Modular Synthesis Of Tetraurea And Octaurea Macrocyclic Compounds And Their Supramolecular Self-assembly With Sulfate Ions

Compared with the relatively mature metal cation coordination chemistry,the development of anion coordination chemistry is relatively slow.At the same time,since the report of crown ethers in 1960s,a large number of macrocyclic molecules have been synthesized,and the interaction between macrocyclic molecules and anions is also a research focus.Macrocycles are widely used in molecular recognition,chemical storage and separation,catalysis,molecular machinery and layered assembly,adaptive materials and drug delivery,etc.It is pointed out that the basis of macrocyclic chemistry is to control the structural information of macrocyclic chemistry,including sequence and symmetry.Specifically,the hydrophilicity and size of the attached side chains on the macrocycle backbone correspond to the morphology of the nanostructures assembled by the macrocycle.The combination of active binding sites in the macrocycle lumen with shape-persistence and size-complementarity determines the binding selectivity for smaller objects such as cations and anions.Based on the above points,we designed and modularized six macrocycles with different structures(L~1-L~6),and they and sulfate can form assembly forms of different structures.The full text is divided into three chapters,the main content is as follows:The first chapter is an introduction:the origin and development of supramolecular chemistry,the development of urea receptors and their assemblies,the development of macrocyclic compounds and the research on their properties,as well as the purpose and significance of this thesis.In the second chapter,we designed and synthesized four kinds of tetraurea macrocycles ligands(L~1-L~4)based on the units of 4,4'-diphenyl-methyl,4,4'-diphenyl-ether,hexamethyl and o-phenyl-diurea-group,as well as they self-assemble with sulfate anions to form supramolecular assemblies.Furthermore,we analyzed the modularization strategy and discussed.In the third chapter,two kinds of octaurea macrocycles ligands(L~5-L~6)with 4,4'-diphenyl-methyl,4,4'-diphenyl ether,hexamethyl and o-phenyl-diurea-group as structural units were designed and synthesized,and supramolecular assembly formed by the anion and sulfate group was designed and synthesized.