Synthesis, Structural Characterization and Properties of Metal Coordination Polymers with 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (bpdh) and Oxygen-Containing Ligands

• Main Authors: Wang, Tzu-Heng, 王子衡
• Other Authors: Wang, Chih-Chieh
• Format: Others
• Language: zh-TW
• Published: 2019
• Online Access: http://ndltd.ncl.edu.tw/handle/yfq9dc

碩士 === 東吳大學 === 化學系 === 107 === Abstract Assembly of 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (bpdh) with first row transition metal salts [Zn(II), Co(II), Mn(II)] in combination with the various O-containing auxiliary ligands, yielded eight coordination polymers (CPs), [Co(bpdh)(C4O4)(H2O)2] (1), [Zn(bpdh)(C4O4)(H2O)2] (2), [Zn(bpdh)2(C5O5)]∙C2H5OH (3), [Mn(bpdh)(5-Nipa)(H2O)2]∙H2O (4), [Co(bpdh)(5-Nipa)(H2O)2]∙H2O (5), [Zn(bpdh)(5-Nipa)] (6), [Co(bpdh)(1,3-BDC-5(OH))(H2O)]∙(bpdh)0.5 (7), [Zn(bpdh)(1,4-BDC-2,5(OH))]∙C2H5OH∙2H2O (8) using slow evaporation technique at room temperature. The compound 1-8 were characterized by single crystal X-ray diffraction analysis and were further characterized by elemental analysis, infrared spectroscopy (IR). Compound 1-2 are isostructural. The bpdh and C4O42- both adopt a bis-monodentate coordination mode connecting the M(II) ions to form two-dimensional (2D) layered metal-organic frameworks (MOFs). Adjacent 2D layers are then arranged in a mutually parallel and interpenetrating manner to construct their 3D supramolecular architectures. Compound 3,4 and 5 have 1D fishbone-like chain. Adjacent chains are then extended to a 2D layer framework though the π-π interaction. In compound 6, both the 5-Nipa and bpdh acts as a bridging ligand with a bis-monodentate coordination mode connecting the Zn(II) ion to form a 2D zigzag-like layered MOF. Adjacent layers are then stacked in ABAB manner via hydrogen-bonding interaction to complete its 3D supermolecular architecture. Compound 7 displays a 2D grid-like structure, having bpdh ligands in the crystal void, and this is further extended by means of intermolecular π-π interaction into a 3D supermolecular structure. In compound 8, the 1,4-BDC-2,5(OH) and bpdh both act as bridging ligands with a bis-monodentate coordination mode, connecting the Zn(II) ion to form a 3D diamond-like MOF. The thermal stability and related solvent ad-/de-sorption properties of 1-8 will be studied by TG analysis and PXRD measurement.