulky carboxylate ligand 2,4,6- triisopropylbenzoate (TiPB) of form trans-[Ru2(TiPB)2(02CCH3)2X] [X = Cl 1, PF6 2] and [Ru2(TiPB)4X] [X = Cl 3, PF6 4] have been synthesised. The corresponding RU2(II,II) complexes trans-[Ru2(TiPB)2(02CCH3)2] 5 and [Ru2(TiPB)4] 6 were also isolated. The Ru-Ru bond length in the RU2(II,II) complex 6 [2.2425(6) A] is the shortest observed for a diruthenium tetracarboxylate and, surprisingly, is 0.014 A shorter than in the analogous RU2(II,III) complex 4, despite an increase in the formal bond order from 2.0 in the RU2(II,II) complex 6 to 2.5 in the RU2(II,III) complex 4. This is rationalised in terms of the extent of internal rotation about the RU2 core. This was supported by DFT calculations on the model complexes [RU2(02CH)4]OI+, that demonstrate the relationship between Ru-Ru bond length and internal rotation. The mixed carboxylate complexes trans-[Ru2(02CCH3)2(02CAr)2Cl] 7 and trans[ RU2(02CCH3)2(02CAr)2] 11 (02CAr 2,6-di(p-tolyl)benzoate) have been synthesised along with [Ru2(02CAr)4(CH2Cb)Cl] 9 and [RU2(02CAr)4] 12 complexes. The structure of 9 is a rare example of a structurally characterised dichloromethane complex. The bulky -02CAr ligand protects the axial positions from intermolecular interactions in the absence of strong nuc1eophiles for 9 and 12, and the effect this has on the electronic structure of the diruthenium core in these complexes was investigated. Complexes [RU2(,l1-0)2CU-TiPB)2(TiPB)2] and [RU2(,l1- OMe )2(,l1-TiPB)2(TiPB)2] were structurally characterised using crystals obtained from decomposition of [Ru2(TiPB)4] solutions. [RU2 TiPB)4] is capable of activating dioxygen, and can act as a biologically-inspired catalyst for the aerobic oxidation of alcohols to aldehydes. The synthesis of the diosmium tetracarboxylates [Os2(TiPB)4Cb] 15 and [Os2(TiPB)2(02CCH3)2Cb] 16 is also reported and the electronic structure of these complexes is probed with the aid of DFT calculations.

A Series of ruthenium(II)-(tpm)(dppz), (phen) and (dppn) complexes have been synthesised which have been designed to show binding to DNA. These complexes have been characterized by a wide range of techniques, including X-ray crystallography. The binding of the complexes with CT-DNA sequence has been studied using a variety of techniques, including, UV-Vis, luminescence and CD spectroscopy as well as viscometry. hi most of the cases, the metal complexes stabilise DNA, bind via intercalation and their binding affinities with CT-DNA are in the micromolar range. We have observed a remarkable modulation of the binding of our complexes to DNA by changing the ancillary ligands of the complex. As a comparison DNA binding properties of some Ru(II)-(tpy)(dppz) and Ru(II)-(tpy)(phen) complexes synthesised in the same way were also explored. These metal complexes stabilise DNA and viscosity measurements also shows intercalation between base pairs.

No description available.

The research reported in this thesis primarily focuses on the thermal and photochemical reactions of half-sandwich ruthenium complexes. The photochemical reactions employ the use of ex situ and in situ UV irradiation of the complexes. The latter of these techniques allows for samples to be irradiated within an NMR spectrometer, the principal method used to monitor reactions when highly unstable products result. The reactivity of [CpRu(PPh3)2Cl] towards a range of substrates is first described, where the thermal and photochemical reactions (applying the ex situ method) are contrasted. Replacement of PPh3 by a range of 2-electron donors, including CO, PEt3, ethene and tBuNC was achieved. Similar treatment is given to the complex, [CpRu(PPh3)2H]. However, this hydride complex proved to be slow to react and only minimal conversion to products was achieved, even using photochemical methods. The reactivity of CpRu(PPh3)2Me toward a range of 2 electron donors was considered in greater detail, particularly its ability to activate Si-H, H-H and C-H adducts under photochemical conditions. Low temperature photochemical techniques, using the in situ method, were employed to determine that both Si-H and C-H bond activation is undertaken by the fragment [CpRu(κ2-2-C6H4PPh2)]. This fragment was shown to activate the C-H bonds of solvent molecules, and form Ru(IV) complexes [CpRu(PPh3)(sol)(SiEt3)H] (where sol = C-H activated solvent, e.g. THF), which were stable at room temperature. The substitution of PPh3 occurs in an analogous fashion to that of the chloride derivative. However, the rate of conversion was increased but no evidence for migration of either CO or ethene into the RuMe bond was observed. The η3-coordinated complexes, [CpRu(PPh3)(η3-Si(Me2)-CH=CH2)], [CpRu(PPh3)(η3-CH2C2H3)], [CpRu(PPh3)(η3-CH2C6H5)] and [CpRu(PPh3)(η3-CH2C10H7)] were synthesised. In the cases of [CpRu(PPh3)(η3-CH2C2H3)] and [CpRu(PPh3)(η3-CH2C6H5)], thermal and photochemical reaction was initiated with substrates to generate the corresponding η1 substituted derivatives. These products were characterised by NMR techniques. Finally, the ability of the fragment, [CpRh(NR3)], to C-H activate benzene was considered. NMR data were collected for the low stability products of the photochemical reaction which strongly indicated that this auxiliary is capable of C-H bond activation. Due to working at low temperatures (233 K) and the large amounts of amine required to generate [CpRh(NR3)], full characterisation by NMR of these species was not attained.

