iClick reactions between Au(I) acetylides PPh3Au-C≡CR, where R = nitrophenyl (PhNO2), phenyl (Ph), thiophene (Th), bithiophene (biTh), and dimethyl aniline (PhNMe2), and Au(I)-azide PPh3AuN3 provide digold complexes of the general formula R-1,5-bis-triphenylphosphinegold(I) 1,2,3-triazolate (Au2-R). Within the digold triazolate complexes the Au(I) atoms are held in close proximity but beyond the distance typically observed for aurophilic bonding. Though no bond exists in the ground state, time-dependent density functional theory interrogation of the complexes reveals excited states with significant aurophilic bonding. The series of complexes allows for tuning of the excited-state "turn-on" of aurophilicity, where ligand to metal charge transfer (LMCT) induces the aurophilic bonding. Complexes containing ligand-localized excited states, however, do not exhibit aurophilicity in the excited state. As a control experiment, a monogold complex was synthesized. The computed excited state of the monogold species exhibited LMCT to the gold ion as in the dinuclear cases, but without a partnering gold ion only a distinct N-Au-P bending occurs, revealing a potential mechanism for the excited-state turn-on of aurophilic bonding. Analysis of the steady-state electronic spectra indicates that LMCT states are achievable for compounds with sufficiently strong electron-donating ligands, and in digold complexes this is associated with enhanced fluorescence, suggestive of an aurophilic interaction.