The spectral changes associated with k1 (see light-grey dotted line in Figure ) describe the relaxation of pheninto phz-centered 3 MLCT states and vibrational cooling, populating a state with excess electron density on the phzsphere of the tpphz ligand. The vibrational cooling is manifested in the blue-shift of the ESA band maximum from 600 to 605 nm. This phen-to-phz intra-ligand charge-transfer (ILCT) is reflected in the build-up of ESA between 520 and 620 nm ( 3 MLCT phz ) accompanied by the decrease of ESA between 620 and 750 nm, typically associated with phen-to-Ru LMCT transitions originating from a 3 MLCT phen state.