We present a joint experimental and computational study of the trinuclear basic carboxylate iron complex Fe Fe O(CH CO ) (H O) III2 II 3 26 2 3, which is a model system for understanding photoinduced ultrafast spin dynamics in magnetic iron-based transition metal oxides. We have carried out femtosecond optical transient absorption spectroscopy of molecules in solution at room-temperature exciting either at 400 or 520 nm and observed a longlived excited-state absorption (ESA) signal from ca. 400–670 nm. The ESA signal is composed of several broadun-resolved bands at 405, 440 and 530 nm. The decay dynamics are complicated and three exponentials with corresponding decay time constants of τ1 = ± 360 30 fs, τ2 = ± 5.3 0.6 ps, τ3 = ± 65 5 ps and a constant offset (τ4 > 500 ps) were needed to fit the data over the full wavelength range. The data indicate that the lowest excited state is populated within the duration of the excitation pulse (<120 fs). Highly correlated coupled-cluster calculations can satisfactorily reproduce the experimental vibrational spectrum and highlight the role of the μ3-oxo bridge connecting the Fe ions to create a highly correlated ground-state and identify the excited state as having a mixture of both charge-transfer and ligand-field/d-orbital characters.