Syntheses, Structures And Properties Of Coordination Polymers With Aromatic Dicarboxylates Modified By Sulfone

Metal-organic frameworks or coordination polymers have attracted much attention in recent years because of their fansinating structures and their potential applications in gas storage and separation, heterogeneous catalysis, magnetic and optical properties. The organic ligands containing dicarboxylate groups offer great potentials for fine control over coordination architectures. Ten new coordination polymers, including one dimensional, two dimensional, and three dimensional motifs, have been prepared, and the luminescence and thermostability of some of the complexes have been characterized.The main results can be summarized as following five parts:(1) We obtained the ligand called S,S-dioxodibenzothiophen-3,7-dicarboxylic acid (H2DBTDC-O2) from organic reaction using biphenyl-4,4-dicarboxylic acid. The ligand was characterized by IR spectra,1H-NMR spectra and X-ray diffraction. The ligand is not a linear one so generate fancinating structures.(2) The assembly of lanthanide metal-organic frameworks with H2DBTDC-O2 (S,S-dioxodibenzothiophen-3,7-dicarboxylic acid):we have revealed three isomophous lanthanide metal-organic frameworks based on the octahedral secondary building units. In the structures, two lanthanide(III) ions are bridged by four syn-syn carboxylate groups and chelated by another two carboxylate groups to generate a [Ln2(COO)6] dinuclear moiety, which serves as octahedral secondary building units (SBUs) to produce the rare sxb 3D net (485463). instead of the default primitive cubic (pcu) net. The frameworks possess relatively large solvent-occupied cavities despite the presence of 2-fold interpenetration. The Eu(III) compound displays intense luminescence as a result of the efficient ligand-to-metal energy transfer.(3) Four coordination polymers constructed from Cd(II) and Mn(II) with H2DBTDC-O2 in different conditions generated different stuctures as expected. In compound 4, two-dimensional sheet based on the three-nuclear second building units while in 5, three-dimentional polymers based on the three-nuclear and four-nuclear alternatively, as expected, the sulfone groups, which are ordered in the surface of the channel, impart the surface with higher polarity, unfortunately, the compound are obtained in low yield.(4) Crystal engineering of coordination polymers with phenylenediacrylic acids and different bipyridyl bridging motifs:three new coordination polymers were synthesized based on the solvothermal reactions of H2DBTDC-O2 with Zn(â…¡) or Mn(â…¡).