Luminescent Group 11 Metal Chalcogen Clusters with Bidentate Phosphine Ligands

Mansha Nayyar, The University of Western Ontario

Abstract

Luminescent group 11 metal chalcogen clusters have been of interest in the past few decades due to their potential applications in light emitting materials. These complexes can be synthesized by a controlled reaction between a phosphine solubilized metal complex (M = Cu, Ag) and trimethylsilylchalcogen reagents (RESiMe₃ and E(SiMe₃)₂, R = organic moiety, E = S, Se) which results in polynuclear metal chalcogen complexes ((M-ER) or (M₂E)) with protective phosphine ligands. These phosphine stabilized clusters can exhibit emission at room temperature (RT) which can be changed depending on the phosphine ligand. This thesis focuses on incorporating 4,6 - bis(diphenylphosphino)dibenzofuran (DBFDP) and related disphosphine ligands in group 11 metal chalcogen clusters to determine how the incorporation of these bidentate phosphines affect the structural and the luminescence properties of these compounds. It was observed that the incorporation of DBFDP in metal chalcogenolate clusters resulted in [(M(EPh))_x(dbfdp)₂] (Ph = phenyl, x = 4, 5, 6) with efficient PLQY’s of up to 73 % at RT while the incorporation of the related DBFDP resulted in [Cu₁₂E₆(etdfbdp)₄] with protective phosphine ligands with red - orange emission at RT. An analysis of the structure and the photophysical properties of group 11 metal chalcogen clusters is discussed.

Keywords: metal chalcogenolates, metal chalcogenides, phosphine ligands, luminescence, emission, photoluminescence quantum yields