Includes bibliographies / 128 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1987

L’objectif de cette thèse est de préparer et caractériser de nouveaux agents théranostiques potentiels à base de complexes de ruthénium portant des molécules biologiquement actives. Pour évaluer potentiel théranostique des nouveaux composés les propriétés de luminescence et la cytotoxicité ont été considérées. Quatre nouveaux ligands portant des substituants a activité biologique: 5-(4-4’-methyl-[2,2’-bipyridine]-4-ylbut-1-yn-1-yl)pyridine-2-carbaldehyde semicarbazone (L1), 3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L2), 5,5-dimethyl-3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L3) and [1-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)-2,5-dioxoimidazolidin-4-yl]urea (L4) ont été prepares, caractérisés et engagés dans la synthese des complexes de ruthénium correspondants. Six complexes ont été obtenus a partir du ligand L1 ([Ru(bpy)2(L1)]2+, [Ru(Mebpy)2(L1)]2+, [Ru(tBubpy)2(L1)]2+, [Ru(Phbpy)2(L1)]2+, [Ru(dip)2(L1)]2+, [Ru(SO3dip)2(L1)]2-) et trios a partir de L2, L3 and L4 ([Ru(bpy)2(L2)]2+, [Ru(bpy)2(L3)]2+, [Ru(bpy)2(L4)]2+) (bpy = 2,2’-bipyridine, Mebpy = 4,4’-dimethyl-2,2-bipyridine, tBubpy = 4,4’-tert-butyl-2,2’-bipyridine, Phbpy = 4,4’-diphenyl-2,2-bipyridine, dip = 4,7-diphenyl-1,10-phenantroline and SO3dip = 4,7-di-(4-sulfonatophenyl)-1,10-phenantroline). Les propriétés spectroscopiques et photophysiques des composés ont été étudiées. La présence des ligands L1-L4 conduit a une décroissance du rendement quantique et de la durée de vie de l’état excité en comparaison des complexes non substitués [Ru(bpy)3]2+. Des calculs DFT montrent que les ligands L1-L4 n’influencent pas la géométrie du complexe mais accroissent le niveau énergétique de la HOMO induisant des band gap HOMO-LUMO plus faibles. Les interactions entre les complexes et l’human serum albumin (HSA) ont été étudiées. Tous les complexes préparaés montrent une tres forte affinité pour HSA – La constante d’association 105 M-1s-1 témoigne de la formation d’adduits Ru-HSA stables. Il a aussi été démontré que les complexes de ruthénium se lient préférentiellement a la poche hydrophobe des protéine, située dans le site 1 de Sudlow dans le sous domaine II A. Des études préliminaires ont montré que les complexes de ruthénium préparés presentent une activité cytotoxique vis-à-vis de diverses lignées de cellules cancéreuses. Cette activité associée aux bonnes propriétés de luminescence (rendement quantique, durée de vie) fait des nouveaux complexes des candidats potentiels pour les applications théranostiques / The main goal of this thesis was synthesis and preliminary characterization of novel ruthenium(II) polypyridyl complexes bearing biologically active molecules as potential theranostic agents. Luminescence for the diagnostic applications, and cytotoxicity for the anticancer, therapeutic applications are considered as the theranostic properties. Four new ligands containing biologically active moieties - 5-(4-4’-methyl-[2,2’-bipyridine]-4-ylbut-1-yn-1-yl)pyridine-2-carbaldehyde semicarbazone (L1), 3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L2), 5,5-dimethyl-3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L3) and [1-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)-2,5-dioxoimidazolidin-4-yl]urea (L4) were synthesized and characterized. The ligands were used to obtain nine novel ruthenium(II) polypyridyl complexes. Six complexes were synthesized with ligand L1 ([Ru(bpy)2(L1)]2+, [Ru(Mebpy)2(L1)]2+, [Ru(tBubpy)2(L1)]2+, [Ru(Phbpy)2(L1)]2+, [Ru(dip)2(L1)]2+, [Ru(SO3dip)2(L1)]2-) and three with ligands L2, L3 and L4 ([Ru(bpy)2(L2)]2+, [Ru(bpy)2(L3)]2+, [Ru(bpy)2(L4)]2+) (bpy = 2,2’-bipyridine, Mebpy = 4,4’-dimethyl-2,2-bipyridine, tBubpy = 4,4’-tert-butyl-2,2’-bipyridine, Phbpy = 4,4’-diphenyl-2,2-bipyridine, dip = 4,7-diphenyl-1,10-phenantroline and SO3dip = 4,7-di-(4-sulfonatophenyl)-1,10-phenantroline). The spectroscopic and photophysical properties of those complexes were determined. The presence of ligands L1-L4 in the structure of the complex decreased luminescence quantum yield and luminescence lifetime in comparison with unmodified [Ru(bpy)3]2+ complex. The theoretical calculations have shown that ligands L1-L4 do not have influence on ruthenium core geometry. However, they increased the energy of the HOMO that resulted in a shorter band gap. The simulated electronic absorption spectra were in a good agreement with the experimental data. The interactions between the studied ruthenium complexes and human serum albumin (HSA) were investigated. All studied Ru(II) complexes exhibited strong affinity to HSA with the association constant 105 M-1s-1, which suggests formation of Ru complex-HSA adducts. It was also determined that ruthenium complexes most likely bind to the hydrophobic pocket of protein, located in Sudlow’s site I in the subdomain II A. Preliminary cytotoxicity evaluation for the studied ruthenium complexes showed their cytotoxic activity towards cancer cell lines. Those results, together with good luminescence properties of the studied ruthenium complexes (luminescence lifetimes and luminescence quantum yield) make them interesting candidates for potential theranostic applications