Luminescent Group 11 Metal (I) Chalcogen Clusters with a Conjugated Diphosphine Ligand
Abstract
Polynuclear Au (I) complexes exhibit rich photochemical properties and have the potential to find applications as molecular sensors, switches, or energy storage devices. Although dinuclear Au (I) complexes with bridging diphosphines have been extensively examined, most of those reported do not contain rigid-diphosphine ligands.
This thesis examines how the rigid diphosphine, 4,6-bis(diphenylphosphino)dibenzofuran (DBFDP) can be incorporated for the controlled assembly of photoluminescent gold (I) metal – chalcogenolate (chalcogenolate = RS-, RSe-; R = organic moiety) and gold (I) chalcogenide (chalcogenide = S2-, Se2-) bimetallic complexes. In these studies, the chalcogen reagents E(SiMe3)2 or RESiMe3 are reacted with the gold coordination complex [(AuOAc) 2(μ-dbfdp)] to yield [Au2E(μ-dbfdp)] and [(AuER)2(μ-dbfdp)], respectively, via the formation and elimination of AcOSiMe3. Further reaction of the [Au2E(dbfdp)] with AuOTf yields higher nuclearity clusters ranging from 4-6, namely [Au4(µ4-E)(µ-dbfdp)2](OTf)2 and [Au6(µ3-E)2(µ-dbfdp)3](OTf)2. A common feature among these di-gold complexes is the bridging nature of the DBFDP ligand.
The preparation, characterization, and photophysical properties of several of these and related gold-chalcogen assemblies clusters are presented.