Design And Synthesis Of Chiral Ligands Based On Dihydrothiazole And Their Complexes

Metal-organic frameworks has been particularly concerned in metal complexes at present.Metal-organic frameworks exhibts great applications in gas storage and separation,heterogeneous catalysis,medicine and sensing due to their high specific surface area,high porosity and continuous large pore structure potential.In this work,4-（4-pyridyl）benzonitrile and 4-（3-pyridyl）benzonitrile were synthesized by coupling reactions,and then chiral ligands based on 4,5-dihydrothiazole-4-carboxylic acid were synthesized by condensation reaction of chiral cystein with cyano group.Several metal-organic framework materials were synthesized by the reactions of these chiral ligands with different metal salts,and their structures were determined by single crystal diffraction and the properties were characterized by various characterizations.This work is divided into three parts:The first part mainly introduces the advantages of metal organic framework materials relative to traditional inorganic materials and the research results of metal organic framework materials in fluorescence and sensing,catalysis,gas storage and adsorption,biomedical research and membrane separation devices.The application of chiral metal organic framework materials in asymmetric catalysis,chiral separation and liquid chromatography separation was introduced in detail.Secondly,the method of synthesizing metal organic framework materials was briefly introduced.Finally,the research background and research progress were introduced.In the second part（chapters 2 and 3）,thre pairs of enantiomeric ligands,namely（R/S）-2-[4-（4-pyridyl）-phenyl]-4,5-dihydrothiazole-4-carboxylic acid(L^1R and L^1S),（R/S）-2-[4-（3-pyridyl）-phenyl]-4,5-dihydrothiazole-4-carboxylic acid(L^2R),and（R/S）-2-（4-carboxyphenyl）-4,5-dihydrothiazole-4-carboxylic acid(L^3R and L^3S),have been synthesiezed and characterized by ¹H&¹³C NMR spectra,mass spectra and circular dichroism spectra.A series of three-and two-demensional metal-organic frameworks have been prepared by the reactions between ligands L¹RR or L¹SS with Co²⁺,Zn²⁺,Ni²⁺,Cd²⁺and Cu²⁺salts,and their structures were determined by single crystal diffraction analysis.The properties of cobalt and copper complexes were charactreized by TGA and circular dichroism spectra.Three mononuclear complexes were obtained by the reactions of liang L^2R with Co²⁺,Mn²⁺and Zn²⁺salts,a pair of two-dimensional metal organic frameworks has been prepared by using ligands L³RR and L^3S,their structures were determined by single crystal diffraction analysis.Furtheremore the photoluminescence properties of some complexes were also investigated.The third part mainly summarized all the work and give an outlook.