Synthesis, Crystal Structure, Fluorescent Property and DFT Study of a Novel 1D Polymer [Zn(HMICD)(bpy)]_n·2nH_2O

A new one-dimensional（1D） polymer, [Zn（HMIDC）（bpy）]n·2n H2O（1, H3MIDC = 2-methyl-imidazole-4,5-dicarboxylic acid, bpy = 2,2-bipyridine）, has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectrum and fluorescence measurements. Complex 1 crystallizes in orthorhombic system, space group Pbca with a = 14.404（3）, b = 8.6900（17）, c = 26.570（5） , V = 3325.8（11） -3, Dc = 1.700 g/cm-3, Mr = 425.70, Z = 8, F（000） = 1744, μ = 1.522 mm-（-1）, the final R = 0.0421 and w R = 0.1018. The Zn（Ⅱ） ion is six-coordinated by O and N atoms from one HMIDC ligand, two O atoms from another HMIDC ligand and two N atoms from the bpy ligand. The HMIDC anion, which acts as a tetradentate ligand, chelates two Zn ions to form a one-dimensional（1D） zigzag chain structure. We analyzed the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with the UV-vis spectrum. And we also discussed the luminescent mechanism of complex 1 in detail.

A Three-dimensional Tm(Ⅲ)-Zn(Ⅱ)Heteronuclear Metalorganic Framework Based on Imidazole-dicarboxylate Ligand:Synthesis,Crystal Structure and Luminescence Property

A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized under solvothermal conditions,and structurally characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.It crystallizes in orthorhombic system,space group Pnma with a = 16.1102（9）,b = 33.5805（19）,c = 16.8593（10） ？,β = 97.344（11）°,V = 9120.7（9） ？-3,Z = 4,F（000） = 5184,the final R = 0.0530 and w R = 0.1306.In complex 1,the Tm（Ⅲ） ions adopt two types of coordination fashions.Complex 1 shows onedimensional（1-D） Tm-Zn heteronuclear zigzag chains,and these chains are further linked by H3 mimda ligands into Tm-Zn heteronuclear 2-D lattice-like arrays.The 2-D heteronuclear units were connected through [Zn6（mimda）6] rings to give rise to the Tm-Zn heteronuclear cages.Finally,H3 mimda ligands connected the cages into a 3-D heterometallic framework by the combination of [TmO7]n and Tm-Zn heteronuclear cages.In addition,the thermal stability and luminescent property have been investigated.

Hydrothermal Syntheses and Crystal Structures of Three Lanthanide(Ⅲ)Complexes Based on Carboxyl Derivatives of 1,10-Phenanthroline

Three lanthanide（III） complexes [Ln（4-NCP）（1,4-BDC）]n·xn H2O（Ln = Pr（1）, Sm（2）, Nd（3）. 4-HNCP = 2-（4-carboxyphenyl）imidazo（4,5-f）（1,10）phenanthroline, 1,4-H2 BDC = benzene-1,4-dicarboxylic acid） have been hydrothermally synthesized and characterized via elemental analysis, infrared spectrometry and single-crystal X-ray diffraction. Structural analyses revealed that complexes 1~3 possess similar porous three-dimensional frameworks with the point symbol {4^（12）·6~3}. Meanwhile, complexes 1~3 exhibit excellent thermal stabilities and complex 2 exhibits characteristic luminescent property.