| Design and synthesis of metal organic coordination polymers with novel structures and excellent properties has been become one of the most flourishing fields in chemical industry,owing to its impressive development prospects in optics,ferromagnetic,store separation,drug delivery,biological probe sensor,proton conduction,heterogeneous catalysis,et al and potential application in industrialization.Dicarboxylic acid has been widely used to construct coordination polymers,not only because of its special carboxylic angle?120o,180o?for directional synthetic complexes but also attributed to flexible groups including methylene,ether bond and hydroxymethyl can be introduced to enrich the diversityofstructuresandproperties.Inthispaper,semi-rigidligand4,4'-?hydroxymethanediyl?dibenzoicacidandrigidligand2,5-dihydroxy-1,4-benzenedicarboxylic acid were chosen to synthesize coordination polymer with metal ions.Eleven novel complexes were obtained by the solvent thermal method with containing N ligands of two different coordination modes?chelating and bridging?including 1,10-phenanthroline?phen?,2,2'-bipyridine?2,2'-bipy?,4,4'-bipyridine?4,4'-bipy?,phenyl diimidazole?BIB?,1,4-bis?imidazol-1-yl-methyl?benzene?BIMB?and transition metal salt Cd?II?,Zn?II?as well as rare earth metal salt Ho?III?,Tb?III?,Firstly.They are named respectively[Cd?HL??phen?]n?1?,[Cd?HL?·C2H5OH]n?2?,{[Cd3?HL?3?4,4'-bipy?·DMF]·1.5H2O}n?3?,{[Zn?HL??BIMB?]n·3H2O}n?4?,{[Zn?H2-DHBDC?0.5?phen?]·?H4-DHBDC?0.5}n?5?,[Cd?H2-DHBDC??2,2'-bipy?2]n?6?,[Cd2?H2-DHBDC?2?4,4'-bipy?2]n?7?,[Zn2?H2-DHBDC??DHBDC?0.5?4,4'-bipy?1.5]n?8?,[Cd2?H2-DHBDC?2?BIB?2]n?9?,{[Ho?H2-DHBDC?1.5?H2O?2]?H2O?}n?10?,{[Tb?H2-DHBDC?1.5?phen?]?H2O?}n?11?.Secondly,these coordination polymers crystal structures,compositions,thermal stabilities and optical properties have been performed by single crystal X-ray diffraction,elemental analysis,thermogravimetry,infrared spectrum,UV-Vis spectrophotometer,fluorescence spectrophotometer and X-ray powder diffraction analysis,respectively.The specific contents are as follows:?1?Complex 1 belongs to triclinic,space group P-1,and is two independent one-dimensional chain structure,one of which is the spiral chain.Complex 2 belongs to monoclinic,space group P2?1?/n,as well as is two-dimensional spiral pipe mesh structure and the inside spiral tube distance of unit Cd...Cd is 10.768?.Complexes 3-4 all belong to triclinic and space group P-1.Nearly linear three nuclear SBU of[Cd3?CO2?3NO]is connected by H3L ligand and 4,4'-bipy to a three-dimensional structure with hole,filled with a large number of solvent water molecules in channel and coordination of DMF molecules.Complex 4 is approximate elliptic nanotube structure and there are many solvent water molecules inside the tube.In addition,the thermal stability shows that they have good thermal stability.Solid fluorescence emission spectrum shows that complexes 2and 3 have well fluorescence properties.complex 3 is a kind of potential separation materials of N2 and H2.?2?Complex 5 belongs to triclinic,space group P-1,it is a zero dimensional structure through bridging ligand.complex 6 belongs to monoclinic,space group C2/c,as well as is a one dimensional structure with"Z"shape.complexes 7 and 8 all belong to monoclinic and space group P21/c.Complex 7 is a three-dimensional structure,eight SUBs are connected by eight H2-DHBDC2-ligands and eight 4,4'-bipyridine molecules to form a closed cube space;complex 8 contains two kinds of coordination of zinc ions and a narrow1D channel in three-dimensional structure.Complex 9 belongs to triclinic,space group P-1,and is a three-dimensional structure.H2-DHBDC2-ligands run through the channel.In addition,the thermal stability shows that they all have good thermal stability.Solid fluorescence emission spectrum shows that complex 7,8 and 9 have good fluorescence properties.?3?Complexes 10 and 11 belong to triclinic,space group P-1,and are similar in structure that two metal centers and four carboxyl ligands constitute a SBU[Ln2?COO?2]?CO2?2]which is connected by ligand further into a 3D structure,while complex 11 is the phenanthroline molecular with chelating ligand model replaces the two coordinated water molecules,which makes the thermal stability and fluorescence of complex 11 are stronger than complex 10.Solid fluorescence emission spectrum shows that complexes 10 and 11 have good fluorescence properties. |
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