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Item Dithione, the antipodal redox partner of ene-1,2-dithiol ligands and their metal complexes(Elsevier, 2020) Basu, Partha; Colston, Kyle J.; Mogesa, Benjamin; Chemistry and Chemical Biology, School of ScienceDefining the oxidation state of the central atom in a coordination compound is fundamental in understanding the electronic structure and provides a starting point for elucidating molecular properties. The presence of non-innocent ligand(s) can obscure the oxidation state of the central atom as the ligand contribution to the electronic structure is difficult to ascertain. Redox-active ligands, such as dithiolene ligands, are well known non-innocent ligands that can exist in both a fully reduced (Dt2−) and fully oxidized (Dt0) states. Complexes containing the fully oxidized dithione state of the ligand are uncommon and only a few have been completely characterized. Dithione ligands are of interest due to their electron-deficient nature and ability to act as an electron acceptor for more electron-rich moieties, such as other dithiolene ligands or metal centers. This article focuses the syntheses, structures, and metal coordination, particularly coordination compounds, of dithione ligands. Various examples of mono, bis, and tris dithione complexes are discussed.Item The Influence of Structure on the Donor-Acceptor Properties of Metallodithiolene Complexes(2024-08) Colston, Kyle J.; Basu, Partha; Deng, Yongming; Pu, Jingzhi; Laulhé, SébastienThe intrinsic charge transfer properties of a given system are dictated by their electronic structure. The movement of electrons from electron rich to electron deficient moieties of a system can spur useful photophysical properties that have been utilized in the development of materials science. Such systems take advantage of redox-active ligands, which can actively participate in electron transfer, and have the versatility to function as either electron donors or acceptors in charge transfer processes. One of the most widely used family of ligands in the development of such materials is dithiolene (Dt), which can exists in two redox extremes; reduced ene-1,2-dithiolate(2-) (Dt2-) and oxidized dithione (Dt0). Dt ligands draw inspiration from the molybdenum cofactor (Moco) found in molybdenum containing enzymes that are present in all phyla of life. The Dt2- and Dt0 ligands play contrasting roles in charge transfer, however, characterization of their electronic structure when both are incorporated into a coordination complex is underexplored. Detailed computational and experimental interrogation of such complexes are presented to highlight the importance of molecular and electronic structures on their charge transfer properties. Such complexes containing a Mo core are also relevant towards the comprehension of the electronic structure of Moco. This investigation focuses on the fundamental understanding of the charger transfer properties of metallodithiolene complexes containing both Dt2- and Dt0 ligands, and progress towards the synthesis of the closest Moco analogs.