A series of luminescent dinuclear mixed-valence gold alkynyl complexes, [(tBuC^N^CtBu)AuIII(CC)AuI(PPh3)], [(RC^N^CR)AuIII(CCCC)AuI(PPh3)] (R = H, tBu), [(RC^N^CR)AuIII(CCC6H4CC)AuI(PPh3)] (R = H, tBu), and [(RC^N^CR)AuIII(CCC6H4CC)AuI(P(C6H4R′-p)3)] (R = H; R′ = OMe, Cl) as well as the precursor complexes, [AuIII(tBuC^N^CtBu)(CCSiMe3)] and [AuIII(tBuC^N^CtBu)(CCH)], have been synthesized and their electrochemical properties have been investigated. The molecular structures of a number of dinuclear mixed-valence gold alkynyl complexes have been determined by X-ray crystallography. For complexes with a butadiynyl bridge, the emission was derived from an admixture of metal-perturbed triplet intraligand (3IL) [π-π∗ (RC^N^CR)] and [π-π∗ (CC-CC)] states while for complexes with a 1,4-diethynylbenzene bridge, the emission was assigned as derived from the excited state of the 3IL [π → π∗ (CCC6H4CC)] origin. Computational studies have also been performed for selected complexes to support the assignment of the spectroscopic origin and the nature of the photophysical properties.
Scopus Subject Areas
- Inorganic Chemistry