Synthesis,Structure And Thired-Order Nonlinear Opticai Properties Of Metal-Organic Iridium Complexes

As a class of highly promising functional compounds,metal-organic iridium complexes have potential applications in the fields of laser dyes,fluorescent probes and electroluminescent materials,and so on,due to their structural diversity and tunability of properties.In recent years,with the progressive research on metal-organic iridium complexes,their applications in the field of nonlinear optics have also been developed.Therefore,the preparation of metal-organic iridium complexes with excellent luminescence properties,good thermal stability and tunable luminescence color to develop new nonlinear optical materials are the current research hotspots for researchers in this field.In this paper,two iridium dichlorobridges[Ir(fppd)2(/μ-Cl)]2 and[Ir(ppz)2(μ-Cl)]2 with good photothermal stability were designed and synthesized based on chelating ligands(C^N)phenylpyridine and phenylpyrazole,respectively.Such iridium precursors reacted with a series of different types of organic auxiliary ligands(N^N),which constructed on the basis of Schiff base,quinoline and bipyridine,build a total of 11 new unreported metal-organic iridium complexes.The synthesized iridium complexes were then cultured as crystalline materials by solvent diffusion method and their crystal structures were determined using single-crystal x-ray diffractometer.The third-order nonlinear optical properties of these iridium complexes were tested by Z-scan technique,and the effects of the structures of organic auxiliary ligands on the properties of metal-organic iridium complexes were studied in combination with other characterization methods.First,the iridium precursor[Ir(fppd)2(μ-Cl)]2 was synthesized by introducing an electronabsorbing group(F-)into the phenylpyridine chelating ligand and reacting with hydrated iridium trichloride.And then,six new metal-organo-iridium complexes(1-6)were obtained by iridium precursor[Ir(fppd)2(μ-Cl)]2 reacting as the molecular building block with three Schiff base organic co-ligands and three quinoline-based organic co-ligands.The structures and properties of the complexes were then tested and characterized accordingly using mass spectrometry,single crystal x-ray diffraction,spectral analysis and Z-scan techniques.The effects of organic auxiliary ligands with different structures and functional groups on the third-order nonlinear optical properties of the metal-organic iridium complexes were investigated.[Ir(fppd)2(pyd-Ph)][PF6](1)[Ir(fppd)2(pyd-Cl)][PF6][CH2Cl2](2)[Ir(fppd)2(pyd-F)][PF6][CH2Cl2](3)[Ir(fppd)2(quline-Me)][PF6][CH2Cl2](4)[Ir(fppd)2(quline-Et)][PF6][CH2Cl2](5)[Ir(fppd)2(quline-Cl)][PF6](6)In addition,the iridium precursor[Ir(ppz)2(μ-Cl)]2 was synthesized with phenylpyrazole as chelating ligand,and then five new metal-organo-iridium complexes(7-11)were obtained by the reactions between two iridium precursors as molecular building units and five bipyridyl ligands.The structure-related properties of these five iridium complexes were also tested and characterized by mass spectrometry,single-crystal x-ray diffraction,spectroscopic analysis,and Z-scan techniques,while the conformational relationships between the changes in the structure and the properties of the chelating ligands were initially explored.[Ir(ppz)2(pgbpy)][PF6](7)[Ir(ppz)2(pgbpy-Me)][PF6][CH2Cl2](8)[Ir(ppz)2(pgbpy-F)][PF6](9)[Ir(fppd)2(pgbpy)][PF6][CH2Cl2](10)[Ir(fppd)2(bpy-Br)][PF6](11)...