Syntheses, Structures And Properties Of Complexes Based On Terphenyl Tetracarboxylate Ligands And Pyrazole Carboxylate Ligands

In this thesis,we chose the tetracarboxylate ligands with terphenyl moieties[1,1':4',1''-terphenyl]-2,2'',5,5''-tetracarboxylicacid?H₄L1?,[1,1':4',1''-terphenyl]-2',4,4'',5'-tetracarboxylicacid?H₄L2?,[1,1':4',1''-terphenyl]-2',3,3'',5'-tetracarboxylicacid?H₄L3?,[1,1':4',1''-terphenyl]-3,3'',5,5''-tetracarboxylic acid?H₄L4?,1H-pyrazole-3-carboxylic acid as the main ligands and some bis-pyridyl ligands as the auxiliary ligands to react with different metal ions.Twenty eight new complexes have been synthesized and characterized by elemental analyses,IR,XRPD and single-crystal X-ray diffraction.In addition,TG,magnetic properties,luminescent properties,adsorption behaviors and catalytic properties of the targeted complexes have been researched.1.Using the single tetracarboxylate ligands with terphenyl moieties,eleven two-dimensional?2D?and three-dimensional?3D?transition metal coordination polymers have been synthesized in the hydrothermal or solvothermal conditions and structurally characterized.We have studied that the solvents and positions of carboxylate groups of the tetracarboxylates ligands have effect on the structures.{[Cd₂?L1??H₂O?₄]·H₂O}_n?1?{[Cd?L1?][?NH₂??CH₃?₂]₂}_n?2?[Cd?L2?0.5?H2O?]n?3?{[Cd?L2?][?NH₂??CH₃?₂]₂·2DMF}_n?4?[Cd?L3?0.5?H2O?]n?5?{[Cd?L3?_0.5?H₂O?]·CH₃OH}_n?6?{[Cd₃?L4?₂][?NH₂??CH₃?₂]₂}_n?7?[Zn₃?L3???₃-OH?₂?H₂O?₄]_n?8?[Co₃?L3???₃-OH?₂?H₂O?₄]_n?9?{[Cu?L1?][?NH₂??CH₃?₂]₂}_n?10?[Cu?L4?_0.5?H₂O?]_n?11?Complex 1 is a?4,8?-connected Al₂Os type 2D structure with the Schl?fli symbol of{4²⁰·6⁸}{4⁶}₂,and the adjacent 2D layers are stacked to result in the 3D supramolecular framework through the O–H???O hydrogen bonding interactions.Complex 2 is a?4,4?-connected PtS type{4²·8⁴}3D framework including the 1D right-handed helix channels.Complex 3 is a?4,8?-connected{4⁴·6²}₂{4⁸·6⁴·8¹⁶}3D framework containing two kinds of channels.Complex 4 is a 3D architecture based on the right-handed helix channels.The DMF organic solvent molecules fill among the L2 ligand,while the counterions NH₂?CH₃?₂⁺occupy the channels of complex 4.Complexes 5–6 are the isostructural.Complex 7 is a 3D architecture based on two kinds of channels,and there are differences between the shapes and sizes.Complexes 8–9 are the isostructural 3D metal-organic framework which contains the oval structures.Complex 10 is a 3D framwork based on right-handed helix channels.Complex 11 is a 3D architecture with the large pores,and the adsorptive selectivity for the CO₂ is better than that for CH₄.Moreover,complexes 10–11 have good catalytic activity for diphenylmethane and its derivatives.2.Six complexes based on the main ligands H₄L1 and H₄L4 have been synthesized in the hydrothermal conditions through introduction of different bis-pyridyl auxiliary ligands.The influence of coordination modes of H₄L1 and H₄L4 ligands on the different complexes has been explored.{[Mn₂?L1??bpfp??H₂O?₂]·6H₂O·CH₃OH}_n?12?{[Mn₂??₃-O??L1??bpe??H₂O?]·H₂O}_n?13?[Ni?HL1??Hbpmp??H₂O?₂]_n?14?[Co₂??₂-OH??HL1??bpmp??H₂O?₄]_n?15?{[Co?L4?_0.5?bpfp?_0.5?H₂O?]