Study On The Properties Of Functional Complexes Based On Aromatic Amino Acids And Rigid Tetracarboxylic Acid

In recent years,chiral,magnetic and luminescent functional complexes have attracted much attention,not only because of its fascinating structure,but also widely used in various fields.In order to construct functional metal organic frameworks,the aromatic chiral amino acid and rigid tetracarboxylic acid ligands were selected,combining with transition metal clusters or chains as structural and functional carriers.Ten novel complexes were prepared by hydrothermal / solvothermal method,and the chiral recognition,fluorescence sensing and magnetic properties were studied.The main research results are as follows:1.Three complexes were prepared from chiral ligand N-(2-carboxybenzyl)-L-histidine:[Co2((L)-cbh)2H2O]·2H2O(1)? [Ni2((L)-cbh)2H2O]·2H2O(2)and[Fe3(COO)2((L)-cbh)2]·2H2O(3).And under the induction of chiral D-camphoric acid,a chiral complex with a quadruple helix chain: [Me2NH2]5[Co(?2-O)(NO3)(qptc)](4).Wherein1 and 2 are isomorphic,all of which are chiral and can be used for chiral recognition of D/L-mandelic acid ? D/L-histidine acid and D/L-tryptophan acid by circular dichroism spectroscopy.In addition,1 has an uncoordinated imidazole nitrogen atom,which can be used as an alkaline catalyst to catalyze the Knoevenagel reaction.3 is a 2D layered structure constituted with a one-dimensional carboxyl ferrite chain SBUs.The magnetic test showed that 1 had an antiferromagnetic behavior,2 had a spin canting antiferromagnetic behavior.2.With 2,2',5,5'-terphenyltetracarboxylic acid as the main ligand,under the control of different nitrogen-containing ligands,two fluorescent materials were obtained with zinc salt:[Me2NH2]4[Zn6(qptc)3(trz)4]·6H2O(5)and [Zn2(qptc)(bpy)]·DMF(6).A series of metal clusters and chains-based magnetic materials are obtained: [Me2NH2]2[Co4(?3-O)2(pz)(qptc)2](7)?[Co4(?3-O)2(qptc)2(H2O)2]·4H2O(8)?[Me2NH2]2[Co3(?3-O)2(qptc)(H2O)3DMF](9)and[Me2NH2][Co3(?3-O)3(qptc)(H2O)](10).5 is an anionic structure based on the three-dimensional atn topology with the Zn4(trz)2 chain,and [Me2NH2]+ cation is filled in its channel.Interestingly,it can selectively adsorb heavy metal contaminants Cr3+ ions in aqueous solution and visualize detecting nitro-explosives TNP with a quenching coefficient KSV of 2.08×106 M-1,higher than the maximum of reported MOF(5.1×105 M-1).6 is a three-dimensional neutral framework constructed by paddle-wheel [Zn2(CO2)4] SBUs.It can selectively detect Fe3+ in DMF solvent,and has a strong fluorescence quenching ability.7 and8 are the tetra-nuclear clusters [Co4(?3-O)2] based the three-dimensional rtl topology and layer structure,respectively.9 and 10 are both three-dimensional structure,but with different metal chain as SBUs: metal chain of alternate connection vertex-sharing and edge-sharing and ribbon chain.In addition,7 and 9 both have pseudostructures and double layer capacitance.