| The metal-organic coordination polymers are composed by metal ions or metal clusters with multidentate organic ligands through coordination bonds,displaying one-dimensional?1D?,two-dimensional?2D?or three-dimensional?3D?structure,which are an important class of novel functional coordination materials.Because of their designability and modification,the unique structures of the complexes can be obtained by the introduction of specific functional groups to the organic ligands.In recent years,the coordination polymers have been extensive studied due to their unique structures and diverse applications such as catalysis,gas adsorption and separation,dye adsorption and separation,drug release,fluorescence sensing,and proton conduction.The selected of the organic ligand plays a very important role in the design of the coordination polymers.Adenine ligand is a purine ligand containing a-NH2 function group and four nitrogen donors,which is a suitbale ligand for the construction of the coordination polymers.In addition,the aromatic polycarboxylic ligands with various coordination modes,which combined with the metal ions can lead to diverse structures.In this thesis,the adenine and polycarboxylic mixed ligands synergically coordinate to the Zn2+ and Cd2+ ions to afford nine coordination polymers under solvothermal conditions,which were formulated as,?1?{?Me2NH2?2 [Zn6??4-O??ad?4?BPDC?4]·x?solvent?}n?2?{?Me2NH2?[Zn6??4-O??ad?2?NDC?4.5]·x?solvent?}n?3?{?Me2NH2?2[Zn4??2-OH??ad?3?BTB?2]·x?solvent?}n?4?{[Zn3?ad?3?5-SIP??H2O?2?DMF?]·x?solvent?}n?5?{?Me2NH2?[Zn2??2-OH??ad??2-STP?]·DMF·H2O}n?6?{[Zn?H-ad??OH-BDC?]·2H2O}n?7?{[Zn?H-ad??CH3-BDC?]·2H2O}n?8?[Cd3?CH3COO?4?ad?2?CH3CN?2]n?9?[Cd3?5-SIP?2?H-ad?2?H2O?6]nH-ad: adenine;H2-BPDC: 4,4 ?-biphenyldicarboxylic;H2-NDC: 1,4-naphthalenedicarboxylic;H3-SIP: 5-sulfoisophthalic;H3-BTB: benzene-1,3,5-tris?4-benzoate?;H3-STP: 2-sulfoterephthalic acid;5-OH-BDC: 5-hydroxylisophthalicacid;5-CH3-BDC: 5-methylisophthalicacid;All complexes were characterized by X-ray single-crystal diffraction,X-ray powder diffraction?PXRD?,thermogravimetric and infrared spectroscopy.And some of the complexes were studied by gas adsorption,dye adsorption and separation,and fluorescence properties.This thesis includes three chapters:The first chapter introduces the research progress of metal-organic coordination polymer materials and the coordination polymers based on the adenine ligand.The second chapter introduces the synthesis,structure,thermal stability and physical properties of the nine metal-organic coordination polymers.Complexes 1-5 are 3D structures with 1D channels,which occupied by the guest molecules including the H2O,DMF and Me2NH2+.It was found that the complex 2 was not pure phase checked by powder X-ray diffraction data.So the physical properties of complex 2 were not carried out.The gas?N2,CO2,CH4,C2H6,C3H8,C2H4,and C2H2?adsorption-desorption properties of the compounds 1,3,4,and 5 were characterized.The activated compound 1 has the Langmuir and Brumauer-Emmett-Teller surface areas of 1800 and 1250 m2/g,respectively.It can uptake a large amouts of the C3H8 and C2H6,but adsorb little CH4,which gives a high selectivity of 144 for C3H8/CH4?5:95?,revealing the potential as a separation agent for the selective removal of propane from natural gas.Furthermore,compound 1 is stable in water solution and the aqueous solution of pH from 4 to 11.Considering the anionic three-dimensional framework and the structural features that the uncoordinated carboxylate O atoms are lined on the surfaces of the channels,and the cationic Me2NH2+ residing in the 1D channels of compound 1,the aqueous-phase adsorption of the organic dyes were investigated.Compound 1 shows an adsorption of a positively charged ion of methylene blue?MB?selectively over a negatively charged ion of resorufin?RS?,which is pertinent to the anionic nature of the framework,and provides a size-exclusive sieving of MB over other positively charged ions of Janus Green B?JB?and ethyl violet?EV?.Thus compound 1 exhibits efficient separation of gases and organic dyes.The efficient aqueous-phase separation of organic dyes for compound 1 presents a rare example of the queous-phase separation of organic dyes with the coordination polymers because most of the coordination polymers are sensitive to the moisture.Compounds 3 is constructed from benzene-1,3,5-tris?4-benzoate?and adenine ligands and displays a 2-fold interpenetrated 3D framework due to the large skeleton of the benzene-1,3,5-tris?4-benzoate?ligand.The single famework will be shifted and contracted when the guest solvents were removed,which leads to a nonporous compound.In addition,in order to study the sulfonate group on the gas adsoption properties,the carboxylate ligands containing the sulfonate group were introduced into the zinc-adenine system,which produced 3D compounds 4 and 5.But the gas adsorption properties of both compounds are not well-investigated due to the activated conditions for these compounds are not successful.The reason is the guest molecules are still reside in the channels and/or the main frameworks are contracted or collapsed.Compounds 6 and 7 are 2D structures based on the adenine and the isophthalate with a substituent on the 5-position of the benzene.Compounds 8 and 9 are 2D structures constructed from acetate or 5-sulfonate-isophthalate and adenine ligand,respectively.The four 2D compounds display nonporous character.The luminescent properties of these compounds are studied.All compounds are luminescent materials.The third chapter is the summary and prospect of the paper. |
PDF Full Text Request