Design And Synthesis Of Several Chiral Metal-Organic Frameworks For Recognition And Separation

The chiral metal-organic frameworks?CMOFs?have attracted great attentions due to extraordinary and innumerable potential applications such as structural tunability,high surface area,prestigious porosity and chemical flexibility.The MOFs have been envisioned in purification of solvent,gas storage,heterogeneous catalysis,drug delivery,sensing and separation.In this thesis two C₂-symmetric biphenol scaffolds carboxyl-functionalized and one3-formyl-4-?pyridin-4-yl?benzoic acid ligand were prepared.These MOFs are well characterized by TGA,EA,IR,and XRD,etc.The two biphenol MOFs were utilized for chiral recognition process.This thesis includes the following four chapters.In chapter 1,the importance of chiral metal-organic frameworks?CMOFs?is briefly presented,it also include their synthetic approaches and applications in chiral recognition and separation,heterogeneous catalysis and chiral sensor.At the end of this chapter the summary and future prospects of the thesis were introduced.In the chapter 2,the C₂-symmetric 1,1?-biphenol ligand?S?-6,6'-dimethyl-3,3'-dibromo-5,5'-di?3,5-bis?carboxyl??phenyl-1,1'-biphenyl-2,2'-diol?H4L1?was synthesized via eight steps.It was used to construct a CMOF S-1 with salt Cd?NO₃?₂.4H₂O by solvothermal process.The chiral host material demonstrated brilliant enantioselective separation of alcohols and sulfoxides with up to 99.4%,97%ee,respectively.MOF also enantioselectively adsorbs lansoprazole with up to91%ee.The adsorbent S-1 can be regenerated and reused for the next three runs almost without apparent loss of enantioselectivity.In the chapter 3,the naphthyl,dihydroxyl functionalized group and axially C₂-symmetric1,1?-biphenol ligand 4',6''-dihydroxy-2',2''-dimethyl-5',5''-di?naphthalen-1-yl?-[1,1':3',1'':3'',1'''-quaterphenyl]-3,3''',5,5'''-tetracarboxylic acid H4L2 was obtained via nine steps.The S-2 was built by self-assembly of chiral biphenol ligand H4L2 and salt InCl₃?4H₂O.The highly efficient enantiomeric resolution of aromatic alcohols and amines has been victoriously demonstrated up to 98%,99.9%ee respectively by S-2.Without any apparent deterioration of enantiomeric separation performance,the host porous adsorbent S-2 can be promptly recycled and reused.In the chapter 4,3-formyl-4-?pyridin-4-yl?benzoic acid ligand HL3 was synthesized.It was used to construct MOFs 3 and 4 by self-assembly of Zn?NO₃?₂·6H₂O and Ni?NO₃?₂·6H₂O respectively.These compounds were characterized by different spectroscopic techniques such as single crystal X-ray diffraction?XRD?,thermogravimetric analysis?TGA?and elemental analysis?EA?.The phase purity of bulk sample was confirmed by comparison of its simulated powder X-ray diffraction?PXRD?.