Functional sulfone dicarboxylic acid coordination polymer synthesis, structure and properties

Title: Functional sulfone dicarboxylic acid coordination polymer synthesis, structure and properties
　　Author: Yan Li
　　Degree-granting units: East China Normal University
　　Keywords: porous coordination polymers;; metal-organic framework;; crystal structure;; topology;; fluorescence
　　Summary:
　　Porous metal-organic frameworks (MOFs) or coordination polymers (PCPs) is the current coordination chemistry of one of the hot, mainly refers to the organic ligands and metal ions or clusters through "self-assembly" role and the formation of highly structured unlimited expansion of the structure of a class of coordination compounds. They have a rare earth magnets rich structure, regulation and control of pore size, large surface area and pore volume, so that we can get the appropriate channels and pores can be "modified" and therefore be applied to gas storage and separation, catalysis, nonlinear optical materials and so on. A large number of organic ligands can not only construct different structures and different topologies, but also gave us "modification" of possibilities. In this paper, the crystal engineering of coordination polymers under the guidance of the sulfone functional dicarboxylic acid ligand as a "pre-modification" of the bridging ligand, with the rare earth ions and transition metal ions assembly, and the introduction of chelation end-bipyridine ligand or a neutral bridging ligand class for structural control, to build nine new one-dimensional, two-dimensional, three-dimensional coordination polymer, study the stability of some of the skeleton of porous materials, luminescent guest molecule The absorption / desorption of the nature and topology.
　　Research work is divided into the following sections:
　　1.S, S-dioxide dibenzothiophene -3,7 - dicarboxylic acid synthesis and characterization: We are from the United acid as a starting point, through organic chemical reactions, have been successfully modified sulfone dicarboxylic acid type ligands . By IR, NMR, single crystal diffraction methods for the characterization of the ligand. This ligand is a rigid structure, and modification of the sulfonyl functional groups; ligand itself is not linear, but there is a certain bent, for the synthesis of novel coordination polymer structure provides the conditions.
　　2.S, S-dioxide dibenzothiophene -3,7 - dicarboxylic acid of the rare earth coordination polymers: (1) H2DBTDC-O2 as a bridging ligand, respectively, with lanthanide ions Eu (Ⅲ), Gd (Ⅲ), Nd (Ⅲ) synthesized three isomorphous coordination polymers. 1-3 in the coordination polymer structure, the two rare earth ions and the formation of six carboxylic oxygen [Ln2 (COO) 6] dual-core unit, by taking μ4 and μ2 bridging ligands to connect way into three-dimensional structure of MOFs. If the dual-core units as six-coordinated nodes, as a bridging ligand connecting lines, forming a sxb topology. In the field of coordination polymers, such as the dual-core unit node, six connecting structure is usually simple cubic (pcu) topology configuration. So we published the article in the novel structure of this report (see page published article 1). Coordination polymer structure in spite of double interludes, but according to PLATON calculations, there are still 30.9% porosity. Solid-state fluorescence tests show that Eu (Ⅲ) compounds have a strong characteristic red fluorescence. Stability tests show that this material at room temperature to 180 ℃ undergoing rapid weight loss, weight loss after a slow, when the temperature reaches 460 ℃, when materials decompose.
　　3.S, S-dioxide dibenzothiophene -3,7 - dicarboxylic acid of Cd (Ⅱ) / Mn (Ⅱ) coordination polymer: the use of ligands under solvothermal conditions in the different synthesized two Cd (Ⅱ ) and two Mn (Ⅱ) coordination polymer. Among them, http://www.chinamagnets.biz/ compound 4 is composed of three core modules of the two-dimensional layered asymmetric structure between layers is ABAB arrangement; compound 5 is composed of three sub-core and quad-core two kinds of cell types of three-dimensional structure consisting of structural units All sulfonyl point hole in the surface played a role in modification of the pore. Compound 6, Mn (Ⅱ) in DMF as solvent in the solvothermal conditions, the formation of a three-dimensional close-packed structure. Compounds 7, Mn (Ⅱ) bridged by monodentate ligands and the ethylene glycol molecules connected into two-dimensional structure.
　　4 neutral chelating or bridging ligand in the S, S-dioxide dibenzothiophene -3,7 - dicarboxylic acid coordination polymers: the use of different lengths and with the principle of rigid, choose a different bipyridine class of neutral bridging ligands with transition metal ions to be assemble three novel coordination polymers. Compound 8 is a one-dimensional double-stranded structure. Compounds 9 and 10, respectively, to 4,4 '-bipy and bpea as ancillary ligands, the use of "pillared strategy" to get a hole in the three-dimensional structure of the compounds, their structural analysis and characterization of a complex thermal stability.
　　Degree Year: 2010