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 = Fe^II(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 (Fe^II) and Mn^III 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, χ_R, or Σχ_R, as well as with binding energies of both the Fe 2p_3/2 and Mn 2p_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(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 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 2p_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, v_co.

中文翻译：

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电化学测量可以用于预测X射线光电子能谱数据吗？锰的二茂铁基-β-二酮基配合物的情况（III）

为了更好地理解分子片段之间的分子内的通信，一系列二茂铁官能化β-二酮盐锰（III）络合物，[Mn（上FcCOCHCOR）的₃ ]，其中R = CF ₃，1，CH ₃，2中，Ph = C ₆ ħ ₅，3，和Fc =铁^II（η ⁵ -C ₅ H ^ ₄）（η ⁵ -C ₅ H ^ ₅），4，混合配体β-二酮盐络合物[锰（FcCOCHCOFc）₂（FcCOCHCOCH ₃）]，5以及acac配合物[Mn（CH ₃ COCHCOCH ₃）₃ ] 6均经过电化学和X射线光电子能谱（XPS）研究。所述二茂铁基（铁^II）和Mn ^III的氧化还原电位，ê °'和光电子线在每个复合物充分消除演示之间的线性相关ë °'和配体的R基团的基团的电负，χ _{- [R} ，或Σχ _{- [R} ，如以及Fe 2p _3/2和Mn 2p _3/2的结合能光电子线。这些关系是随着分子片段之间的有效通信一致1 - 5。因此，根据这些关系，现在有可能从已知的锰和/或二茂铁基氧化还原电势预测[Mn（R ¹ COCHCOR ²）₃ ]配合物中的Mn和Fe核电子结合能。配体红外羰基的拉伸频率已成功地与结合能相关，以作为内球重组所需能量的量度。特别地，它成为可能解释为什么，在电化学氧化或光致电离，二茂铁的Fe ^II的内壳层1 - 5与带有吸电子基团的配体（如二茂铁基）配位体相比，与带有吸电子基团（CF ₃）的配位体需要更多的能量。XPS确定的实体I_比率（卫星和主要金属2p _3/2光电子线的强度之比）不仅表示电荷转移的数量，而且还表示内部球的重组程度。就像束缚能量一样，量I_比也与振动频率v _co所描绘的内球重组的能量需求有关。