This thesis has been divided into five sections. The first chapter introduces the main themes of this thesis, including the description of the concepts of supramolecular chemistry, crystal engineering, hydrogen bonding and graph set analysis. The final section of chapter one describes a typical X-ray experiment used to determine the structures of the compounds presented in this thesis. Chapter two describes the synthesis and single crystal structures of copper(I) complexes with pyridine- and pyrazine-carboxylic acids. A series of novel solvent inclusion compounds of copper(I) complexes with pyridine- and pyrazine-carboxylic acids and the hydrogen bonding patterns adopted are also discussed. Chapter three reports the potential uses of boronic acids as building blocks for the design of novel solid-state architectures utilising hydrogen bonds. Novel copper(I) pyridine-/pyrazine-carboxylate complexes with boronic acid co-crystals are presented in which the heterodimeric boronic carboxylate R22(8) ring motif is present in all cases. Chapter four discusses the synthesis of novel ditertiary phosphines bearing functional groups with hydrogen bonding potential either via a three-step or single step synthetic route which involves a well known method of reductive amination followed by an efficient Mannich-based condensation. Complexation studies of these P,P-bidentate ligands with various transition metal centres such as Pt(II), Mo(0), Ru(II) and Au(I) are also presented. The effect on the structural motifs observed in these series of compounds by the regioselective incorporation of functional groups with potential hydrogen bonding capability such as hydroxyl and amide is also given. Finally, chapter five contains the synthesis and coordination studies of new phosphorus donor ligands leading to ideas for further work.
A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.
Crystal structure data:
For all structures in this thesis where a crystal structure diagram is shown, X.rtf and X.res files are included in the directory “Tables and Res Files” within the relevant subdirectory for each chapter, where X is the compound number assigned in the thesis. The .rtf files contain the tabulated output from each determination, including information concerning the data collection strategy and the resulting bond lengths, bond angles and hydrogen bonds. The .res files contain the xyz coordinates for the structures and can be read into a number of crystal structure visualisers (e.g. SHEXTL XP or Mercury) for viewing as required.