Ruthenium(II) Complexes with (3‐Polyamino)phenanthrolines: Synthesis and Application in Sensing of Cu(II) Ions

This work deals with the development of water-soluble optical sensors based on ruthenium(II) tris(diimine) complexes that exhibit high molar absorptivity and are emissive in aqueous media. Palladium-catalyzed arylation of polyamines with 3-bromo-1,10-phenanthroline (Brphen) and [Ru(bpy)2(Brphen)](PF6)2 (bpy = 2,2’-bipyridine) was explored to prepare Ru2+ complexes with 1,10-phenanthrolines (phen) substituted by linear polyamines (PAs) at position 3 of the heterocycle ([Ru(bpy)2(phen–PA)](PF6)2). The most convenient synthetic pathway leading to the target molecular probes includes the preparation of phen–PA ligands, followed by ruthenium complexation using cis-Ru(bpy)2Cl2. Complexes bearing a polyamine chain directly linked to phenanthroline core are emissive in aqueous media and their quantum yields are comparable to that of parent [Ru(bpy)3](PF6)2. Their structure can be easily adapted for detection of various analytes by modification of amine groups. As an example, we prepared the emissive complex Ru(N2P2phen) which is suitable for the dual channel (spectrophotometry and luminescence (ON–OFF probe)) selective detection of Cu2+ ions at the physiological pH levels with limits of detection (LOD) by spectrophotometry and fluorescence spectroscopy equal to 9 and 6 μM, respectively, that is lower than the action level in drinking water for copper as prescribed by the US Environmental Protection Agency.