Design,Synthesis And Crystal Structure Of Chiral MOFs Ligand

Chirality is widespread in nature.The synthesis and performance of chiral metal-organic framework materials(chiral MOFs)is a hot area of current research,because it is widely used in asymmetric catalysis,enantiomer separation,and second-order Nonlinear optical materials and chiral drug delivery.During the study of the synthesis of chiral metal-organic framework materials,it was discovered that chiral ligands play a very important role,especially some axial chiral ligands with C₂symmetry binaphthyl or biphenyl skeleton characteristics.Under this background,this thesis intends to carry out the design,synthesis and performance study of axial chiral ligands containing pyridine functional groups or carboxylic acid functional groups with C₂symmetry binaphthyl skeleton.The main research contents are as follows:4-bromo-2-hydroxy naphthalene was used as the starting material,and racemic4,4'-dibromo-[1,1'-binaphthalene]-2,2'-diol was obtained through oxidative coupling reaction,and then the racemic 4,4'-dibromo-[1,1'-binaphthalene]-2,2'-diol was chirally resolved to obtain optically pure(R)-4,4'-dibromo-[1,1'-binaphthalene]-2,2'-diol and(S)-4,4'-dibromo-[1,1'-binaphthalene]-2,2'-diol.Further,through the Suzuki coupling reaction between(R)-2,2'-dihydroxy-4,4'-dibromo-1,1'-binaphthyl and4-pyridine boronic acid,a new pyridine functional group-containing axial hand the sex ligand(R)-4,4'-di(pyridin-4-yl)-[1,1'-binaphthalene]-2,2'-diol was obtained,and its structure was analyzed by X-ray single crystal diffraction characterization.Suzuki coupling reaction between(S)-4,4'-dibromo-[1,1'-binaphthalene]-2,2'-diol and(3-methoxy-4-(methoxycarbonyl)phenyl)boronic acid makes(S)-2,2'-dihydroxy-4,4'-bis(3-methoxy-4-methoxycarbonylphenyl)-1,1'-binaphthyl was obtained,followed by tribromo Boron demethylation,The method of demethylation resulted in a new axial chiral ligand(S)-4,4'-(2,2'-dihydroxy-[1,1'-binaphthalene]-4,4'-diyl)bis(2-hydroxybenzoic acid)containing carboxylic acid functional group.The work on using these two new axial chiral ligands to construct chiral MOFs is underway.3-Hydroxyquinoline was used as the raw material,and the iodine reaction was carried out according to the literature method to obtain 4-iodo-3-hydroxyquinoline,and then the hydroxyl group in the4-iodo-3-hydroxyquinoline molecule was protected to obtain 4-iodo-3-methoxyquinoline.Then the Ullmann coupling reaction catalyzed by active copper powder was used to obtain racemic3,3'-dimethoxy-4,4'-biquinoline.3,3'-dimethoxy-4,4'-biquinoline single crystal was obtained in a mixed solvent of chloroform and petroleum ether,and its structure was characterized by X-ray single crystal diffraction.Next,3,3'-dimethoxy-4,4'-biquinoline is demethylated to obtain racemic3,3'-dihydroxy-4,4'-biquinoline,then it is chirally resolved to obtain optically pure3,3'-dihydroxy-4,4'-biquinoline.