Photolysis of the dinuclear complex [Ru(bpy)(2))(2)-(bpzt)](3+) (bpzt is 3,5-bis(Pyrazin-2-yl)-1,2,4-triazole) leads to a unique labilization of the metal moiety bound to the triazole N4 site. This is contrary to results obtained for the analogous compound based on the 3,5-bis(pyridin-2-yl)-1,2,4-triazole (Hbpt) ligand for which both the N1 and the N4 site were subject to photochemical substitution. This observation is explained by changes in the rate of relaxation to the lowest excited state as a result of the different nature of the LUMO in these complexes.