In order to better understand intramolecular communication between molecular fragments, a series of ferrocene-functionalized beta-diketonato manganese(III) complexes, [Mn(FcCOCHCOR)(3)] with R = CF3, 1, CH3, 2, Ph = C6H5, 3, and Fc = Fe-II(eta(s)-C5H4)(eta(s)-C5H5), 4, the mixed ligand beta-diketonato complex [Mn(FcCOCHCOFc)(2)(FcCOCHCOCH(3))], 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 (Fe-II) and Mn-III redox potentials, E degrees', and photoelectron lines were sufficiently resolved in each complex to demonstrate a linear correlation between E degrees' and group electronegativities of ligand R groups, chi(R), or Sigma chi(R), as well as with binding energies of both the Fe (2)p(3/2) and Mn (2)p(3/2) 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((RCOCHCOR2)-C-1)(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 Fe-II 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 I-ratio (the ratio between the intensities of the satellite and main metal (2)p(3/2) 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 I-ratio was also found to be related to the energy requirements for the inner-sphere reorganization depicted by the vibrational frequency,