Structural studies of coordination networks based on multitopic organic ligands and silver(I) salts
Venkataraman, Dhandapani
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https://hdl.handle.net/2142/20040
Description
Title
Structural studies of coordination networks based on multitopic organic ligands and silver(I) salts
Author(s)
Venkataraman, Dhandapani
Issue Date
1996
Doctoral Committee Chair(s)
Moore, Jeffrey S.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Chemistry, Organic
Chemistry, Physical
Language
eng
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.
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