Studies On The Rare Earth Complexes With Pendant Macrocy Clic Ligands And The Relative Luminescent Chemosensors

Rare-earth ions have unique electronic structure and bonding characteristics, so rareearth complexes show distinct luminescent properties. Recently, the design and assemblyof functional luminescent rare-earth complexes have become a challenging issue.Amide-type ligands have the advantages in simple synthesis, adjustable structure andchangeable sensitive conjugate groups, which make their complexes indicating goodluminescent properties. In order to investigate the coordination properties of the pendantmacrocyclic ligands with rare earth ions, and the influence of different skeleton and thefunctional terminal groups of the ligands and different anions to luminescent properties ofthe rare earth complexes, eight kinds of pendant macrocyclic amide type ligands L^Ⅰ～L^â…§,four kinds of other pendant macrocyclic ligands L^Ⅸ～L^â…«and their rare earth complexeshave been synthesized and characterized in this dissertation. Then the luminescentproperties of the complexes were systematically studied, and the ion-selective experimentsof the terbium nitrate complexes with ligands L^â… , L^â…¡and L^â…¢and the solvent molecularrecognition of the terbium nitrate complexes with ligand L^â…¥were accomplishedsubsequently.The dissertation includes following five chapters:Chapter 1: A brief review of investigation progress of rare earth luminescent complexesand luminescent chemosensor were summarized.Chapter 2: Pendant macrocyclic ligands L^Ⅰ～L^â…¤have been designed and synthesizedusing five kind of amide-type terminal groups as arms and benzo-15-crown-5 as theskeleton, and 51 rare earth complexes include rare earth nitrate and picrate with L^Ⅰ～L^â…¤have been synthesized and characterized. Two ligands L^â…¥and L^â…¦have been designedand synthesized containing different terminal groups and using benzo-12-crown-4 as theskeleton, and their 18 rare earth nitrate and picrate complexes also have been synthesizedand characterized. The ligands L^â…§have been synthesized using N-benzylsalicylamide asterminal group and using benzo-18-crown-6 as the skeleton, and four rare earth nitratecomplexes also have been synthesized and characterized. Based on crystal diffractionanalysis, the influence of the counter anions to the complex structures, hydrogen bondsandÏ€-Ï€stacking interactions in building novel supermolecule, and space topological structures in supermolecules have been studied.Chapter 3: Photoluminescence studies of europium and terbium complexes show that allthe terminal groups have good sensitive function to europium and terbium ions. Theskeletons and terminal groups of the ligands, the counter anions have effects on theluminescent properties of the rare earth complexes.Chapter 4: Four pendant macrocyclic ligands have been synthesized usingbenzo-15-crown-5, diaza-18-crown-6, cyclen and calix[4]arene as the skeleton, and 19rare earth nitrate complexes were synthesized. Then the luminescent properties of a part ofthe luminescent rare earth complexes were studied. The results indicated that the rare earthcomplexes had good luminescent properties. Because the luminescence of europiumnitrate complexes with the ligand of L^â…ªand L^â…«could stimulated by visible light, theyhad a good application potentiality in biosystem.Chapter 5: The ion-selective experiments of the terbium nitrate complexes with ligandsL^â… , L^â…¡and L^â…§had been studied, the results indicated that the complexes had specialfluorescent response to Hg²⁺ in the test of a dozen of metal ions; then the study of solventmolecular recognition of the terbium nitrate complex with ligand L^â…¥shown that thecomplex has distinct fluorescent response in acetonitrile.The ligands involved in the dissertation are listed as follows:L^â… : 4,5-bis {{[2'-(N-benzylaminoformyl)]-phenoxyl}methyl}-benzo-15-crown-5L^â…¡: 4, 5-bi {{2'-[2"-(N-methylpyridineaminoformyl)]phenoxyl}methyl} benzo-15-crown-5L^â…¢: 4,5-bi {{2'-[3"-(N-methylpyridineaminoformyl)]phenoxyl} methyl} benzo-15-crown-5L^â…£: 4,5-his {[(2'-phenylaminoformyl)-phenoxyl]methyl}-benzo- 15-crown-5L^â…¤: 4,5-bi{ [2'-(N-(2"-methylfuranaminoformyl)phenoxyl]methyl}-benzo-15-crown-5L^â…¥: 4,5-bis {[(2'-benzylaminoformyl)-phenoxyl]methyl}-benzo-12-crown-4L^â…¦: 4, 5-bi {{2'-[2"-(N-methylpyridineaminoformyl)]phenoxyl} methyl} benzo-12-crown-4L^â…§: 4,5-bis {[(2'-benzylaminoformyl)-phenoxyl]methyl}-benzo-18-crown-6 L^â…¨: 4,5-bis {[(2'-carboxyphenoxy)-phenoxyl]methyl }-benzo-15-crown-5L^â…©: 1,10-bis [N-benzyl-4'(4"-terpyridine)]-4,7,13,16- tetraoxacyclooctadecaneL^â…ª: 1,4,7,10-Tetrakis[(N,N-bisisopropylmethylcarbamoyl)methyl]-1,4,7,10-tetra-azacyclododecaneL^â…«: 5,11,17,23-Tetrakis(1,1-dimethylethyl)-25,27-bis(N-benzylaminoformyl)-26,28-dihydroxycalix[4]arene...