Syntheses,Structures And Properties Of Coordination Compounds With Bis(1,2,4-triazol-4-yl)

Nowadays,industrial wastewater has become a serious global environmental issue with the development of modern industry.Coordination polymers(CPs)have attracted great interest because of their potential application for wastewater treatment.Bis(4H-1,2,4-triazol)ligandsare very strong coordination ability with a variety of coordination models,They and metal ions with carboxylic acid ligands construct coordination polymers which have changeable space structures and unique properties and functions.Synthesis coordination polymers with bis(4H-1,2,4-triazol)ligandshas important research significance in environmental protection.In this thesis,we choose one semi-flexible 1,3-bis(1,2,4-triazol-4-yl)benzene(mtrb)as the main ligand,with a series of polycarboxylic acids as the second ligand and metal ions Cu(Ⅱ),Cd(Ⅱ),and Zn(Ⅱ).Then we have got 12 coordination polymers,and their crystal structures were measured,and the photocatalysis,adsorption and fluorescence properties of some of them were studied.Part One:Three Cu(Ⅱ)coordination polymers have been synthesed based on mtrb:{[Cu4(OH)2(mtrb)2(meip)(SO4)2]·9H2O}.(1),{[Cu4(OH)2(mtrb)2(sub)(S04)2]·8H2O}｝(2),{[Cu4(OH)2(mtrb)2(btc)2(H2O)2]·H2O}n(3).CPs 1-3 are both copper(II)coordination polymers based on a tetranuclear hydroxyl-copper cluster unit;1 and 2 are the 2D network;3 features the(3,8)-connected 3D metal-organic structure.1-3 all show a high photocatalytic degradation efficiency of photocatalytic degradation of organic dye under UV irradiation.CPs 1 and 2 show good catalytic property,and they can be well applied to the degradation of organic pollutants in wastewater.Part Two:{[Cu4(OH)2(mtrb)2(1,4-bda)2]Br2·6H2O}n(4)was designed and synthesized by using the mtrb ligand and metal Cu(Ⅱ)with means of(1,4-bda),4 is an unusual porous cationic metal-organic framework based on a tetranuclear hydroxy-copper(Ⅱ)cluster displays fast and highly efficient dichromate trapping through a single-crystal to single-crystal proces.To study the adsorption capacity of Cr2O72-ions,through five kinds of anion interference experiments,and 4 shows very well selective adsorption of Cr12O72-ions,thus it can be a very well applied in heavy metal wastewater treatment.Part Three:We continued to use the mtrb ligand and the metal Cd(Ⅱ)and Zn(Ⅱ)through the different carboxylic acid ligand debugging design of the synthesis of six different structures of complexes:{[Cd2(mtrb)0.5(meip)2(H2O)]·H2O}n(5),{[Cd(mtrb)SO4]·2H2O}n(6),[Zn(mtrb)(meip)·H2O]n(7),[Zn(mtrb)(hip)·H2O]n(8),[Zn(mtrb)(nbdc)]n(9),[Zn(mtrb)(nip)]n(10).5 is the 3D network;6 and 8 are the 2D network;7,9,10 are the 1D chain.5-8 all exhibit strong fluorescence intensity.Part Four:We also use the mtrb ligand and the metal Cu(Ⅱ)to provide different solvent environments with reduced carboxylic acid ligands,two complexes were synthesized:{[Cu8(mtrb)4Br5](SO4)1.5·2H2O}n(11),{[Cu2(mtrb)Br]Br}n(12).11 is a three overlapping diamond 3D network;12 is the 1D chain.CPs 11 and 12 all have d’0 electron configurations and luminescent properties,and complex 11 also has the good performance of the catalytic degradation of organic dyes.