Study On Synthesis Of Phenanthroline Derivatives-Copper(?) Chromophores And Sensitized Luminescence Of Yb(?)

Lanthanide(?)luminescence has attracted intensive research efforts because of its distinct advantages such as high color purity induced by narrow emission bands,long radiative lifetimes of the excited states in the range of microseconds to milliseconds,large Stokes' shifts,and relatively immovable emission positions.But direct excitation of the Ln(?)centers always leads to inefficient luminescence because of the extremely weak absorption from f-f forbidden transitions of the Ln(?)ions.In order to improve the luminescence yields of Ln(?)ions,one of the most feasible strategies is to use d-block metallorganic antenna chromophores as sensitizers.Among the many chromophores,the oriented synthesis of organometallic complexes for Cu(I)is easy to be carried out due to the high coordination selectivity of Cu(I)ions,the organometallic complexes of Cu(I)often display good phosphorescent properties at room temperature.We have synthesized a series of imine-copper(I)-bisphosphine complexes with empty coordination site in this paper,and selected some complexes as chromophores to study near-infrared sensitized luminescence of Yb(?)ions.There are four chapters in this thesis:Chapter 1 reviewed the significance and prospects of diimine-copper(I)-phosphine complexes,the advantages of d-block transition metal as antenna chromophores for sensitizing lanthanide ions luminescence,present status and the main problems of d-block metallorganic antenna chromophores for Ln(?)sensitization luminescence,and the starting points of the thesis are stated.In Chapter 2,twelve neutral imidazo[4,5-f][1,10]phenanthroline-Cu(I)-diphosphine complexes were synthesized,and their structures were characterized by IR spectra,1H and 31 P NMR,ESI-MS and X-ray single crystal diffraction analysis.The luminescent properties of these twelve complexes were studied by UV-vis absorption spectra,emission spectroscopies and emission quantum yields.In Chapter 3,neutral imidazo[4,5-f][1,10]phenanthroline-Cu(I)-diphosphine complexes were used as building blocks,and the ratios between these complexes and Yb(hfac)3 units were studied through spectra titration.And then the neutral imidazo-[4,5-f][1,10]phenanthroline-Cu(I)-diphosphine complexes were further used to study the Yb(?)near-infrared luminescence.In Chapter 4,the synthesis,structures and photophysical properties of a series ion Cu(I)-diphosphine complexes of DOP are introduced and studied.