Structural characterisation of new RuII[9]aneS3 polypyridylic complexes †

Abstract

A large number of new [Ru II ([9]aneS 3 )(L)Cl] ϩ complexes (where L is a polypyridyl bidentate ligand) were synthesized from the precursor [Ru ([9]aneS 3 )(dmso)Cl 2 ] in the search for new DNA intercalators. The ancillary ligands used have different molecular architectures which include cross bridges, pyridyl units, phenanthroline and diamine derivatives. The related complex [Ru ([9]aneS 3 )(ind)Cl 2 ], containing the monodentate ligand indazole, was also prepared. The diimine complexes [Ru ([9]aneS 3 )(pdi)Cl] ϩ and [Ru ([9]aneS 3 )(phi)Cl] ϩ were prepared in situ from the ligands pda (o-phenylenediamine) and dap (phenanthrene-9,10-diamine), respectively, via Ru assisted amine/imine oxidation. All complexes were characterised through 1 H NMR, IR, UV-Vis and electrospray mass spectrometry. Furthermore, the PF 6 salts of seven [Ru ([9]aneS 3 )(L)Cl] ϩ and [Ru ([9]aneS 3 )(dip)Cl]BF 4 (dip = 4,7-diphenylphenanthroline) have been investigated by X-ray single crystal diffraction. The crystal structures are presented and analysed in terms of the molecular assemblies of the complex cations and anions and the molecular hydrogen bonding interactions. The π-stacking geometric arrangements of the extended aromatic systems dppz (dipyrido[3,2-a : 2Ј,3Ј-c]phenazine) and dip in their metal complexes are also discussed.

Characterization and differentiation of ruthenium(II) complexes with 1,4,7‐trithiacyclononane and nitrogen heterocycles by electrospray mass spectrometry

“…The presence of [M − 64] + and [M − 92] + ions confirms that M + really corresponds to the monocharged inner sphere ion [Ru II Cl([9]aneS 3 )tpy] + and that tpy is acting as a bidentate ligand. This behaviour was expected both from our x‐ray, NMR and elemental analysis results17 and from literature data 23. Terpyridine acts as a tridentate ligand only in the absence of significant steric hindrance from the other ligands and if mer coordination is available 23…”

“…The [Ru II Cl([9]aneS 3 )Y]X complexes (Y = bpy, dbp, bq, phen, dip, 5‐phen, 5,6‐dione, dppz, dhdmf, dipa, dpk, dpm and tpy, Fig. 1, and X = Cl − ,PF 6 − ) and [Ru II Cl([9]aneS 3 )dmsoZ]Cl, where Z is imid or ind and dmso is dimethyl sulfoxide, were synthesized by the reaction of the thioether, [9]aneS 3 , with the complex cis ‐[Ru II Cl 2 (dmso) 4 ], in which the intermediate compound [Ru II Cl 2 ([9]aneS 3 )(dmso)] was formed, followed by the addition of the nitrogen ligands, under mild conditions: reflux, 80–95 °C, ethanol 15–17…”

“…All the complexes were characterized by elemental analysis and UV–visible; IR and 1 H NMR, spectroscopy. The complexes with bpy and phen15 and dipa, bq, dip, dppz, dpk and dpm17 were also characterized by single‐crystal x‐ray diffraction spectroscopy.…”

Photolabile Ru Model Complexes with Chelating Diimine Ligands for Light‐Triggered Drug Release

“…A microwave assisted reaction in ethanol (140 °C, 90 min) was preferred to prolonged reflux for obtaining [Ru([9]aneS 3 )(bq)Cl]Cl ( 5 ) in good yield. All complexes, already reported in the literature either as Cl or PF 6 salts,, were characterized by NMR and UV/Vis spectroscopy (Supporting Information, Figure S1), and mass spectrometry. They are well soluble in ethanol, chloroform, DMSO, and – with the exception of 3 and 4 – also in water.…”

Structural studies on supramolecular adducts of cyclodextrins with the complex [Ru([9]aneS3)(bpy)Cl]Cl

“…For this purpose, some of us have developed a series of Ru(II) complexes with the face-capping ligand trithyacyclononane ( [9]aneS 3 ) and planar aromatic amines suitable for DNA intercalation [17]. The crystal structures of these compounds were found to be largely stabilised by hydrogen bonding interactions and the coordinated planar aromatic amines exhibit p-stacking arrangements which mimic the structure of polypyridyl complexes intercalated with DNA.…”