Design,Synthesis And Properties Of Stable Chiral Metal-Organic Frameworks Based On Biphenyl

Owing to the highly crystalline,ultraporous and easily functionalization features of chiral metal-organic frameworks(CMOFs),they have shown widely promising applications in asymmetric catalysis,enantioselective sepration and chiral optoelectronic materials.In this thesis,based on the chiral biphenyl platform,we have designed and synthesized a series of chiral linkers with different lengths,shapes and electronic effects.These chiral ligands can react with various metal ions to form a series of CMOFs with novel structures,high stability and unique properties.We have also explored their applications in asymmetric catalysis,chiral separation and chiral luminescent materials.The main content is as follows:(1)We have designed and synthesized three carboxylate functionalized chiral biphenol ligands.Three linkers are reacted with Zr⁴⁺to give two flu topological structures and three ith topological structures.Two-step postmodification of the chiral dihydroxy groups of flu frameworks afforded chiral Ir complexes embedded solid catalysts.The obtained solid catalyst can effectively catalyze the asymmetric hydrogenation of?-dehydroamino acid esters with up to 98%ee.(2)We have reported the synthesis of three chiral crown ether-based carboxylate ligands with different lengths.The chiral ligands were further reacted with Zr⁴⁺to generate three isoreticular CMOFs.Under the reversal-phase chromatographic conditions,the CMOFs can be used as chiral stationary phases(CSPs)to separate racemic amino acids and their derivatives,as well as some important drugs.(3)We have designed and synthesized a novel carboxylate linker based on the chiral imidodiphosphoric acid.This novel linker can react with Ln³⁺to form two different CMOFs when the acetic acid or trifluoroacetic acid was used as modulator.The framework can catalyze the actalization reaction of aromatic aldehydes,the ee value of the product was up to 98%.Moreover,the Eu and Tb containing CMOFs showed different circularly polarized luminescent performance.(4)The isophthalic acids were introduced into the chiral biphenyl backbone to generate three chiral tetracarboxylate linkers.The linkers were futher reacted with zinc ions to afford three isoreticular CMOFs.The CMOFs can be efficient catalysts to catalyze the cycloaddition reaction between carbon dioxide and epoxides under mild conditions.