Distance calculations show that the PF - 6 counter anion is not effected by Species A, this could be because the ground-state dipole of the Ir[tBu] + is pointing in the same direction as the Species A dipole, or because Species A decays faster than the reorganizational response time of the PF - 6 counter anion. In Species B, the distance between the ions decrease by 0.4 Å which can be explained by the intramolecular dipole moment of Ir[tBu] + reorganizing to point away from the dF(CF 3 )ppy ligands as the excited electron settles closer to the dtbpy ligand. This change in dipole direction causes the PF - 6 counter anion to move between the two dF(CF 3 )ppy ligands of the Ir[tBu] + complex which, due to the smaller size of the dF(CF 3 )ppy ligands compared to the dtbpy ligand, allows the PF - 6 to get closer to the positively-charged iridium center.