The Self-assembly And Property Of Metal-organic Cages Based On Carbazole

Metal-organic cages exhibit a wide range of applications due to their unique physicochemical properties and the cavities present in them.It is an area of concern to achieve the host guest chemistry through the controllable microenvironment.In this thesis,we designed a series of ligands based on carbazole,and obtained metal-organic cages by means of self-assembly.The inclusion effect between the guest molecules and the cages demonstrated the potential in the detection and catalysis aspect.?1?With the similar structure but different sites,two carbazole-based ligands L1 and L2were designed and synthesized to coordinate with metal ions Zn²⁺for the construction of various helicate Zn-L1 and Zn-L2 with diverse cavity sizes.The helicate with larger cavity Zn-L1 realized the selectively detection to PA among the common six explosives,that the smaller one Zn-L2 couldn't achieve.The existence of the host-guest molecule was confirmed by means of ESI mass spectrum,fluorescence titration and ITC experiment,which showed the important role host-guest chemistry played during the detection process.?2?A metal-organic helicate Fe-L3 was designed and synthesized using the carbazole based ligand L3 and the metal ions Fe²⁺.The formation of the inclusion Fl?Fe-L3 was proved through ESI mass spectrum and fluorescence titration.Cyclic voltammetry experiment indicated the potential application of the molecular helicate Fe-L3 in the proton reduction.Photocatalysis proton reduction process was achived with the Fe-L3 as catalyst,the Fl as photosensetizer,the triethylamine as electron donor.The optimal reaction conditions were obtained by using the control variable method.A mononuclear copper complex Fe-L4 was designed to mimic the one corner of the cage Fe-L3.The limiting step for the efficient production of hydrogen was electron transformation,which could be enhanced in the presence of host-guest molecule Fl?Fe-L3.Furthermore,in the process of crystallization,the allosteric regulation behavior between M₂L₃ helicate and the M₄L₆ tetragon was also investigated.