Structure And Properties Of Coordination Polymers Constructed By Dicarboxylic Acids With A Rigid Skeleton

Coordination polymers has received extensive attention from academia and industry as novel inorganic-organic hybrid materials with both metal and organic properties.Compared with traditional inorganic porous materials,coordination polymers have many advantages due to their tunable structure and function.Therefore,coordination polymers can be applied to storage,separation,sensing,drug delivery and catalysis.In this thesis,we focus on two kinds of rigid dicarboxylate ligands?terephthalic acid and thiophene-2,5-dicarboxylic acid?,various transition metal ions(Ni^II/Co^II/Cu^II/Zn^II)and the N-donor ligands as the additional ligand to synthesize nine special construction coordination polymers under hydrothermal or solvothermal conditions.Furthermore,all polymers structures and properties were analyzed by X-ray single crystal diffraction,FTIR,element analysis,PXRD,TGA and fluorescence.This paper includes the following two parts:?1?Under hydrothermal or solvothermal conditions,sulfur-containing ligand with rigid V-type thiophene-2,5-dicarboxylate?H₂tdc?and rigid N-donor ligands?bipy,bpe?in the presence of nickel?II?,cobalt?II?salts have given rise to threenewcoordinationpolymers{[Ni?tdc??bipy?]·2H₂O}_n?1?,[Ni₂?tdc?₂?bpe?₃]_n?2?,{[Co?tdc??bpe?]₂·H₂O}_n?3?.In addition,H₂tdc reacts with flexible N-donor ligands?bpp,bpa?and Co?II?/Cu?II?metals to obtain four coordinationpolymers:[Co₃?tdc?₃?bpp??DMF?₂]_n?4?,{[Co₂?tdc?₂?bpp??H₂O?₃]·4H₂O}_n?5?,{[Cu?tdc??bpp?]₂}_n?6?,[Cu₂?tdc?₂?bpa?]_n?7?.Compounds 1,3,5 and 7 display three dimensional structure with 2-fold interpenetration,while compound 2 show a two dimensional layered structure,which further penetrate to form a 2D?3D structure.Compound 4 possess a two dimensional layered structure with sql net and compound 6 exhibit three dimensional structure with 3-fold interpenetration.The activity and mechanism of photocatalytic that compounds 1-5 to degrade organic dyes were also studied.The analysis results show that compounds 1,3,4 and 5 have photocatalytic degradation activity for CoR,Mo,CBB,and MG,respectively.While compound2 has both degradation activity for CoR and Mo.Therefore,it is indicated that compounds 1-5 has potential application value in photocatalytic degradation of organic dyes.?2?Two coordination polymers{[Zn₃?OH?₂?bdc?₂]·2DEF}_n?8?and[Zn?bdc??DMF?]_n?9?were synthesized by using terephthalic acid?H₂bdc?and zinc nitrate under solvothermal conditions.Compound 8 is a three-dimensional structure with 1D diamond shaped channel.Compound 9 is a 2D 4-connected sql net with a diamond shaped window.In addition,the two coordination polymers have the following potential applications:first,they can be used as luminescent sensors that show a fast and sensitive detection for pollutant Fe³⁺,CrO₄^2-and Cr₂O₇^2-ions in aqueous media;second,compound 8 as adsorbents that can rapidly remove congo red dye from solution;third,compound 8 as an antenna that can selectively sensitize Tb³⁺ions.These compounds materials that combine optical-sensing,adsorption,and sensitization properties have potential applications.