Luminescent diphosphine gold complexes with potential as sensors : structures, optical properties and reactivity with metal ions

• Main Author: Crawford, Deborah Elizabeth
• Published: Queen's University Belfast 2015
• Subjects: 681
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.680175

This project involves the study of new molecular sensors based on luminescent compounds that can change their emission properties in the presence of an analyte, in particular 'spectroscopically silent' metals, particularly those important in nature, such as Zn or Cu. Gold(l) complexes exhibiting Au--Au (aurophilic) interactions are often highly luminescent, and their emission can be related to the presence of such weak interactions. There is, however, a lack of understanding on how to control the extent of the interactions and the influence that these may have on the structures and optical behaviour of the compounds. The present work involves the systematic study of the influence that Au--Au and other weak interactions (Au--X, X = 0, S) have on the overall structures of digold(l) compounds as well as on their luminescence spectra, both in solid and solution states. These secondary interactions were investigated by varying both the heteroatom present in the bridging diphosphine ligand and the range of thiolate and alkyne co-ligands coordinated through the Au(l) atom. The potential of the compounds as optical sensors towards other metal ions has been investigated. Within this study, some very interesting X-ray crystal structures were obtained and described e.g. an unusual Au4Ag4 cluster.