Aspects of Metallosupramolecular Chemistry
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
This thesis details the silver(I) coordination chemistry of thirty four alkene-containing ligands. The synthesis of thirty two of these ligands is described of which fifteen are unreported compounds. The ligands were designed to fully explore the potential of the silver(I)-alkene synthon in metallosupramolecular chemistry.
Five series of ligand were designed each exploring a different facet of ligand design. Three series explored different ligand cores which included benzene, naphthalene and single atoms such as carbon, oxygen and nitrogen. Another series explored ligands of higher denticity including tri-, tetra- and hexa-substituted benzenes. The last series investigated ligands with functional groups in addition to olefins, in particular, heterocyclic nitrogens. A metal-centred ligand was created from a bifunctional ligand subunit.
The silver(I)-alkene synthon has been used to create a range of assemblies. Polymeric structures were favoured with a variety of one-dimensional polymers with linear, ladder, helical and necklace type structures. Two-dimensional networks were formed, with some showing porosity. Three-dimensional metallopolymers were formed, including an interpenetrated three-dimensional network. Discrete complexes are commonly of the type Ag2L2 but with the occasional formation of Ag2L.
It is shown that silver(I)-alkene interactions can coexists with other stronger interactions such as silver(I)-nitrogen. The deliberate use of bifunctional ligands allowed the formation of many interesting assemblies including an Ag3L2 heterotopic helicate. A Cu(I) complex with copper(I)-alkene interactions was identified.
Techniques used to characterise the ligands and complexes include NMR, mass spectrometry, elemental analysis and X-ray crystallography. The crystal structures of seven organic compounds and forty six complexes are discussed.