Dissertation > Mathematical sciences and chemical > Chemistry > Polymer chemistry ( polymer ) > Polymer physics and physical chemistry of polymers > The chemical nature of polymers

Syntheses, Structures and Properties of Metal-organic Coordination Polymers Based on Long-Chain Aromaticmulticarboxylate

Author ZhangQingFeng
Tutor YuanAiHua;LuoJunHua
School Jiangsu University of Science and Technology
Course Materials Physics and Chemistry
Keywords Aromatic polycarboxylic acid of the long-chain Coordination polymers Topology Hydrothermal Synthesis Crystal structure Adsorption properties Magnetic Fluorescence spectroscopy
CLC O631.3
Type Master's thesis
Year 2011
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Crystal engineering under the guidance of the metal - organic coordination polymers and supramolecular chemistry has become one of the hot spots of today's chemical research. Self-assembled supramolecular coordination bonds, hydrogen bonds and π-π interactions force ions and organic ligands guide the metal center, the design and synthesis of novel coordination polymer structure and study gas adsorption, molecular catalysis, non- linear optics and optical, electrical, and magnetic field of functional materials with important academic significance and potential applications. The papers in supramolecular self-assembly under the guidance of thinking as the main long-chain aromatic polycarboxylic acid ligands, combined with the bipyridine or imidazole butane ancillary ligands, and transition metals (Zn, Cd) or lanthanide rare earth metals ion synthesized 12 novel coordination polymers assembled under hydrothermal or solvothermal conditions, using X-ray diffraction analysis, elemental analysis, infrared spectroscopy, thermal gravimetric analysis, powder X-ray diffraction, gas adsorption, characterization of solid-state fluorescence, magnetic and other means of the synthesis of new compounds, structural characterization and performance testing. Selection of 3,3 ', 5,5' - azo-biphenyl tetracarboxylic acid (H 4 ABTC) long chain aromatic organic ligand with the transition metal ion M 2 (M = Zn, Cd) by solvothermal reaction three novel structure is similar to the three-dimensional coordination polymer {Zn 2 (abtc) (H 2 O ) 2 ] · 3H 2 O · 2DMF} n (1), {[Cd 2 ((abtc ) (H 2 O) (DMA) 2 ] · (H 2 O) · 3 (DMA)} n (2) and {of Cd 2 (the abtc) (DMF) 3 · 3DMF} n (3) successfully cultivate their single crystal, parsing the crystal structure and characterization of the series of coordination polymers. coordination polymers 1 belongs to the monoclinic system, P2 1 / c space group; 2 belongs to monoclinic crystal system, P2 1 / c space group; the three tetragonal symmetry, P4 3 2 1 2 chiral space group. these three These complexes are by ABTC tricarboxylic acid 4 - carboxylic acid ligands secondary structural units are connected to each other forming a three-dimensional skeleton structure having a certain porosity. optional 3,4 ', 5 - biphenyl as the first ligand, 2,2 '- bipyridine or 1,4 - Imidazoles butyric alkoxy as the auxiliary ligand, the transition metal ion M 2 (M = Zn, Cd) through the water The thermal reaction of three new coordination polymers, {[2,2 '-bipy] [Zn (HBPT)] · H 2 O} n (4) , {[2,2 '-bipy] [Cd (HBPT)] · 2H 2 O} n (5) and {[1,4-BBI] [Cd 3 (BPT) 2 (H 2 O)] · 5H 2 O} n (6). coordination polymer 4 is a \biphenyl-tricarboxylic acid, in the reaction with the lanthanide metal ions under the conditions of a solvothermal reaction five isomorphic coordination polymers, {Ln (BPT) (H 2 O) (DMF) · 3H 2 O} n (Ln = Nd, Sm, Eu, Gd, Tb, 7-11). coordination polymers of the series in the monoclinic system, C2 / c space group, the use of [Ln 2 2 -CO 2 ) 2 2 -CO 2 ) 2 ] unit as a secondary structural units (SBUs), through the BPT 3 - carboxylic acid with body These secondary structural units are connected to each other, thereby forming a three-dimensional porous skeleton structure. room temperature solid fluorescence analysis showed that each of these polymers exhibit good rare earth metal-fluorescence properties, also studied the series of magnetic polymer. synthesized A alkynyl-containing long-chain aromatic carboxylic acid ligands (H 4 PBEC), under solvothermal conditions with Cu (NO 3 ), 2 < / sub> synthesized by the reaction of a new coordination polymers 12, single-crystal diffraction analysis shows that 12 is a hexagonal space group R-3, the dual-core Cu (II) ions to form the famous waterwheel-like secondary structure unit, these basic structural unit is connected by PBEC4-carboxylic acid ligands, eventually forming a three-dimensional porous framework materials. fluorescence spectra analysis showed that the Cu (II) ions in the coordination polymers the ligand H 4 PBEC fluorescence properties of quenching gas adsorption analysis showed the complex N 2 and H , 2 has a higher adsorption capacity.

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