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|Title:||Structural studies of coordination networks based on multitopic organic ligands and silver(I) salts|
|Doctoral Committee Chair(s):||Moore, Jeffrey S.|
|Department / Program:||Chemistry|
|Degree Granting Institution:||University of Illinois at Urbana-Champaign|
|Abstract:||This thesis outlines the use of silver-nitrogen coordination bonds for the construction of supramolecular networks. Based on the complexes of silver(I) with multitopic ligands, certain recurrent relationships have been identified between topicity of the organic ligand and the network connectivity that can be used as guidelines for the construction of supramolecular structures. When crystallized from non-polar solvents, the characteristic network motif in the complexes of silver(I) triflate with ditopic, linear ligands is always 2-connected infinite chains. In contrast, trigonal, tritopic ligand complexes form 3-connected structures. A tetratopic, tetrahedral ligand formed 3-connected nets with AgOTf. In the complexes of ditopic ligands with AgPF$\sb6$, both 2-connected infinite chains and 4-connected diamondoid units are found as basic motifs. Since the organic ligands that are used in this study consist of aromatic units, the packing of these networks is greatly influenced by either aromatic $\pi$-$\pi$ or silver-aromatic interactions. A correlation between the degree of interpenetration and the cavity sizes that are generated in a single net using the geometrical requirements of the $\pi$-stacking interactions has also been obtained.
Two coordination networks based on tritopic organic nitriles and silver(I) triflate had particularly interesting structure and properties. The porosity in these networks have been invoked by the complete exchange of solvent. The coordination network that resulted from a bent tritopic reversibly loses and re-absorbs guest species at 110$\sp\circ$C without undergoing a change in phase or morphology.
|Rights Information:||Copyright 1996 Venkataraman, Dhandapani|
|Date Available in IDEALS:||2011-05-07|
|Identifier in Online Catalog:||AAI9625207|