Synthesis And Electrochemiluminescence Of Novel Ruthenium And Iridium Conjugated Polymer Complexes

Compared to organic small molecules,the delocalized π-electron cloud in the conjugated polymer chain skeleton acts like a "molecular wire," and electrons or energy can migrate along the rigid D-π-A polymer conjugated chain to form a cumulative effect contributing to its amplified performance.When functional groups with different steric and electronic effects were incorporated in the conjugated polymer backbone to modify its microstructure,the optoelectronic properties of the conjugated polymer can be regulated at the molecular level.It is desirable to obtain polymers with high molar absorption coefficient,strong intramolecular charge transfer(ICT)capability as well as good carrier mobility and enhanced fluorescence quantum efficiency.Phosphorescent transition metal complexes have attracted great interest in the fields of chemistry,bio-sensing,and bio-imaging because of their high quantum efficiency,long emission lifetime,adjustable emission wavelength,large Stokes shift,visible light excitation,and light stability.Based on the advantages of conjugated polymers and transition metal complexes,we introduced ruthenium and iridium complexes into the polymer backbones to obtain conjugated polymer materials with excellent properties.The photophysical properties,electrochemical properties,and electrochemiluminescence(ECL)behaviors in solution and aggregation states have been studied in detail to develop new ECL emitters.The main works of this dissertation are as follows:1.The Amplified Electrochemiluminescence Response Signal Promoted from the Ir(Ⅲ)-containing Polymer Complex.With N,N’-(1,2-dialkyl)-bis(1-phenyl-methanimine)as the ancillary ligand and linker and 9,9-dibutyl-fluorene as the chromophore,we synthesized a conjugated polymer via Palladium-catalyzed Sonogashira coupling reaction.Then coordination reaction of[Ir2(2-ppy)4(μ-Cl)2]and N-containing bidentate ligands in the polymer(-CH=N-CH2-CH2-N=CH-)generated the Ir(Ⅲ)containing polymer complexe as a novel ECL luminophor.The photophysical,electrochemical and ECL properties of the Ir(Ⅲ)-containing polymer complex were studied and indicating that incorporating a small amount of Ir(Ⅲ)can significantly enhance the ECL signal of the polymer,attributed to the effective metal-ligand charge transfer(MLCT).2.Synthesis and ECL Study of Conjugated Polymers of ruthenium and iridium Complexes.In order to regulate the optical and ECL properties of these coordination polymers at the molecular level,we coupled the aggregation-induced luminescence((AIE)unit Tetrastyrene and the ECL group ruthenium or iridium complexes via Suzuki polimerization reaction.The results show that after introduction of an AIE unit,the ECL signals of the Ru and Ir coordination polymers obviously enhanced in their aggregation state(film or nanoparticle),compared with their solution phase.