| Coordination polymers formed by the coordination of organic ligands and metal ions or metal clusters have the characteristics of easy separation,simple synthesis,and beautiful structure.Therefore,they have developed rapidly in the field of supramolecular materials.By rationally designing organic ligands with different structures or functional groups,using them for the construction of new functional materials has potential application value.Through literature research,we found that the complexes constructed by sulfonic acid-based organic ligands have a unique position and value in the field of coordination chemistry.The non-planarity of the three oxygen atoms of the sulfonic acid group makes it easy to form a high-dimensional coordination polymer structure,and the sulfonic acid oxygen that is not involved in the coordination can form hydrogen bonds with solvent water or small molecules to stabilize the structure of the compound or apply it to small molecule recognition.Regarding the organic body part of sulfonic acid-based ligands,quinones,which are widely present in nature,have attracted our attention due to their unique redox and photooxidation properties.In particular,there are multiple benzene ring conjugates in anthraquinone and phenanthrenequinone,which have potential applications in photocatalysis,energy storage,and batteries.However,the current work on the structure identification and functional research of complexes based on anthraquinone sulfonic acid ligands is very limited.Therefore,in this paper,we selected the anthraquinone-1,8-disulfonic acid ligand,2,7-dicarboxylic acid-9,10-phenanthrenequinone and 4,4'-dicarboxylic acid benzophenone as organic ligands.Thirty-four complexes of different dimensions and topologies were synthesized by coordination with different lanthanide metals,transition metals and auxiliary complexes,[Fe2M(?3-O)(CH3COO)6)](M=Fe2+,Co2+,Ni2+)metal clusters on the basis of three ligands.We determined its structure through X-ray single crystal diffraction,and conducted purity identification and some basic properties of the synthesized complex through X-ray powder diffraction,ultraviolet-visible spectroscopy,fluorescence spectroscopy,infrared spectroscopy,and thermogravimetric analysis.Based on the excellent redox properties of quinone compounds,we conducted a systematic study on the catalytic activity of synthetic complexes.Based on the unique fluorescence characteristics of lanthanide metals,we also studied the ion recognition performance of the synthesized lanthanide metal complexes.The thesis is divided into five chapters,the content is as follows:The first chapter:Overview of coordination polymers,synthesis and properties of transition metal complexes or lanthanide metal complexes based on sulfonic acid ligands,research progress of quinone ligand complexes,construction of functional porous coordination polymerization based on metal clusters.It also briefly expounds the meaning of the topic and the content of the research.The second chapter,Using dipotassium anthraquinone 1,8-disulfonate(1,8-K2AQDS)as the organic ligand,thirteen complexes of different dimensions were synthesized,and the structure of the complex was determined by X-ray single crystal diffraction.The purity and some basic properties of the compounds were identified by X-ray powder diffraction,IR,fluorescence,UV-Vis and thermogravimetric analysis.We further studied and summarized the coordination modes of the complexes.In these complexes,{[La K(AQDS)2(H2O)4]·3(H2O)}n(1),{[Pr K(AQDS)2(H2O)4]·3(H2O)}n(2),{[Nd K(AQDS)2(H2O)4]·3(H2O)}n(3)as the homeomorphism,presenting a three-dimensional non-porous close-packed supramolecular structure;[Sm K(AQDS)2(H2O)8]n(4),[Eu K(AQDS)2(H2O)8]n(5),[Gd K(AQDS)2(H2O)8]n(6),[Tb K(AQDS)2(H2O)8]n(7),[Dy K(AQDS)2(H2O)8]n(8),[Ho K(AQDS)2(H2O)8]n(9),[Er K(AQDS)2(H2O)8]n(10),[Tm K(AQDS)2(H2O)8]n(11),[Yb K(AQDS)2(H2O)8]n(12),[Lu K(AQDS)2(H2O)8]n(13)presenting a one-dimensional chain structure.The thirteen compounds all have?