·2H₂O}_n?16?{[Co?L4??bpe??H₂O?·H₂O]·[NH₄]₂}_n?17?Complex 12 is a 3D framework,and each?₆-bridging L1^4-ligand links six Mn²⁺ions to form a 2D layer structure.The adjacent layers are connected by the bpfp ligands to generate the 3D framework.Complexes 13–15 and 17 are 2D layers,and they are expanded to 3D supramolecular framework by the hydrogen bonding interactions.In 13,the secondary building unit[Mn₄N₂??₃-O?₂?COO?₈]is formed by the Mn²⁺ions and oxygen atoms.In 14,the Ni²⁺ions link HL1^3-ligands to form one-dimensional?1D?“Z”-type chain,which are constructed 2D structure by the bpmp bridged ligands.In 15,the 2D layer shows that it is?3,3,4?-connected{4·9·10}{4·9²}{4²·9·10³}topological structure.In 17,the adjacent Co²⁺ions link L4^4-ligands to form one-dimensional?1D?wave-like chain along the c axis.Complex 16 is a?4,6?-connected{4³·6³}₂{4⁶·6⁶·8³}3D framework.In respect of properties,complexes 12–15 display fluorescence quenching.Complex 13 possesses the water vapor adsorption ability.The magnetic results exhibit that complex 12 is ferromagnetic coupling,while complex 13 shows anti-ferromagnetic coupling.3.Eleven new complexes based on transition metals or main group metals and H₂pca ligand have been synthesized in the hydrothermal or room temperature conditions.The influences of coordination modes of ligands and presence of the water molecules on the construction of complexes have been investigated.M?Hpca?₂?H₂O?₂?M=Mn?18?,Fe?19?,Cd?20??Cu?Hpca?₂?H₂O?₂·2H₂O?21?Cr?Hpca?₃·2H₂O?22?Cu₂?pca?₂?H₂O?₄?23?M₂?pca?₂?H₂O?₆·2H₂O?M=Ni?24?,Cu?25??[Cd??₂-Cl??Hpca??H₂O?]_n?26?[Pb₂?Hpca?₄]_n?27?Mn?Hpca?₂?phen?·3H₂O?28?Complexes 18–20 are the isostructural mononuclear,and the 2D layers are formed by the O-H···O hydrogen bonding interactions.They are expanded to 3D supramolecular framework by the O-H···O and N-H···O hydrogen bonding interactions.The main structure of complex 21 is the same as that of 18-20,however the presence of the lattice water molecules has the effect on the formation of the final supramolecular framework.Complex 22 is a dipolymer,and 3D supramolecular framework is generated through the hydrogen bonding interactions from the lattice water molecules.Complex 22 is a dinuclear structure,and both 1D supramolecular chain and the 3D supramolecular framework are formed by the hydrogen bonding interactions between the carboxylic oxygen atoms.Complexes 24–25 are the isostructural,and they are 3D supramolecular frameworks based on the dinuclear structures.There are the tetrahedral water clusters in the 3D supramolecular frameworks.Complex 26 is a 3D supramolecular framework based on4-connected{4⁴·6²}2D structure.Complex 27 is a 2D layer,and the adjacent 2D layers are stacked to construct the 3D supramolecular framework by the hydrogen bonding interactions,in which Hpca^-ligand exhibits the various coordination modes.Complex 28 is mononuclear structure,and the 3D supramolecular framework is formed through hydrogen bonding interactions.The“chair-like”hexanuclear water clusters are generated by the hydrogen bonding interactions between the lattice water molecules.In fluorescence,complexes 20,26,27 have the good fluorescence property.