Electronic Thesis and Dissertation Repository

Thesis Format

Integrated Article


Master of Science




Corrigan, John F.


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

Summary for Lay Audience

Group 11 metals refer to copper, silver and gold while chalcogens refer to the group 16 elements oxygen, sulfur, selenium and tellurium. The chalcogens in combination with group 11 metals can form group 11 metal chalcogenolate or chalcogenide clusters. Chalcogenolates (RE-, R = organic moiety, E = S, Se) have a 1- charge on the chalcogen atom which has the ability to bond to group 11 metals with a 1+ charge resulting in a core made of M-ER (M = Cu, Ag) with a ratio of 1:1 between M:E. The R groups in the chalcogenolates provide kinetic control in the assembly of the desired compound. Moreover, phosphorus containing organic compounds (phosphine ligands) can also be incorporated in these compounds which can provide a way to change the properties (such as luminescence - emission of light in the visible region) of group 11 metal chalcogenolate clusters. On the other hand, chalcogenides have a 2- charge on the chalcogen and when reacted with M(I), they result in a M2E core with a 2:1 ratio between the M and E. The metal is protected by the incorporation of phosphine ligands and provides kinetic control in synthesizing the desired species and preventing the formation of bulk M2E. The protective phosphine ligands can result in properties such as luminescence for group 11 metal chalcogen clusters which have potential applications in light emitting materials, optical sensors and bioimaging. This thesis describes the incorporation of a custom / tailored phosphine ligand that has the ability to bond two metal atoms in group 11 metal chalcogen clusters and an examination of their luminescence.