Synthesis, Structural Characterization and Properties of Metal Coordination Polymers with 4,4’-bipyridyl-N,N’-dioxide (bpno) and Oxygen-Containing Ligands

• Main Authors: MEI-CHI, HUANG, 黃媚琦
• Other Authors: CHIH-CHIEH, WANG
• Format: Others
• Language: zh-TW
• Published: 2015
• Online Access: http://ndltd.ncl.edu.tw/handle/32656371422636674065

碩士 === 東吳大學 === 化學系 === 103 === ABSTRACT This thesis describes the synthesis, structural characterization and thermal stability of ten metal coordination polymers by using different metal ions with 4,4’-bipyridyl-N,N’-dioxide (bpno) and oxygen-containing or nitrogen-containing ligands, including KNCS (Potassium thiocyanate), Na2BDC (Terephthalic acid , disodium salt), K22,6-NDC (2,6-Naphthalenedicarboxlic acid, dipotassium salt), H2C4O4 (3,4-Dihydroxy-3-cyclobutene-1,2-dione), Na2C5O5 (Croconic acid, disodium salt). All of them were prepared in conventional solution method and fully characterized by Infrared Spectroscopy, elemental analysis, single-crystal X-ray diffraction method. Their thermal stability and solvent adsorption properties are studied by thermogravimetric (TG) analysis, and in-situ powder X-ray diffraction method. The chemical formulae of ten complexes are described as follows, including: [Cd(bpno)(NCS)2]n (1), [Co(bpno)(BDC)(H2O)2][Co(H2O)6](BDC)(H2O) (2), [Co(2,6-NDC)(H2O)4][Co(bpno)(2,6-NDC)(H2O)2] (3), [Cd(bpno)(C4O4)(H2O)2]n (4), {[Sc(bpno)(H(C4O4)2)(H2O)2]•2H2O}n (5), {[Sc(bpno)(C4O4)(C2O4)0.5(H2O)2]}n (6), {[Nd2(C4O4)3(H2O)11]•2(H2O)}n(7), {[Ho(C2O4)0.5(C4O4)(H2O)4]•2(H2O)}n(8), [Ho(C4O4)1.5(H2O)3]n(9), and [Sm2(C5O5)2(H2O)14][Sm2(C5O5)4(H2O)10](bpno) (10). Compound 1 exhibits a three-dimensional (3D) metal-organic framework. In compound 2, the 3D supramolecular architecture is composed of two parts, a monomer and a one-dimensional (1D) polymeric chain, where, in compound 3, the 3D supramolecular architecture is composed of a 1D polymeric chain and a two-dimensional (2D) grid-like framework. Compound 4 and compound 5 are both 2D metal-organic frameworks (MOF). Compound 6 is a 1D chain-like coordination polymer, where compounds 7 and 8 are both 1D ladder-like coordination polymers. The structure of 9 is a 2D MOF. Compound 10 is a monomer structure. Hydrogen bonding and - interactions play important roles on the stabilization of these 3D supramolecular architectures.