The ground and excited state properties of two metallo-tetrophenyltetraben/oporphyrms (MTPTBP) have been investigated by a combination of DFT/TDDTT and transient absorption spectrometry to thaw a complete picture of the excited state deactivation The Cu(II) and Co(II) complexes were chosen to investigate, the impact of the half-filled d orbitals on the photophysical properties of the tetrapyrrole macrocycle The first observed transient in CuTPTBP was assigned to the triplet state that equilibrated with a ligand to-metal charge transfer (LMCT) state Ground state repopulation completed within 53 ps occurred via a lower-lying LMCI state The dependence of the observed lifetime on solvent polarity confirmed the participation of the LMCT state in the overall deactivation process For CoTPTBP, the first observed transient a pi-localized triplet state converted to a hot d d state wherein intramolecular cooling occurred and completed within 3 Ps The cooled d d state decayed to the ground state in an exponential manner with a 17 ps lifetime