Synthesis of flexible bis-intercalating Ruthenium(II) complexes

We report the synthesis, resolution and characterisation of a number of novel ruthenium(H) complexes. Four mononuclear complexes, [Ru(dpq)(2)(3-Br-phen)](2+), [Ru(dpq)(2)(4-Cl-phen) ](2+), [Ru(dpq)2(5-Cl-phen)](2+) and [Ru(dpq)(2)(phen)](2+) were synthesised (dpq = dipyrido[3,2-d:2',3'-f[quinoxaline, phen = 1,10-phenanthroline, 3-Br-phen = 3-bromo-1,10-phenanthroline, 4-Cl-phen = 4-chloro-1,10-phenanthroline, 5-Cl-phen = 5-chloro-1,10-phenanthroline). These complexes were resolved using the chiral TRISPHAT anion, [tris (tetra chlorocatecholato) phosphate (V)](-). Racemic mononuclear complexes were used in the synthesis of the racemic dinuclear complexes, [(Ru(dpq)2)2 mu-(phen-n-SOS-n-phen)](+4) (SOS = 2-mercaptoethyl ether, n = 3, 4 or 5). Resolved mononuclear complexes were used to synthesise stereoselectively the AA- and AA-enantiomers of their respective dinuclear complexes. All metal complexes were characterised by H-1 NMR, ESI-MS, UV/Vis and luminescence spectroscopy. Resolved metal complexes were further characterised using CD spectroscopy and chiral H-1 NMR titrations. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim., Germany, 2007)