The alkyne azide "click" reaction was successfully used to prepare new Bodipy-functionalized triazoles and triazolium cyclometalation conditions as well as with transmetalation procedures involving a triazolyldene silver intermediate, as demonstrated by the successful formation of a metallacyclic palladium diner and an iridium chelate. Both complexes were characterized by X-ray diffraction, and spectroscopic studies demonstrate unperturbed photoluminescence of the Bodipy chromophore (emission around 545 nm, quantum yields in the 0.35-0.7 range, and excited-state lifetimes between 3 and 7 ns). The palladium dimes 4 was cleaved using N,N-dimethylarninopyridine (dmap) and,acridine to afford monomeric triazolylidene palladium complexes 5 and 6. While dmap is a classical spectator ligand, acridine acts as photoluminesence quencher and quenching constants were determined as K-sv = 0:86 and 1.6 X 10(4) M-1 for,complexes 4 and 5, respectively. This dual reactivity of acridine as ligand and quencher was utilized for a ligand displacement assay that allowed modification of the organometallic site of the hybrid complex to be monitored:by emission spectroscopy.