Structural characterisation of new Ru-II[9]aneS(3) polypyridylic complexes

A large number of new [Ru-II([9]aneS(3))(L)Cl](+) 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](+) and [Ru([9]aneS(3))(phi)Cl](+) 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 H-1 NMR, IR, UV-Vis and electrospray mass spectrometry. Furthermore, the PF6 salts of seven [Ru([9]aneS(3))(L)Cl](+) and [Ru([9]aneS(3))(dip)Cl]BF4 (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 pi -stacking geometric arrangements of the extended aromatic systems dppz (dipyrido[3,2-a:2',3'-c]phenazine) and dip in their metal complexes are also discussed.