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Metal-Organic Coordination Polymers Containing Pyridine-2,3-dicarboxylic Acid N-Oxide (2,3-PDCO)

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posted on 07.01.2009, 00:00 by Li-Li Wen, Zhen-Da Lu, Xiao-Ming Ren, Chun-Ying Duan, Qing-Jin Meng, Song Gao
Ten novel metal-organic coordination polymers, [M53-OH)2(2,3-PDCO)4(H2O)4·xH2O] (2,3-PDCO = pyridine-2,3-dicarboxylic acid N-oxide, M = Mn2+ and x = 3 for 1, M = Co2+ and x = 3 for 3, M = Cd2+ and x = 1.5 for 10), [Mn(2,3-PDCO)(4,4′-bpy)(H2O)2] (2), [M2(2,3-PDCO)2(4,4′-bpy)(H2O)2·xH2O] (M = Co2+ and x = 1 for 4, M = Zn2+ and x = 0 for 7), [M(2,3-PDCO)(L)·H2O] (M = Co2+ and L = bbix (1,4-bis(benzimidazol-1-ylmethyl)-benzene) for 5, M = Zn2+ and L = bix (1,4-bis(imidazol-1-ylmethyl)-benzene) for 8), [Cu(2,3-PDCO)(4,4′-bpy)·H2O] (6), [Zn2(2,3-PDCO)2(bbi)] (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) (9), were obtained under hydrothermal conditions and characterized structurally. The networks exhibit a variety of topologies and coordination modes at the metal centers. 1, 3, and 10 are isostructural and possess three-dimensional (3D) frameworks with penta-nuclear metal clusters as secondary building units (SBU). 5 and 7 individually exhibit a one-dimensional (1D) infinite chain and two-dimensional (2D) rectangular grid architecture with 14-membered metallocycle as SBU. Both 6 and 8 adopt 2D chiral rectangular grid, whereas 2 features a 3D compact framework, all of which contain 1D single-chain SBU. 4 and 9 exhibit 2D brickwalllike layer structure and 2D bilayer framework, respectively, both of which consist of 1D ladderlike chain SBU. To the best of our knowledge, they are the first examples with pyridine-2,3-dicarboxylic acid N-oxide introduced into the coordination polymeric framework. Even if these complexes do not possess any chiral ligand, 6 and 8 have chiral space groups and second-harmonic generation (SHG) responses. The thermal stabilities for 110, the photoluminescence properties for 7, 8, 9, and 10, as well as magnetic behaviors for 1, 2, 3, 4, 5, and 6 were examined, and the results indicated that the complexes seem to be good candidates of novel hybrid inorganic−organic photoactive materials with excellent thermal stability, whereas they do not have long-range ordering or other peculiar magnetic phenomena.