Towards the introduction of communication between metallo-supramolecular [M2L3]2- and [M2L3]4+ assemblies.
Degree GrantorUniversity of Canterbury
Degree NameMaster of Science
In this thesis the construction of a number of supramolecular entities was undertaken with the intention to probe their spin-crossover properties. The introduction of communication between metal complexes within the crystal lattice through non-covalent interactions was investigated in an attempt to probe cooperativity of any spin crossover (SCO). The coordination of two distinct ligands to create supramolecular [M2L3] assemblies was investigated. Sulfonated helicates [Fe(OH2)6][Fe2L33], [Co(OH2)6][Co2L43], [Ni(OH2)6][Ni2L43], K2[Fe2L33], Ca[Fe2L33] and [Fe(OH2)6]0.2Rb1.6[Fe2L33] were constructed from the precursor ligand 6,6’-oxy-bis(3-aminobenzenesulfonic acid). Preliminary investigations in the occurrence of SCO were conducted on the [Fe(OH2)6][Fe2L33] and [Co(OH2)6][Co2L43] metallo-helicates. In conjunction, phosphate supramolecular assemblies [Fe2L53]4+, [Zn2L53]4+, [Fe2L63]4+, [Co2L63]4+, [Ni2L63]4+, [Co2L73]4+, [Ni2L73]4+ and [Cu2L73]4+ were also synthesised from the precursor ligand bis(4-aminophenyl)phenyl phosphate, however, further refinement of the crystallisation process is needed before spin-crossover studies can take place.