-?stappings and hydrogen bonding due to the conjugated rings in the anthraquinone ligands and the hydrogen bonding between the uncoordinated sulfonate oxygen atoms and the solvent water.We studied these thirteen complexes'catalytic and fluorescence properties.The experiments showed that all the thirteen complexes could catalyze the oxidation of phenyl methyl sulfide to phenyl methyl sulfoxide,and the complex[Er K(AQDS)2(H2O)8]n(10)showed the best catalytic activity among them.Then we explored the universality of the catalyst and proved the catalytic characteristics of the catalyst.We also studied the fluorescence properties of the complex[Eu K(AQDS)2(H2O)8]n(5).The experimental results show that the complex 5 can specifically identify Fe3+ions,which is a enhanced Fe3+fluorescence probe,and the excellent anti-interference performance of the complex for Fe3+recognition has been proved by experiments.Subsequently,dipotassium anthraquinone 1,8-disulfonate(1,8-K2AQDS)was replaced with anthraquinone 1,8-disulfonate(1,8-H2AQDS)by ion exchange resin.By changing the p H of the solution,six complexes with different dimensions and topological structures were synthesized,and their structures were determined by X-ray single crystal diffraction.In these complexes,{[Pr2(AQDS)3(H2O)11]·3.5(H2O)}n(14)and{[Ce2(AQDS)3(H2O)11]·6(H2O)}n(15)presenting a three-dimensional non-porous close-packed supramolecular structure;{[Gd(?2-OH)(AQDS)(H2O)]·(H2O)}n(16),{[Dy(?2-OH)(AQDS)(H2O)]·(H2O)}n(17),{[Yb(?2-OH)(AQDS)(H2O)]·(H2O)}n(19)presenting a one-dimensional chain structure;{[Tm3(?3-OH)4(?6-O)0.5(AQDS)2(H2O)7]2·5(H2O)}(18)presenting zero dimensional finite structure.The structure of these clusters enriches the types of complexes and provides a strategy and method for constructing clusters.In third chapter,We synthesized thirteen complexes with transition metals based on the anthraquinone 1,8-disulfonic acid(1,8-H2AQDS)ligand and phenanthroline or 4,4'-bipyridine auxiliary ligand.Their structures were determined by X-ray single crystal diffraction.The purity of the complexes was determined by X-ray powder diffraction.{Cd(AQDS)(phen)(H2O)2}(20),{Co(AQDS)(phen)(H2O)2}(21),{Mn(AQDS)(phen)(H2O)2}(22),{Ni(AQDS)(phen)(H2O)2}(23)and{Zn(AQDS)(phen)(H2O)2}(24)presenting a hetero-isomorphous mononuclear structure;{Cu(AQDS)(phen)2·(DMA)2}(27)and{Cu(AQDS)(phen)2·(DMF)2}(28)also presenting a mononuclear structure;{Cu(AQDS)(phen)2}n(25),{Cu(AQDS)(phen)(CH3OH)2·(CH3OH)}n(26),{Cd(AQDS)(4,4'-bpy)(H2O)(CH3OH)·(CH3OH)}n(29),{[Cu2(AQDS)2(4,4'-bpy)2(H2O)4]·n H2O}n(31)presenting a one-dimensional chain structure;{Cu(AQDS)(4,4'-bpy)1.5·DMA}n(30)presenting a one-dimensional ladder structure.The catalytic effect of the complex on the coupling of imines was explored.The experimental results showed that the complex{Cu(AQDS)(phen)2}n(25)showed the best catalytic effect,and it was confirmed by 1H-NMR of product structure.In fourth chapter,we synthesized three iron-based MOFs using pre-synthesized metal clusters[Fe2M(?3-O)(CH3COO)6)](M=Fe2+,Co2+,Ni2+)as secondary building units(SBUs),and photosensitive ligands 2,7-dicarboxylic acid-9,10-phenanthone and 4,4'-dicarboxylic benzophenone as organic ligands,and successfully introduced photosensitive quinone ligands or benzophenone ligands into MOFs.In these structures,[Fe3(?3-O)(PQDC)3(H2O)3)]n(32)presents three-dimensional porous structure.[Fe2Co(?3-O)(BPDA)3(H2O)3]n(33)and[Fe2Ni(?3-O)(BPDA)3(H2O)3]n(34)presents two-dimensional porous structure.Subsequently,we have also designed two new ligands,and the synthesis process is in progress.We will further optimize the synthesis process and explore the related properties.The fifth chapter,summary and prospect. |
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