Construction Of Coordination Polymers Based On Schiff-base Ligands And Transition Metal

Coordination polymers have been extensively studied during the past decade due to their attractivestructures and topologies as well as their potential applications as multifunctional materials in magnetism,conductivity, luminescence, gas adsorption and storage, catalysis and so on.12coordination polymers havebeen synthesized and structurally characterized by IR, thermogravimetric （TG） analyses, luminescentspectroscopy, XRPD and single-crystal X-ray diffraction. It is found that not only the different coordinationmodes of ligand L but also the coordination interaction of the other ligating anionic species （such as SCN－NO－3and I－） and solvent systems could affect the polymeric structures.The text has divided into three chapters which were introduced as follows:（Ⅰ） Herein four Cd（II） and one Ag（I） coordination polymers were synthesized using the twoasymmetrical Schiff base ligands, L¹4-（pyridine-2-yl）methyleneamino-1,2,4-trizaole and L²4-（pyridine-4-yl）methyleneamino-1,2,4-trizaole, respectively. For L¹, we obtained three coordinationpolymers:2D framework [Cd13L²ï¼ˆSCN）₆]_n（1） featuring1D inorganic chains linked tridentate bridgingligands,2D framework [CdL¹I₂]_n（2） containing hexanuclear macrometallacyclic ring units and1D chainstructure {[AgL¹NO₃]}_n（3）. For L², the coordination polymers referred to include a3D polymeric array[CdL²ï¼ˆSCN）₂]_n（4） formed by the coordination interactions between the inorganic2D sheets and bidentateorganic bridging ligands, and a3D chiral supramolecular framework [CdL²I₂]_n（5） containing helicalchains on21axis.（Ⅱ） Two types of the biphenic dihydrazide bridged terminated ligands L³ï¼ˆbis（pyridin-3-ylmethylene）biphenyl-2,2′-dicarbohydrazide） and L⁴（bis （pyridin-4-ylmethylene） biphenyl-2,2′-dicarbohydrazide） were designed and synthesized. Coordination chemistry of these newligands with M （II）（M=Zn、Cd and Mn） was investigated, and five coordination polymers were obtained.The coordination polymers referred to include three2D sheet frameworks {[Cd（L³NO₃）₂]（H₂O）₆}_n（6）,{[Zn（L³SCN）₂]（H₂O）₂（CH₃OH）_0.5}_n（7）,{[MnL³ï¼ˆNCS）₂]·（H₂O）₄}_n（8）, and two1D chain frameworks{[CdL⁴I₂]（H₂O）₂（CH₃OH）}_n（9） and {[CdL⁴（NO₃）₂]（H₂O）₈}_n（10）.（Ⅲ） Two chiral porous coordination polymers {[AgL⁵（DMF）][AgL⁵]₂(PMo₁₂O₄₀) DMF3H₂O}_n（11）and {[（AgL⁵）₃](PW₁₂O₄₀)·6H₂O}_n（12）, were synthesized based on Schiff-base ligand L⁵（2,5-bis（3-pyridyl）-3,4-diaza-2,4-hexadiene）, AgNO₃3and [PX12O₄₀]–（X=MoVI, WVI）, respectively.