Syntheses,Structures And Properties Study Of New Metal-Quinolone Coordination Complexes

The aim of this thesis is to synthesize new metal-quinolone coordination complexes on the basis of different quinolones, aromatic polycarboxylate ligands and metal ions (or their multi-nuclear clusters). In this dissertation, we have focused our study on the syntheses, structure and properties of metal-quinolone complexes with kinds of ligands, analysis influence of ligands and metal ions on the formation of the metal-quinolone complexes and to explore the relationships between structures and properties for these new compounds. We have prepared a series of new metal-quinolone complexes on the basis of hydrothermal technique. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by IR spectra, TG, X-ray powder diffraction and elemental analyses. The luminescent properties and magnetic properties of these compounds have been studied.1. Five new metal-quinolone complexes with entangled and helical characters have been hydrothermally synthesized on the basis of metal ions or their multi-nuclear clusters connected by aromatic polycarboxylate ligands and two different quinolones: [Cd3(ppa)2(oba)2(H2O)3]·0.25H2O (1) [Cd2(saraH)2(bpdc)2]·4.5H2O (2) [Mn(sara)2]·2.5H2O (3) [Mn(ppaH)(oba)]·3H20 (4) [Zn(ppaH)(sdba)]·1.5H2O (5)Compound 1 is the first 3D interpenetrated metal-quinolone complex, containing unique 5-fold interlocking tri-flexure helices and 15-fold interwoven helices, defines an unprecedented 3-fold interpenetrated double-edged pseudo-diamondoid (pseudo-dia) network. Compound 2 is an uncommon 2D self-threading network containing unusual meso helices. Compound 3 exhibits a novel (2D→3D) polythreaded architecture containing left- and right-handed helices. The structures of compounds 4 and 5 are closed to be isostructural and consist of novel 1D polymeric chains spanning two different directions, which display an intriguing 1D→3D inclined polycatenation of supramolecular ladders. The fluorescent study on the compounds based on d10 metals of compounds 1,2 and 5 are also discussed.2. A serses of new metal-quinolone complexes have been hydrothermally synthesized on the basis of metal ions or their multi-nuclear clusters connected by aromatic polycarboxylate ligands and a serses of quinolones: [Cd3(ppa)2(bpdc)2(H2O)2]·5H2O (6) [Cd2(sara)2(μ2-Cl)2]·5H2O (7) [Cd(cfH)(bpdc)]·H2O (8) [Cd(norfH)(bpdc)]·H2O (9) [Mn(norfH)(bpdc)]·H2O (10) [Mn2(cfH)(odpa)(H2O)3]·0.5H2O (11) [Co2(norfH)(bpta)(μ2-H2O)(H2O)2]·H2O (12) [Co3(saraH)2(Hbpta)2(H2O)4]·9H2O (13) [Zn(levofH)(sdba)]·H2O (14) [Co(cfH)(oba)(H2O)2] (15) [Ni(cfH)(oba)(H2O)2] (16) [Mn(cfH)(bpda)(H2O)]·2H2O (17) [Mn(ppaH)2(bpdc)] (18) [Mn(lomeH)2(bpdc)]·4H2O (19)Compound 6 is a unique 3D metal-ppa complex containing the intertwined homo-axis covalent helices. Compound 7 is an unprecedented 3D helical metal-quinolone complex constructed by inorganic Cl- ions. Compounds 8-10 consist of novel 2D arm-shaped helical layers. Compounds 11 and 12 consist of novel 2D arm-shaped helical layers based on tetranuclear metal clusters. Compound 13 exhibits a novel 2D bilayer structure, which represents the first example of metal-quinolone complexes with 2D bilayer structure. Compound 14 is a unique chiral metal-levofH complex containing right-handed helices. Compounds 15 and 16 are isostructural and feature 1D helical structure. Compound 17 exhibits a double-chain-like ribbon formed from the interconnection of [Mn2(cfH)2(μ-CO2)2] dimers with bpda ligands. Compounds 18 and 19 contain similar 1D zigzag chain. The fluorescent study on the compounds based on d10 metals of compounds 6,8 and 9 and the magnetic properties of compounds 10-13,17 have been studied.