Abstract
This thesis describes the synthesis and characterisation of a series of new homoleptic and heteroleptic [Pd2L4] helicates, synthesised from a series of new ligands based on the previously reported 1,4-bis(3-pyridyloxy)benzene ligand. The anion exchange process on these homoleptic and heteroleptic helicates was also explored.
Chapter 1 gives a brief introduction into supramolecular chemistry, and the ideas behind the self-assembly of homoleptic and heteroleptic architectures with some key examples from the literature. Considerations for the binding of ions inside a supramolecular architecture are also addressed.
Chapter 2 discusses the synthesis and characterisation of ligands 1 – 6, where the ligands vary in the difference in the sterics of the central group. Chapter 2 then moves into detailing the synthesis and characterisation of the homoleptic helicates [Pd2(1)4], [Pd2(3)4] and [Pd2(5)4]. The work done shows that varying the sterics of the central group of the ligand leads to a preference for some homoleptic cages over others. The anion exchange process on the homoleptic helicates [Pd2(1)4], [Pd2(4)4] and [Pd2(5)4] with the tetrabutylammonium salts of ClO4-, ReO4- and NO3-, is also discussed.
Chapter 3 details the synthesis and characterisation of the dynamic libraries of the heteroleptic helicates [Pd2(1)x(3)4-x], [Pd2(1)x(5)4-x] and [Pd2(3)x(5)4-x]. The anion exchange process on the heteroleptic helicates [Pd2(1)x(3)4-x], [Pd2(1)x(4)4-x] and [Pd2(1)x(5)4-x] with the tetrabutylammonium salts of ClO4- and ReO4- is also discussed.
Chapter 4 details the synthesis and characterisation of the dynamic libraries of the heteroleptic tri-ligand helicates [Pd2(1)x(2)y(3)z], [Pd2(1)x(3)y(6)z], [Pd2(1)x(4)y(5)z], [Pd2(2)x(3)y(6)z] and [Pd2(3)x(5)y(6)z].
Appendix 2 and 3 contain details on the synthesis and characterisation, and anion exchange processes for the other homoleptic and heteroleptic helicates synthesised from ligands 1 – 6. The experimental information for chapters 2, 3 and 4 are in appendix 2, 3 and 4, respectively.