In contrast to phenPer, the initial TA spectrum of Rh III phenPer (Δt=0.5 ps) in acetonitrile reveals comparably strong ESA at 540 nm (see Fig. ), which is typically associated with a Per-centered radical cation (Per •+ ). Since that ESA is less-pronounced in toluene compared to the *Per ESA (see Fig. ), the 540 nm feature hints to the population of a charge separated state (see Fig. and) in acetonitrile. In addition, the initial TA spectrum in acetonitrile shows characteristic S1 → Sn ππ* absorption of *Per at 706 nm. We associate the existence of *Per and Per •+ signals in the initial TA spectrum with the excitation of two different conformers, assuming conformational isomer dependent oscillator strengths for ππ* and ILCT transitions. Within the first 0.6 ps (τ1 = 0.6±0.1 ps) the characteristic *Per ESA and *Per SE at around 475 nm vanish, accompanied by the rise of ESA at around 480 nm (plateau). We ascribe the latter ESA to ππ* transitions on a formally reduced phen-moiety (phen •-). Consistent with our findings, literature reports similar rates (0.1 up to 1.5 ps) for the formation of a rylene radical cation 34 or anion in PDI substituted systems. The phen-centered intraligand charge-separated state decays via ligand-to-metal charge transfer (LMCT) with τ2 = 6.9±2.5 ps forming the fully charge-separated (CS) species [(phenPer •+ )Rh II (Cp*)Cl] + . This is reflected in the decay of ESA at around 480 nm (ππ*phen •-). The CS species decays with 280±150 ps (τ3). In parallel to the charge-transfer cascade, the remaining fraction of the population of the ILCT state relaxes back to the ground state with τ4 = 47±20 ps (see Fig. ).