| This dissertation presents experimental results from the synthesis and structural, chemical, and physical characterization of representative low-dimensional coordination polymers. The structural, thermal, and magnetic properties of a series of clathrated porous network solids, [Ni(4,4′-bipy) 3(H2O)2)(ClO4)2·1.4(4,4 ′-bipy)·3(H2O),1, [Co(4,4 ′-bipy)3(H2O)2](ClO4) 2·1.4(4,4′-bipy)·3(H2O), 2, and [Cu(4,4′-bipy)3(DMSO)2 ](ClO4)2·2(4,4′-bipy) 3, are described first. These materials consist of chains of transition metal ions (Ni(II), Co(II), and Cu(Il)) bridged by 4,4′-bipyridine spacer ligands. The chains pack to form two-dimensional, non-interpenetrated sheets with hydrophobic, rectangular cavities within the framework. The sheets, in turn, pack to form three-dimensional structures with oblique channels containing enclathrated guest molecules and counterions extending throughout the solid. These enclathrated guests molecules are easily lost, suggesting that the samples are thermally unstable. The magnetic properties of 1, 2, and 3 are similar in the sense that only very weak exchange interactions are present between the metal centers.; The host-guest properties of 1 and 2 were investigated. Gas chromatography experiments determined that both hosts exchange clathrated bipy molecules with trialkylphosphine oxide probe molecules, TMPO, TEPO, and TPPO. While the uptake of TMPO by both 1 and 2 is essentially complete, steric constraints are believed to limit the uptake of TEPO and TPPO by the host. The trialkylphosphine oxides interact with acid sites within the host as determined by 31P MAS NMR spectroscopy. TMPO interacts with both coordinated water molecules (strong acid sites) and lattice waters (weak acid sites) in compound 1 and coordinates directly to the metal centers in compound 2. However, TEPO and TPPO seem to attack only the weaker acid sites within the hosts. X-ray diffraction patterns show that the loss of bipy and uptake of the probe causes significant structural rearrangements in 1 and only mild structural changes in 2. However, the nature of these guest-exchanged products is unknown. These experiments showed that solid-state NMR spectroscopy can be used to investigate host-guest interactions.; Finally, the structural and magnetic properties of three azido-bridged copper(II) ladder-like coordination polymers, [Cu2(PhPyPy) 2-μ-(N3)2(N3)2], 4, [Cu2(terpy)2-μ-(N3)4Cu 2-μ-(N3)2(N3)2], 5, and [Cu2(terpy)2-μ-(N3) 2(N3)2Cu3-μ-(N3) 4(N3)2], 6, are discussed. (Abstract shortened by UMI.)... |
