Syntheses,Crystal Structures And Luminescent Properties Of Multicarboxylate Based Zinc Coordination Polymers

Coordination polymers（CPs）are usually constructed from metal ions and organic ligands through coordination interactions.Due to the versatile structures and special properties,CPs have significant potential applications in luminescence,catalysis,magnetism,gas storage and separation,drug delivery and so on.Multicarboxylate ligands have been widely used to construct CPs because of their strong ability of coordination and abundant coordination modes,and CPs constructed by d¹⁰electronic configuration Zn²⁺ion are suitable for the evaluation of luminescent properties.In this thesis,three CPs have been synthesized with multicarboxylate ligands and Zn²⁺ion by the solvothermal/hydrothermal method.The final structures have been characterized by various methods including elemental analysis（EA）,powder X-ray diffraction（PXRD）,infrared（IR）spectrum,thermogravimetric（TG）analysis and single-crystal X-ray diffraction.The fluorescence properties of three CPs have been studied as well.The main contents are as follows:1.By assembling Zn²⁺ion with dicarboxylic acid ligand,1,4-bdc（1,4-bdc=1,4-benzenedicarboxylic acid）and the auxiliary ligand,DPNDI（DPNDI=N,N′-di（4-pyridyl）-1,4,5,8-naphthalenetetracarboxydiimide）,a 2D CP{[Zn（bdc）_0.5（DPNDI）（NO₃）]·DMF}_n（CP-Z1）has been synthesized（DMF=N,N’-dimethylmethanamide）,which exhibits a 4-connected‘sql’-type topology.Luminescent experiments suggest that CP-Z1 can serve as a potential probe for sensitively detecting Al³⁺ion in aqueous solution.2.The tricarboxylic acid ligand,H₃btc（H₃btc=1,3,5-benzenetricarboxylic acid）and the auxiliary ligand,Hcptpy（Hcptpy=4-（4-carboxyphenyl）-2,2’:4’,4"-terpyridine）were used to explore the coordination chemistry with Zn²⁺ion,and a 3D CP with 1D channels[Zn₂（cptpy）（btc）（H₂O）]_n（CP-Z2）was obtained under hydrothermal conditions,which could simplify as a new（3,3,4,4）-connected topology.Luminescent results indicate that CP-Z2could be regarded as a highly sensitive probe for detecting paraquat（PAQ）and Fe³⁺ion in aqueous solution.3.A polyfluorinated-aromatic tetracarboxylic acid has been designed and synthesized via the acylation reaction,H₄bdtfa[H₄bdtfa=tetrafluoro-bis-（3,5-dicarboxyphenyl）terephthalamide],which was assembled with Zn²⁺ion to produce a 2D CP{[Zn₂（bdtfa）（py）₃（H₂O）]·2DMF}_n（CP-Z3）（py=pyridine）.CP-Z3 could simplify as a 4-connected‘sql’-type topological structure,and the neighbouring layers are connected by hydrogen bonds andπ···πstacking interactions to give a 3D supramolecular architecture.Luminescent results reveal that CP-Z3could be considered as a potential probe for sensitively detecting nitroaromatics.