Synthesis And Application Of Ruthenium1,10-phenanthroline Derivatives-based Luminescent Probes

Ru(II) complexes with1,10-phenanthroline ligands have been widely used as novel andpromising luminophores for the development of luminescent probes, due to their goodwater-solubility, high fluorescence quantum yield, high chemical-and photostability, largeStokes shifts, red emission and relatively long lifetimes. In this thesis, three ruthenium(II)complex-based luminescent probes for cupric ion or hydrazine detection were successfullydesigned and synthesized by the modification of the1,10-phenanthroline ligand.An “on-off” ruthenium(II) complex-based luminescent probe (RuHPIP) for cupric iondetection were developed with2-hydroxyphenylimidazo group as ionophore. Copper(II) ionscould selectively coordinate with this probe and induce its phosphorescence quenchinggreatly, which could be applied to detect cupric ion in aqueous solution with good sensitivityand selectivity. In addition, the non-luminescent system (RuHPIP+Cu) could rapidly andspecifically interact with sulfide to yield RuHPIP, along with a remarkable luminescenceenhancement, which could be used to detect sulfide in tap water samples with good recovery(95%-105%).A novel ruthenium(II) complex RuMAZO with o-phenylazoaniline group as reactive sitewas developed as an “off-on” luminescent probe for divalent copper detection. Througth theoxidative cyclization reaction with Copper(II) ions, nonemissive RuMAZO was transformedinto highly luminescent RuTAZO. Based on this mechanism, RuMAZO could serve as asensitive and selective luminescent probe for cupric ions detection in aqueous solution withvery low limit of detection (7.12ppb) over wide linear range (0.1-10μM). Furthermore, usingthis probe, a faithful luminescent method for the detection of cupric ions in human serumsamples was established with good recovery (95%-100%).A novel ruthenium(II) complex Rubg containing phthalimide modified1,10-phenanthroline ligand was achieved as a luminescent probe for high concentration of hydrazine detection in aqueous solution without adding any organic solvent. However, itsstructure should be further optimized to improve its selectivity and detection limit.