Synthesis,Structure And Properties Of Azoles Carboxylic Acid Complexes

In this paper,three azoles carboxylic acid ligands,3,5-di-(triazol-1-yl)-benzoic acid(HL1),2,4-di-(triazol-1-yl)-benzoic acid(HL2)and 5-((4-(tetrazol-5-yl)phenyl)oxy)isophthalic acid(HL3)were selected as organic ligands to synthesize 10 complexes with different transition and rare earth metal salts under solvothermal conditions.The crystal structures were obtained by X-ray single crystal diffraction and the properties were further studied by IR,PXRD,TGA,UV and fluorescence.1.Three complexes of[CdLlata(H2O)]·H2O(1),[Cd2(L1)2bda(NO3)H2O]·2H2O(2)and[Cd2(L1)2(Tpa)0.5NO3(H2O)3](3)were synthesized by solvothermal reaction of Cd(NO3)2-4H2O and 3,5-bis-(triazol-1-yl)-benzoic acid(HL1)with the existence of 2-aminoterephthalic acid,succinic acid and terephthalic acid.Complex 1 is connected by the ligands to form a 2D layered structure,while complexes 2 and 3 are connected by the ligands to form a 3D framework.Solid state fluorescence experiments show that complexes 1 and 2 have excellent optical properties.Complex 1 can selectively detect Cu2+(LOD:1.97 ?m)and MNO4-(LOD:1.12 ?m),and complex 2 can detect Fe3+(LOD:1.99 ?m)and MNO4-(LOD:4.70 ?m).Amino acid and antibiotic sensing experiments show that complex 1 can detect arginine(LOD:5.40 ?m)by fluorescence enhancement effect and tetracycline hydrochloride(LOD:0.43 ?m)by quenching effect and complex 2 can detect tryptophan(LOD:5.72 ?m)and tetracycline hydrochloride(LOD:0.63?m).The dye adsorption experiments show that complexes 1,2 and 3 have certain adsorption capacity for Congo red dye.2.Three isomorphic complexes[SmL1(NO3)]·H2O(4),[PrL1(NO3)]·H2O(5),[CeL1(NO3)]·H2O(6)were synthesized by using 3,5-di-(triazol-1-yl)-benzoic acid(HL1)as ligand and rare earth metal ions of Sm3+,Ce3+ and Pr3+.In this paper,we only discuss the structures and characterization of three complexes because our team has explored the related properties of the isomorphic Eu-MOF.In addition,a new complex[CuL1(NO3)H2O](7)was synthesized by using HL1 as ligand and transition metal Cu(?)ions.The complex[Cd0.5L2(H2O)](8)was synthesized by using 2,4-bis-(triazol-1-yl)-benzoic acid(HL2)as ligand and transition metal of Cd(II)ions.Solid state fluorescence experiments show that complex 7 has no fluorescence property,while complex 8 has better fluorescence property,The anion and cation sensing experiments show that complex 8 can selectively detect Fe3+(LOD:0.76 ?m)and MnO4-(LOD:0.96?m)with low detection limit.Amino acid and antibiotic sensing experiments show that complex 8 can detect valine by fluorescence enhancement effect and tetracycline hydrochloride by quenching effect(LOD:0.28 ?m).The dye adsorption experiments show that complex 8 has certain adsorption capacity for MG and CR dyes.3.Two unstable complexes[Co2L3(H2O)2]·2H2O(9)and[Zn2L3(H2O)2]·2H2O(10)were synthesized by using 5-((4-(tetrazol-5-yl)phenyl)oxy)isophthalic acid(HL3)as ligand and Co(NO3)2·6H2O,Zn(NO3)2·6H2O under solvothermal conditions.X-ray single crystal diffraction analysis shows that the two complexes are isomorphic and belong to monoclinic system with the space group of P21/m.IR and PXRD results show that the structures of the two complexes have collapsed after leaving the mother liquor.