Metal directed supramolecular assemblies for optical materials : chemosensor design and application

This dissertation reports the design, synthesis and characterisation of several metallosupramolecular assemblies incorporating 8-hydroxyjulolidine-9-carboxaldehyde or 4- (diethylamino)salicylaldehyde groups. These groups are well known as strong electron donors, and as such, they are potentially favourable for the development of electro-optical materials, especially chemosensors. Furthermore, the presence of their aldehyde functional group makes these moieties ideal for condensation reactions with primary amines, and the resulting imine (chapter 2-4) or dihydropyrimidine (chapter 5-7) groups are situated near the OH of the phenol groups; thus the synthesised ligand has an ideal preorganised polydentate coordination environment. In this dissertation, several supramolecular assemblies based on either 8-hydroxyjulolidine- 9-carboxaldehyde or the 4-(diethylamino)salicylaldehyde group were investigated by a range of techniques, including NMR, FT-IR, ESI-HRMS, SEM-EDS, Raman, STA, UVVis and fluorescence spectroscopy. In addition to these techniques, 13 crystal structures were also determined by SC-XRD using the MX1 and MX2 beamlines at the Australian Synchrotron. These structures showed various conformations, many of which are mediated by the coordinating metal ions, anions, and the experimental conditions, etc. Furthermore, two ligands show great potential as chemosensors for nanomolar colourimetric detection of Cu2+, and a protocol has been developed for colourimetric detection of exchangeable Cu2+ on soils