From the reactions between Mo-2(DAniF)(3)pivalate (DAniF = N,N'-di(p-anisyl)formamidinate) and the carboxylic acids LH, the title compounds Mo-2(DAniF)(3)L have been prepared and characterized: compounds I (L = O2CC CPh), II (L = O2CC4H2SC CH), and III (L = O2CC6H4-p-CN). The new compounds have been characterized in their ground states by spectroscopy (H-1 NMR, ultraviolet visible absorption, near-infrared absorption, and steady state emission), cyclic voltammetry, and density functional theory calculations. The compounds show strong metal Mo-2 to ligand L delta-pi* transitions in their visible spectra. The nature of the S-1 (MLCT)-M-1 and T-1 states has been probed by time-resolved (femtosecond and nanosecond) transient absorption and infrared spectroscopy. The observed shifts of the C C and C N vibrational modes are found to be consistent with the negative charge being localized on the single L in the S-1 states, while the T-1 states are Mo-3(2) delta delta*. The present results are compared to earlier studies of the photoexcited states of trans-Mo-2(2,4,6-triisopropylbenzoate)(2)L-2 compounds that have been assigned as either localized or delocalized.