In order to better understand intramolecular communication between molecular fragments, a series of ferrocene-functionalized β-diketonato manganese(III) complexes, [Mn(FcCOCHCOR)3] with R = CF3, 1, CH3, 2, Ph = C6H5, 3, and Fc = FeII(η5-C5H4)(η5-C5H5), 4, the mixed ligand β-diketonato complex [Mn(FcCOCHCOFc)2(FcCOCHCOCH3)], 5, as well as the acac complex [Mn(CH3COCHCOCH3)3], 6, were subjected to an electrochemical and X-ray photoelectron spectroscopy (XPS) study. The ferrocenyl (FeII) and MnIII redox potentials, E°', and photoelectron lines were sufficiently resolved in each complex to demonstrate a linear correlation between E°' and group electronegativities of ligand R groups, χR, or ΣχR, as well as with binding energies of both the Fe 2p3/2 and Mn 2p3/2 photoelectron lines. These relationships are consistent with effective communication between molecular fragments of 1-5. From these relationships, prediction of Mn and Fe core electron binding energies in [Mn(R1COCHCOR2)3] complexes from known manganese and/or ferrocenyl redox potentials are, therefore, now possible. Ligand infrared carbonyl stretching frequencies were successfully related to binding energy as a measure of the energy required for inner-sphere reorganization. In particular it became possible to explain why, upon electrochemical oxidation or photoionization, the ferrocenyl FeII inner-shell of 1-5 needs more energy in complexes with ligands bearing electron-withdrawing (CF3) groups than in ligands bearing electron-donating groups such as ferrocenyl. The XPS determined entity Iratio (the ratio between the intensities of the satellite and main metal 2p3/2 photoelectron lines) is an indication not only of the amount of charge transferred, but also of the degree of inner-sphere reorganization. Just as for binding energy, the quantity Iratio was also found to be related to the energy requirements for the inner-sphere reorganization depicted by the vibrational frequency, vco.