Synthesis And Exploration Of Metal Organic Coordination Cavities Based On Tridentate Ligand

Metal-organic coordination compounds with cavities have wide applications in host-guest recognition,ion detection,gas storage and separation,chemical catalysis and drug delivery and so on;due to their adjustable and unique cavity structure,In this dissertation,series of metal-organic tubular complexes and metal-organic porous complexes were prepared by selecting suitable tridentate ligands and different metal nodes.The dissertation is divided into the following four parts:Part I.The synthesis and applications of metal organic tubes and metal organic porous complexes were briefly described in the introduction part.Part II.Two novel metal-organic tubes with similar structure but different size were synthesized through self-assembly of Ligand L¹(tris(pyridin-4-ylmethyl)amine)with zinc halide in the N,N-dimethyl acetamide(DMA)solution.Induced by cyclohexane,ligand L¹ can self-assemble with zinc bromide and zinc chloride to lead to metal organic tubes 1[Zn₃(L¹)₂Br₆]_n and 3{[Zn₃(L¹)₂Cl₆]},respectively;while Zn I₂ cannot lead to similar tubular structure under the same conditions.Tube 3 can encapsulate tetrahydropyran,1,4-dioxane,1,3-dioxane to form corresponding encapsulated complexes,5{[Zn₃(L¹)₂Cl₆](Pyran)}_n,6{[Zn₆(L¹)₄Cl₁₂](1,4-dioxane)₉}_n and 7{[Zn₆(L¹)₄Cl₁₂](1,3-dioxane)₄}_n.separately.While only more polar 1,4-dioxane and1,3-dioxane molecules can be encapsulated in tube 1 to form encapsulated complexes 9{[Zn₃(L¹)₂Br₆](1,4-dioxane)₃}_nand 10{[Zn₆(L¹)₄Br₁₂](1,3-dioxane)₅}_n,Part III.A novel metal organic porous complex 11[Co₃(L¹)₄(SCN)₆]_n with free thiocyanate was constructed from ligand L¹ and cobalt thiocyanate,which shows excellent acid-base resistance and thermal stability;moreover,it can selectively and effectively adsorb mercury ions from water.Also,two new metal organic porous complexes 12{[Zn₆(L²)₄(NO₃)₄](NO₃)₈}_n and 13{[Zn₆(L²)₄(Cl O₄)₅](Cl O₄)₇}_nwere prepared through reaction of ligand L²(1,1,1-tris[(4-(pyridin-4-yl)phenoxy)methyl])ethane with zinc nitrate and zinc perchlorate,respectively.Part IV.The summary and outlook on our researches were presented in this part.