Photophysics of pyridylporphyrin Ru(II) adducts: Heavy-atom effects and intramolecular decay pathways

Eight adducts between different pyridylporphyrins and ruthenium complexes, MPyP[RuCl2(DMSO)(2)(CO)], c-DPyP[RuCl2(DMSO)(2)(CO)](2), TrPyP[RuCl2(DMSO)(2)(CO)](3), TPyP[RuCl2(DMSO)(2)(CO)](4), (MPyP)(2)[RuCl2(DMSO)(2)], {c-DPyP[RuCl2(DMSO)(2)]}(2), MPyP[RuCl2(CO)(3)], and {c-DPyP[RuCl2(CO)(2)]}(2), have been investigated. The results show that in all the adducts the porphyrin singlet is quenched. to a greater or lesser extent, relative to the parent-free molecule. This study provides insight into the mechanisms of singlet quenching in the adducts. Two mechanisms for singlet quenching, both related to the heavy-atom effect of the ruthenium center and experimentally distinguishable by transient spectroscopy, are examined. Enhanced intersystem crossing within the porphyrin chromophore is demonstrated for the series of adducts MPyP[RuCl2(DMSO)(2)(CO)], c-DPyP[RuCl2(DMSO)(2)(CO)](2), TrPyP[RuCl2(DMSO)(2)(CO)(3)], and TPyP[RuCl2(DMSO)(2)(CO)(4)], where a nice correlation is observed between the magnitude of the effect and the number of ruthenium centers attached to the pyridylporphyrin chromophore. Singlet-triplet energy transfer from the pyridylporphyrin chromophore to the ruthenium center(s) is an additional efficient quenching channel for adducts containing ruthenium centers with weak field ligands and low triplet energies, such as (MPyP)(2)[RuCl2(DMSO)(2)] and {c-DPyP[RuCl2(DMSO)(2)]}(2).