Study On The Crystal Structure And Catalytic Performance Of Chiral Phenoxyisopropionic Acid Ligands

In this work,we designed and synthesized two chiral dicarboxylic ligand named(R)-4-(4-(1-carboxyethoxy)phenoxy)-3-chlorobenzoic acid(L1)and(R)-4-(4-(1-carboxyethoxy)phenoxy)-3-fluorobenzoic acid(L2).Ten chiral coordination polymers(CCPs)were built by the two chiral ligands with transition metals:[Zn(L1)(H2O)]2·H2O(CCP-1),[Cd(L1)(H2O)]2·H2O(CCP-2),[Co(L1)(H20)]2·H2O(CCP-3),[Zn(L1)(bimb)]2·EtOH-H2O(CCP-4),[Zn(L2)(bimb)]2·EtOH-H2O(CCP-5),[Co(L1)(bimb)]2·EtOH·H2O(CCP-6),[Zn(L2)(biim-4)]2.2H2O(CCP-7),[Zn(L2)(bix)]2·2H2O(CCP-8),[Zn(L2)(bix)]2·CH3OH·H2O(CCP-9),[Zn(L2)(dmbpy)]·2H2O(CCP-10),in which CCP 3-5 have been synthesized and reported by this term before,and the other seven complexes were novel.Herein we reported the structures of the seven novel CCPs,and asymmetric catalysis properties of CCP 1-6,and SHG activities of CCP 1-10.1)We synthesized L1 and L2 by(R)-(+)-2-(4-Hydroxyphenoxy)propionic acid reacting with 3,4-dichlorobenzonitrile or 3,4-difluorobenzonitrile in base environment followed by hydrolysis reactions.The products were characterized by H NMR,FT-IR.Circular Dichroism spectrum(CD)is used for their asymmetry analysis,which is also confirmed by single-crystal X-ray diffraction.2)We synthesized seven novel complexes CCP 1,2,4,7-10 based on L1 or L2 and N-donor mixed ligands,which are characterized by single-crystal X-ray diffraction,FI-IR,elemental analysis,powder X-ray diffraction(PXRD),Circular Dichroism spectrum(CD)and thermal gravimetric analysis(TGA).The effect of N-donor ligand length on the configuration of carboxylic acids in the complex is also studied.3)The asymmetric catalytic activities for Henry reactions of CCP 1-3 are investigated under different reaction conditions such as solvent and temperature.Similarly,we also studied the asymmetric catalytic activities of CCP 4-6 in Aldol reactions.Furthermore,SHG-active properties of CCP 1-10 have been studied.Furthermore,the structure of ligand 1 and 2 effected by N-donor have been studied here.