Two arylgold(III) complexes with fluorenyl and diphenylamine substituents, were synthesized and characterized. Photophysical properties of the complexes were examined in toluene and tetrahydrofuran (THF) solutions. Photoluminescence is solvent-dependent: phosphorescence from a metal-perturbed triplet intraligand excited-state in toluene shifts to phosphorescence from a solvent-stabilized triplet ligand-to-ligand charge transfer excited-state in THF. Both exhibit high intersystem crossing efficiencies.

The arylgold(III) complex Au(III)-DPA and its alkynyl analog Au(III)-ADPA are synthesized and characterized using steady-state and time-resolved optical spectroscopy and density functional theory calculations. Both complexes embed the fluorenyl moiety with substitution at the 2,7-positions, and both carry diphenylamine (DPA) substituents. The photophysical properties of the molecules are examined in toluene and tetrahydrofuran (THF) solutions. Both complexes possess similar ground-state absorption spectra, which are a combination of ligand centered π-π* transitions and metal-perturbed π-π* transitions. The excited-state luminescent properties of the molecules are solvent dependent. In toluene, Au(III)-DPA displays featureless phosphorescence, and Au(III)-ADPA exhibits structured phosphorescence both ascribed to a metal-perturbed triplet intraligand (³IL) π-π* state. In THF, however, both Au(III)-DPA and Au(III)-ADPA exhibit broad, red-shifted phosphorescence indicative of a solvent stabilized triplet ligand-to-ligand charge transfer (³LLCT) state. The intersystem crossing efficiencies of both complexes are also investigated. Pulsed laser experiments reveal high intersystem crossing values (>0.79) for both complexes in both solvents, indicating that intersystem crossing is the dominant pathway for singlet excited-state decay. Density functional theory calculations indicate frontier orbitals centered on the substituted fluorenyl ligands highest occupied molecular orbital (HOMO) and the cyclometalating ligand lowest unoccupied molecular orbital (LUMO), supporting the assignment of ³LLCT excited states in more polar solvents.