Synthesis And Characterization Of Heteronuclear Ru-Ln Metal Complexes

Ru-Ln Complexes exhibit the characteristic lanthanide luminescence with narrowemission spectra, long-lived time and large stokes’ shifts, which are suitable in theapplication of biological analyst. In this work, two novel nitrogen and oxygenheterocyclic ligands have been designed, and a series of heteronuclear Ru-Ln metalcomplexes have been synthesized by the nitrogen and oxygen heterocyclic ligandsselectively coordinated with Ru blocks and rare earth compounds [Yb (III), Nd (III) andEr (III)].The following are the main content of this dissertation：1. Three new heteronuclear Ru-Ln complexes [Ru(phen)2(pdtp)Ln(TTA)3](PF6)2(Ln=Nd2, Er3, Yb4) have been synthesized by the reaction of [Ru(phen)2(pdtp)](PF6)2and Ln(TTA)3. The desired products, purified by column chromatography, werecharacterized by elemental analyses, ESI-MS spectrometry, UV-Vis, and IRspectroscopies. The results show that complexes2-4display the characteristic NIRlanthanide luminescence in solid state and the1,2-dichloroethane solution because a Ruchromophoreâ†'Ln photoinduced energy transfer to low-lying emissive states of thelanthanide ions. From the degree of quenching of the Ru-based emission in the1,2-dichloroethane solution, Ruâ†'Ln energy-transfer rates can be estimated, which are inthe order Yb> Nd> Er.2. To utilize amide reaction, a new Ru metal complexes[Ru(DPQ)2(phen-NH-DTPA)](NO3)2was synthesized by the reaction of[Ru(DPQ)2(phen-NH2)](ClO4)2and multi-carboxylate ligand DTPAA. HeteronuclearRu-Nd complex was prepared by the reaction of NdCl3and[Ru(DPQ)2(phen-NH2)](ClO4)2. The complexes were characterized and photophysicalproperties have been investigated. The results show that the desired two Ru (П)complexes are well soluble in water, and Ru-Nd complex exhibit the characteristic NIRlanthanide luminescence in solid state and water solution because a Ru chromophoreâ†' Nd photoinduced energy transfer to low-lying emissive states of the lanthanide ion.3. A new bridging ligand phen-N2Na was prepared by the reaction of1,8-naphthalic anhydride with5,6–diamino-1,10-phenanthroline. Two new Ru metalcomplexes of [Ru(phen)2(Phen-N2Na)](PF6)2and [Ru(bpy)2(Phen-N2Na)[(PF6)2weresynthesized. The complexes were characterized and photophysical properties have beeninvestigated. When introducing a large Ï€-conjugation chromophore1,8-naphthalimideunit to the Phen ligands, the1MLCT absorption band of Ru complexes turn wider, but theemission intensities are quenched. The interaction between the complex[Ru(bpy)2(Phen-N2Na)](PF6) and calf thymus DNA, investigated by spectroscopicmeasurements, is mainly intercalative as well as weak electrostatic.