Syntheses,Structures And Properties Of Coordination Polymers Based On O-/S-Spacers Of Semi-rigid Bis-pyridyl-bis-amide Ligands

In this thesis,two semi-rigid bis-pyridyl-bis-amide ligands with O-/Sspacers N,N?-bis?pyridine-3-yl?-4,4?-oxybis?benzoic-yl?dicarboxamide?3-poba?and N,N?-bis?pyridine-3-yl?thiophenyl-2,5-dicarboxamide?3-bptpa?were selected as the main ligands,and multiple polycarboxylates [1,4-cyclohexanedicarboxylic acid?1,4-H2CHDC?,1,3-benzenedicarboxylic acid?1,3-H2BDC?,5-methylisophthalic acid?5-H2MIP?,5-nitroisophthalic acid?5-H2NIP?,2,5-pyridinedicarboxylic acid?2,5-H2TPD?,5-aminoisophthalic acid?5-H2AIP?and 1,3,5-benzenetricarboxylic acid?1,3,5-H3BTC?] have been used as the auxiliary ligands to react with transition metal atoms under hydrothermal/solvothermal conditions.Twenty-one new complexes have been synthesized and characterized by IR,elemental analysis,UV-vis diffuse-reflectance spectra?DRS?,PXRD and single-crystal X-ray diffraction.The TG,fluorescent properties,and photocatalytic properties of some coordination polymers have been studied.1.Using a semi-rigid bis-pyridyl-bis-amide with O-spacer?3-poba?as main ligand and various polycarboxylates as auxiliary ligands,twelve transition metals complexes with different structural features have been hydrothermally/solvothermally synthesized and structurally characterized.The influence of the 3-poba ligand,organic polycarboxylates and the central metals on the structures of complexes has been investigated.[Zn₂?3-poba??1,4-CHDC?₂]·2H₂O?1?[Zn?3-poba??5-MIP?]·3H₂O?2?[Zn?3-poba??1,3-BDC?]·H₂O?3?[Cd2?3-poba??1,4-CHDC?₂]·2H₂O?4?[Cd?3-poba??5-MIP?]·2H₂O?5?[Cd?3-poba??1,3-BDC?]·2H₂O?6?[Cd?3-poba??5-NIP??H₂O?]·H₂O?7?[Cd?3-poba??2,5-TPD?]·DMA?8?[Cd?3-poba??2,5-TPD?]·2H₂O?9?[Zn?3-poba??2,5-TPD?]·2H₂O?10?[Zn?3-poba??1,3-BDC?]·H₂O?11?[Zn2?3-poba??5-AIP?2]·2H₂O?12?Single crystal X-ray diffraction analysis reveals that twelve complexes display five different 2D networks.Complexes 1 and 4 show similar [Zn4?COO?₈] subunits and similar?4²·6⁷·8??4²·6?topology.Complexes 2,3,10 and 11 exhibit the 4-connected?44·62?topology.Complexes 5,6,8 and 9 possess?3,5?-connected?4²·6⁷·8??4²·6?topology.Complex 7 is constructed from the meso helical [Cd?3-poba?]n chains and linear [Cd?5-NIP?]n chains to form a 2D wave-like network.Complex 12 is a?3,4?-connected binodal?6³??6⁶?topology.In complexes 1–12,the semi-rigid bis-pyridyl-bis-amide ligand adopts a ?2-bridging mode in 1-4,7 and 10-12?via ligation of two pyridyl nitrogen atoms?and a ?3-bridging coordination mode in 5,6,8 and 9?via ligation of two pyridyl nitrogen atoms and one amide oxygen atom?,which play an important role in the construction of final polymeric structures.Furthermore,the photocatalytic properties of 1–12 under UV light irradiation and 7–12 by loaded polymer under visible light irradiation have been investigated.2.By changing the N-donor ligand with different spacer,semi-rigid bis-pyridyl-bis-amide with S-spacer?3-bptpa?as main ligand,nine CoII/ZnII/CdII transition metals complexes with different structural features have been hydrothermally/solvothermally synthesized and structurally characterized.The influence of central metals and organic carboxylates on the structures of these complexes,and the influence of structures on their performances has been investigated.[Co?3-bptpa??1,3-BDC?]·2H₂O?13?[Co?3-bptpa??5-MIP?]·2H₂O?14?[Co?3-bptpa??1,3,5-HBTC?]?15?[Co?3-bptpa??5-NIP?]·2H₂O?16?[Co?3-bptpa??1,3-BDC?]·2H₂O?17?[Zn?3-bptpa??1,3-BDC?]·DMA·2H₂O?18?[Zn?3-bptpa??5-MIP?]?19?[Cd?3-bptpa??1,3-BDC?]·2H₂O?20?[Cd?3-bptpa??5-MIP?]·4H₂O?21?Complexes 13-21 display different coordination features: 2D networks or 3D frameworks.Complexes 13-16 display the similar 2D networks with?3,5?-connected topology with the point symbol of?4²·6⁷·8??4²·6?.Complexes 17,20 and 21 show similar 3D ?-Po frameworks,which possess 6-connected uninodal node(4¹²·6³)topology.Complexes 18 and 19 are similar 2D networks,which feature 4-connected uninodal?4²·6²?topology.The versatile structures reveal the effect of the substitute groups of carboxyl group on the architectures.Furthermore,the photocatalytic properties of 13–21 and the photoluminescent sensing behavior of 18–21 for Fe³⁺ ions have been investigated in detail.