| Metal-organic framework as functional materials with repeating structural units are formed by self-assembly of metal centers and organic ligands by coordination bonds.Among them,metal ions,organic ligands pH,metal-ligand ratio and so on may affect the structure and properties of the complexes.Complexes with special functions can be obtained by selecting different metal ions and designing organic ligands,which has a good applications in gas storage,purification and separation,luminescence,catalysis and magnetic materials.In this paper,bis?4-carboxyphenyl?phosphinic acid was selected as the O-donor ligand,and a nitrogen-containing ligand was introduced.Twenty-five complexes were synthesized under the conditions of hydrothermal method and solvent evaporation method.In addition they were characterized by single-crystal,infrared spectroscopy,thermogravimetric analysis and fluorescence spectroscopy.This paper is mainly divided into following four parts.The first part mainly introduces the application of complexes in gas adsorption and separation,small molecule detection,catalysis and magnetism.The research status of carboxylic acid complexes and the purpose and significance of the topic are also studied.The second part is about the synthesis,structural analysis and thermal stability analysis of seven porous metal complexes with bis?4-carboxyphenyl?phosphinic acid,including[Zn?HBPO?]n·2n DMF·1.5nH2O?1?,[Zn3?HBPO?3]n·6n?2A-5mpy?·nH2O?2?,[Cu3?BPO?2?H2O?2]n·4nDMF·4H2O?3?,[Cu3?BPO?2?DMF??H2O?2]n·2nDMF·3nH2O?4?,[Co3?BPO?2?DMF?2?H2O?6]n·2nDMF·nH2O?5?,[Mn2?HBPO?2?H2O?]n?6?,[Mn3?BPO?2?H2O?4]2n·2nDMF·2nH2O?7?,Where H3BPO=bis?4-carboxyphenyl?phosphinic acid,2A-5mpy=2-amino-5-methyl-pyridine.Structural analysis shows that 5 is a two-dimensional structure,and the other six compounds are three-dimensional structures.Among them,The topology symbol of 1 is{42.63.8}and the 2 is{42.64}while the5 is{42.6.82.10}2{42.6}2{8}.The third part mainly about ten complexes were synthesized by bis?4-carboxyphenyl?phosphinic acid and bridging ligands?dpp,dpe,4,4'-bipy?,chelate ligands?phen,2,2'-bipy and their derivatives?,including[Zn2?HBPO?2?dpp?]n·nH2O?8?,[Zn?HBPO??dpe?0.5]n?9?,[Cd?HBPO??dpe?0.5]n?10?,[Cd?HBPO??dpe?0.5·H2O]n·nDMF?11?,[Cd?HBPO??phen?]n?12?,[Cd?HBPO??phen?]n·2nH2O?13?,[Cd?HBPO??4,4'-bipy?0.5]n?14?,[Cd?HBPO??2,2'-bipy?]n?15?,[Cd?HBPO??4,4'-m-2,2'-bipy?]n·nH2O?16?,[Cd?H2BPO?2?4,4'-tBu-2,2'-bipy?2]·2H2O?17?,Wherein dpp=4,4'-?1,3-propanediyl?bis-pyridine,dpe=1,2-di?4-pyridyl?ethylene,phen=1,10-phenan-throline,4,4'-bipy=4,4'-bipyridyl,2,2'-bipy=2,2'-bipyridyl,4,4'-m-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridyl,4,4'-tBu-2,2'-bipy=4,4'-di-tert-butyl-2,2'-bipy-ridyl.Single-crystal analysis that the complexes 8,9,10 and 14 are three-dimensional structure,while the 11 and 12 possess two-dimensional structures.The 13,15 and 16 exhibits one-dimensional chain structures,and 17 are single-core structure.In addition,We also discuss the factors which affects the structure and properties of complexes such as different experimental methods,counter-ions and auxiliary ligands.Moreover,photoluminescence properties of the complexes were also studied in detail.In the fourth part,eight complexes were synthesized on bis?4-carboxyphenyl?phosphinic and flexible dimethylene benzimidazole ligand,including[Co4?HBPO?4?1,2-bix?2]n·nH2O?18?,[Co2?HBPO?2?1,4-bix?]n·nH2O?19?,[Zn2?HBPO?2?1,4-bix?]n·nH2O?20?,[Zn?HBPO??1,4-bix?0.5]n·2nDMF·nH2O?21?,[Zn?HBPO??1,4-mbix?0.5]n·nDMF·2n H2O?22?,[Cu2?HBPO?2?H2O?2]n·n?1,4-mbix?·5nH2O?23?,[Cd6?BPO?4?1,3-bix??H2O?8]n·3nH2O?24?,[Cd?HBPO??DMF??H2O?]n·nH2O?25?,Wherein 1,n-bix?n=2,3,4?=1,n-?dimethylenebenzene?diimidazole,1,4-mbix=1,4-??2-methylimidazolyl?methyl?benzene.Single-crystal diffraction showed that 1822 were two-dimensional structures,while23 and 25 were one-dimensional chains structure and 24 is a three-dimensional network. |
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