Preparation And Properties Of Tridentate Chiral Carboxylic Acid Metal Complexes

In this dissertation,based on the previous work experience of our group,we designed and synthesized two pairs of novel tridentate chiral carboxylic acid ligands with novel structures:(2R/S,2'R/S)-2,2'-((5-Carboxy-1,3-phenylene)bis(oxy))dipropionic acid(R/S-H₃CPA)and(R/S)-5-((1-carboxyl-ethoxy))Methyl)isophthalic acid((R/S)-H₃CMIA).In the solvothermal reaction with transition metals and rare earth metals,a total of twenty chiral carboxylic acid metal complexes with four spatial structures were constructed,namely[Cd(R)CPA-PH]·3H₂O(CCP-1)?[Cd(S)CPA-P H]·3H₂O(CCP-2)and[M(R)CMIA]·2H₂O{M=Zn?Co?Cd?Ni}(CCP-3?5?7?9),[M(S)CMIA]·H₂O{M=Zn?Co?Cd?Ni}(CCP-4?6?8?10),[Ln(R)CMIA]·H₂O{L n=Ce?Sm?Eu?Tb?Pr}(CCP-11?13?15?17?19),[Ln(S)CMIA]·H₂O{Ln=Ce?S m?Eu?Tb?Pr}(CCP-12?14?16?18?20).We confirmed the structure of the above 20 chiral carboxylic acid complexes using single crystal X-ray diffraction,and for further characterized of their structure by using powder X-ray diffraction,infrared spectroscopy,elemental analysis,thermogravimetric analysis(TGA)and other measurement methods.It was found that the complex CCPs 7-8 due to the participation of co-ligands phenanthroline in the coordination process,their spatial structure shows a one-dimensional chain structure,while the CCPs 3-10 have the same steric structure and coordination configuration,and show a two-dimensional network stacking structure in the P1 space group.In addition,the chiral rare earth metal coordination polymers we prepared exhibit two different coordination modes due to different atomic radii.The central metals of CCPs 11-18 are all eight-coordinated,and the central metals of CCPs 19-20 are all nine-coordinated,and CCPs 11-20 exhibit a similar three-dimensional network stacking structure in space.The above complexes are all based on chiral ligands.Therefore,we performed circular dichroism and SHG activity analysis of these coordination polymers and found that they exhibited significant positive and negative Cotton effects in the CD spectra,and they has a certain SHG effect.We have studied the nitroaromatic compounds recognition and metal cation fluorescence selective recognition,the photocatalytic degradation ability,fluorescence properties and fluorescence lifetime on the prepared coordination polymers.