| Recent significant developments in the field of supramolecular self-assembly have largely relied on the discovery and utilization of metal-ligand coordination bonding, which has allowed formation of discrete and self-organized aggregations of molecular clusters in solution. By carefully designing precursors, two- and three-dimensional supramolecular assemblies can be obtained. These supramolecules have shown their significance: the ease of synthesis compared to traditional methods and their novel properties, which cannot be attained by common organic or inorganic compounds.;In this dissertation, platinum(II)-pyridyl coordination bonds were utilized in the self-assembly of discrete structures in solution. A supramolecular equilibrium between a two-dimensional dimeric rhomboid and trimeric hexagon was studied. The equilibrium was controlled by changes in concentration and temperature. Based on these experiments, thermodynamic equilibrium constants, standard enthalpy and entropy changes were determined for the equilibrium.;Three-dimensional self-assemblies were prepared from a tritopic pyridyl linker along with a cis-platinum(II) unit. Two types of truncated tetrahedra were self-assembled and characterized by nuclear magnetic resonance and mass spectrometry. Crystallization of the structures was accomplished by partially exchanging the triflate counterion with cobalticarborane in order to determine their crystal structures by X-ray diffraction. When manganese(II), which possesses the same angle as platinum(II), was used with the same tritopic pyridyl linker, an indiscrete polymer formed upon crystallization. The weaker manganese(II)-pyridyl coordination bond does not allow formation of discrete structures in solution. This example illustrates the difference between discrete molecular architecture (DMA) and inorganic crystal engineering (ICE).;Finally, three-dimensional discrete trigonal prism self-assemblies are presented. Four different size and topological structures were assembled from different pyridyl linkers. This experiment probes the self-assembly's limitations to molecular topology and aggregation size. |
