A new cyclic gold(I) triazolate trimer, [Au(3,5-i-Pr(2)Tz)](3) (1), exhibits fully overlapping aurophilically bonded dimer-of-trimer units that lead to multiple phosphorescence bands in both the solid state and solution. The conformation of the hexanuclear unit exhibits reversible interconversion between C-2 and D-3 effective symmetries, depending on the crystal temperature or solution concentration, the variation of which leads to isoemissive and isosbestic points. Solutions of 1 exhibit remarkable quenching properties that demonstrate molecular recognition with high selectivity and hypersensitivity for some reagents, as influenced by protonation via Bronsted acids, pi intercalation, and/or energy transfer. The quenched phosphorescence of 1 by acetic acids can be regenerated by NEt3.