Study On The Constructions And Properties Of Coordination Polymers Based On Thioether Isomeric Tricarboxylic Acid Ligands

Coordination polymer(CPs)has become one of the most widely used materials because of its adjustable pore size,large specific surface area and exposed metal sites.These excellent properties make it widely used in in the fields of adsorption,separation,catalysis,luminescence,sensing,magnetism and energy storage.Although many CPs have been synthesized in the past few decades,it is still a great challenge to realize the structural regulation of performance and broaden the application range of CPs materials.In this paper,we designed and synthesized two ligands 5-(carboxyl-3-thio)methyl)isophthalic acid(H₃L1)and 5-(carboxyl-2-thio)methyl)isophthalic acid(H₃L2).Under the condition of solvothermal reaction,eight new functional CPs were constructed by using these two ligands and metal ions in d and f regions.The full text is mainly divided into the following four chapters:Chapter 1:The concept,synthesis methods and different application prospects of coordination polymers are briefly described.Chapter 2:Two different three-dimensional CPs were constructed by using H₃L1 and4,4?-bipy with Cd(II)and Zn(II)ions:{[Cd₃(L1)₂(4,4?-bipy)2H₂O]·2H₂O}_n(1)and{[Zn₃(L1)₂(4,4?-bipy)H₂O]·H₂O}_n(2).Both 1 and 2 have unique solid state fluorescence properties.In addition,the excellent fluorescence properties of complex 1 make it possible to selectively recognize Cr O₄^2-,Cr₂O₇^2-and Fe³⁺.Chapter 3:Three different three-dimensional CPs were constructed by using H₃L1 and4,4?-bipy with Cu(II),Ni(II)and Mn(II)ions in the d zone:{[Cu₂(L1)(4,4?-bipy)(OH)]·H₂O}_n(3),{[Ni₃(L1)₂(4,4?-bipy)₂(H₂O)₈]·DMF}_n(4)and{[Mn₃(L1)₂(4,4?-bipy)(DMA)₂]·H₂O}_n(5).3 can selectively adsorb CO₂from the mixture of CH₄/CO₂.In addition,3 can also cyclize CO₂into cyclic carbonate.The basic properties of 4 and 5 are characterized.Chapter 4:Three isomorphic three-dimensional CPs were constructed by using H₃L2 with three different rare earth metal ions Eu(?),Tb(?),Dy(?)in the f zone:{[Ln(L2)(CH₃CH₂OH)₂]·H₂O}_n(Ln=Eu(?)(6),Tb(?)(7),Dy(?)(8)).Both 6 and 7have strong solid-state fluorescence.In addition,a series of novel Eu/Tb bimetal doping CPs with modulated luminescence are also obtained.7 has good fluorescence recognition selectivity for nitrobenzene.8 shows antiferromagnetic interaction.