Design, Synthesis, Structure And Luminescence Properties Of Rare Earth Complexes With Amide Ligands

The special optical,electrical and magnetic properties of coordination complexes explain that the study of functional coordination complexes combining the advantage of inorganic-organic compounds is still an important research goal in coordination chemistry.This work proposed new ideas in the self-assembly of supramolecules,as well as controlled design strategies of functional coordination compounds through investigations of the crystal structures and properties of supramolecular complexes with series of amide ligands.A series of functional coordination compounds with potential uses have been synthesized and their fluorescence properties have also been investigated in detail.This thesis is divided into six parts:1.The background of this work is concisely introduced with the emphasis on the current survey of luminescent rare earth complex,supramolecular self-assembly and regulation of structures.2.For the first time we synthesized the complexes of quinoxaline-dione based on quinoxaline backbone with their 1,4 position modulated using amide arms and the fluorescence properties of the related complexes were investigated.The influence of length of terminal amide arms on the structure of complex as well as luminescence properties are also studied in detail.Three ligands were involved in this part:L¹:1,4-di(N,N-diethylacetamido)-2,3(1H,4H)-quinoxalinedioneL²:1,4-di(N,N-diisopropylacetamido)-2,3(1H,4H)-quinoxalinedioneL³:1,4-di(N,N-di-n-butyl-acetamido)-2,3(1H,4H)-quinoxalinedione3.With pentaerythritol as backbone group and three structural related aromatic salicylamide as terminal group,three tetrapodal ligands have been synthesised together with series of their rare-earth complexes.By changing counter anion,terminal group as well as minor alteration of electronic density and ion radii of rare-earth ion,we have successfully tuned the structure and properties of this kind of complexes.Three ligands were involved in this part:L⁴:1,1,1,1-tetrakis {[(2'-(2-benzylaminoformyl))phenoxyl]methyl}-methane L⁵:1,1,1,1-tetrakis {[(2'-(2-picolyaminoformyl))phenoxyl]methyl}-methaneL⁶:1,1,1,1-tetrakis {[(2'-(2-furfurylaminoformyl))phenoxyl]methyl}-methane4.Two new structure-related tripodal ligands featuring salicylamide pendant arms have been designed and synthesized together with their rare-earth nitrate complexes with the ultimate aim of self-assembling lanthanide polymers with interesting luminescent properties by changing backbone groups.Two ligands were involved in this part:L⁷:1,3,5-tris {[(2'-furfurylaminoformyl)phenoxyl]methyl}-2,4,6-trimethylbenzeneL⁸:1,1,1-tris {[(2'-furfurylaminoformyl)phenoxyl]methyl}-ethane5.A novel flexible salicylamide ligand L⁹ as well as its rare-earth nitrate complexes have been prepared by using triethylene glycol and salicylpicolylamide.The structure and luminescent properties of the rare-earth complexes have been studied in detail,as a result,a novel luminescence sensor for Zn²⁺has been developed.L⁹:1,9-bis[2-(2'-picolylaminoformyl)-1,4,7,9-tetraoxadecane6.With salicylamide as terminal group,substituted benzene or naphthalene as backbone group,three semi-rigid bridge ligands have been synthesised together with their nitrate rare-earth complexes.The influence of backbone group on structure and luminescence properties of the complexes has been explored.The ligands in this section are as follows:L¹⁰:2,5-bis {[(2'-furfurylaminoformyl)phenoxyl]methyl}-1,4-bimethylbenzeneL¹¹:3,6-bis {[(2'-furfurylaminoformyl)phenoxyl]methyl}-1,2,4,5-tetramethylbenzeneL¹²:1,4-bis {[(2'-picolylamino-formyl)phenoxyl]methyl}-2,3-dimethoxynaphthalene...