Synthesis And Luminescent Property Studies Of Azacalixpyridine-encircled Silveralkynyl Cluster Compounds

As a kind of typical metal cluster material,the silveralkynyl cluster complexes have many unique physical and chemical properties,and have been widely used in catalysis and luminescent materials.The silver alkynylcluster aggregate can be used as a building blockin the assembly of various alkynyl cluster-based supramolecular compounds.In addition,the terminal part of the organic silver alkynylcluster can be modified by the introduction of organic multidentate ligands to form a bifunctional building unit,thus being useful in the construction of a series of novel,functional metal organic coordination assembly.In the assembly of the silver alkynylsupramolecular compound,the macrocyclic compound is receivingmore and more attention,because it can reduce the entropy loss effectively due to its macrocycle effect.The formation of silver alkynylclusters in the inner space of the macrocycle ligand,thus performing coordination-driven assembly,is beneficial to the formation of a well-defined,functional and stable supramolecular assembly.The intermolecular silver alkynyl cluster coordination of azacalix pyridine macrocycle compounds,and the effect of many alkynyls,can be a supplement to the silver alkynyl cluster-macrocycle compounds research.The main research contents of this thesis are the synthesis of the silveralkynylcluster centered macrocyclic supramolecular compound.And we want to explore the effect of multiple alkynyl groups on the number and nuclearity of silveralkynylcluster centered macrocyclic supramolecular assembly.The main contents of this thesis include the following two parts:(a)By modifying the aza-pyridine[8]building unittrimers,we first synthesized a modified aza-pyridine[8],by further reaction of the above-mentioned modifying groups,we have synthesized a alkynyl-modified aza-pyridine[8] macrocyclic compound 21,and performed supramolecular assembly without other ligands.After the compound was turned into the silvercarbide,we obtained the coordination structure of the silveralkynylclustercentered macrocyclic supramolecular compound by screening the silver salts,solvent and concentration.(b)By synthesizing multi-alkynylligands 1,2-diethynylbenzene and 1,2,4,5-tetraethynylbenzene,and exploring the multi-alkynylligand effectin the aza-pyridine[8] macrocycle supramolecular assembly,we obtained the macrocycle-multi-alkynyl ligand complexes.In the bi-alkynyl compound,two alkynyl groups on the same side of the macrocyclic ring form two kind of silveralkynylcluster,one in the macrocycleinner space and the other outside the macrocycle.In the tetra-alkynyl compound,two macrocycles are coordinated.Considering the effect of the structure on the photophysical properties of the compound,we investigated the luminescent properties of macrocycle-multi-alkynyl ligand compounds.The microsecond-ranged lifetime of the compound and the oxygen-quenching property of the luminescence spectrum indicate phosphorescent mechanism of the macrocycle-multi-alkynyl ligand compounds.