| Summary: | 博士 === 中原大學 === 化學研究所 === 99 === This thesis includes five parts discussing the syntheses, structures and thermal and luminescent properties of a series of metal complexes containing the flexible N,N’-di(3-pyridyl)adipoamide (L1), N,N’-di(2-pyridyl)adipoamide (L2), N,N’-di(4-pyridyl)adipoamide (L3) and N,N’-di(3-pyridyl)dodecanedioamide (L4) ligands. All complexes have been characterized by IR, UV-vis and emission spectra, EA and TGA analysis and single-crystal X-ray diffraction.
In the part I, the reactions of L1 with AgPF6 and AgSbF6 in CH3CN afforded the 1D concavo-convex chains {[Ag(L1)](PF6) • 2CH3CN}∞, 1a and {[Ag(L1)](SbF6) • CH3CN • 0.5H2O}∞, 2a, while the reactions of L1 with AgBF4 and AgNO3 in CH3CN, and AgPF6, AgSbF6, AgBF4 and AgCF3SO3 in DMF gave the 1D zigzag chains {[Ag(L1)](BF4) • CH3CN}∞, 3a, and {[Ag(L1)](NO3) • CH3CN}∞, 4, and {[Ag(L1)](PF6) • 4DMF}∞, 1b, {[Ag(L1)(DMF)](SbF6)}∞, 2b, {[Ag(L1)](BF4) • 4DMF}∞, 3b and {[Ag(L1)](CF3SO3) • DMF}∞, 5, respectively. In complexes 1a and 2a which show 1D concavo-convex chains, the L1 ligands adopt the AAA trans syn-anti conformation, whereas in other complexes which show the 1D zigzag chains, the L1 ligands adopt the AAA trans syn-syn conformations. The shapes and the sizes of the anions as well as the identity of the solvents are important in determining the structural diversity. For the complexes with the CH3CN solvents, the larger PF6- and SbF6- anions which adopt the octahedral geometry induce the 1D concavo-convex chains, while the smaller BF4- and NO3- anions which adopt the tetrahedral and triangular geometries induce the 1D zigzag chains. For complexes with the DMF solvents, all the complexes adopt the 1D zigzag chain, regardless of the shapes and sizes of the anions.
In the part II, the complexes {[Ag(L1)](ClO4) • CH3CN}∞, 6, {[Ag(L1)](ClO4)}∞, 7, [Ag2(L1)2](p-TsO)2 • 2CH3CN (p-TsO = p-Toluenesulfonate), 8, and [Ag(L1)(p-TsO)]∞, 9, are reported. Complexes 6 and 7 form 1D linear chains, while 8 and 9 show a 0D dinuclear metallocycle and a 2D pleated grid with a {4,82} topology, respectively. Reversible crystal to crystal transformation was observed in 6 and 7 upon removal and uptake of the acetonitrile molecules, while the process is irreversible in 8 and 9, which are concomitant with changes in supramolecular structures, ligand conformations and luminescent properties. The main driving forces for the structural transformations are the Ag---N and Ag---O interactions.
In the part III, using dipyridyladipoamide ligands and benzenedicarboxylate ligands, eight Zn(II) or Cd(II) complexes have been synthesized under hydrothermal conditions. The complexes [Zn(1,2-BDC)(L1)]∞, 10; [Zn2(1,3-BDC)2(L1)(H2O)2]∞, 11; [Zn2(1,4-BDC)2(L2)(H2O)2]∞, 12; {[Zn2(1,2-BDC)2(L3)(H2O)2] • 2H2O}∞, 13; {[Cd(1,2-BDC)(L1)(H2O)] • H2O}∞, 14; [Cd2(1,3-BDC)2(L1)(H2O)4]∞, 15; {[Cd2(1,4-BDC)2(L1)2] • (H2O)3}∞, 16; [Cd2(1,4-BDC)2(L2)(H2O)2]∞, 17, are reported. Complex 10 is a 1D loop-like chains, complex 13 exhibits 1D chains with loops and complex 15 shows 1D ladder chains, whereas complexes 11, 12, 14 and 17 show 2D pleated nets, and complex 16 exhibits a 3D framework. The bonding modes of BDC2- ligands play an important role in determining the structural dimension. In complexes 10 – 15 and 17, the BDC2- ligands adopt the μ2 bonding mode, whereas in complex 16, the BDC2- ligands adopt both the μ2 and μ4 bonding modes to form 3D frameworks.
In the part IV, using dipyridyladipoamide ligands and pyridinedicarboxylate or benzenetricarboxylate ligands, nine complexes have been synthesized under hydrothermal conditions. The complexes {[Zn2(2,5-PDC)2(L1)(H2O)2] • 2H2O}∞, 18; [Zn2(2,6-PDC)2(L1)]∞, 19; {[Zn2(3,4-PDC)2(L1)(H2O)6] • 4H2O}∞, 20; {[Cd(2,6-PDC)(L1)(H2O)] • 4H2O}∞, 21; [Zn(1,3,5-HBTC)(L1)]∞, 22; {[Cd(1,2,3-HBTC)(L1)(H2O)] • H2O}∞, 23; {[Cd2(1,3,5-HBTC)2(L1)(H2O)2] • 2H2O}∞, 24; {[Zn3(1,2,4-BTC)2(L1)(H2O)4] • 4H2O}∞, 25; {[Cd3(1,3,5BTC)2(L3)3(H2O)3] • 3H2O}∞, 26, are reported. Complexes 20 and 21 exhibit 1D ladder chains. Complexes 18, 19 and 22 possess 2D pleated nets and complex 24 shows a 2D layer structure. Complexes 23, 25 and 26 show 3D frameworks. In complexes 25 and 26, the BTC3- ligands adopt the μ4 and μ3 bonding modes to form 3D frameworks.
In the part V, using N,N’-di(3-pyridyl)dodecanedioamide (L4)ligands and multicarboxylate ligands, five complexes have been synthesized under hydrothermal conditions. The complexes [Zn(2,4-PDC)(L4)(H2O)]∞, 27; {[Zn(1,3,5-HBTC)(L4)] • 2H2O}∞, 28; {[Zn(3,4-PDC)(L4)] • 0.5L4}∞, 29; {[Cd(1,2-BDC)(L4)(H2O)] • 0.5L4}∞, 30; {[Cd(1,3,5-HBTC)(L4)1.5] • 2H2O}∞, 31, are reported. Complex 27 exhibits 1D tube like chains, while complex 28 possess 1D infinite chains and complex 29 shows 1D fish-bone chains. Complexes 30 and 31 show 2D pleated nets.
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