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首页> 外文期刊>RSC Advances >Significance of the electron-density of molecular fragments on the properties of manganese(III) β-diketonato complexes: an XPS and DFT study
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Significance of the electron-density of molecular fragments on the properties of manganese(III) β-diketonato complexes: an XPS and DFT study

机译：分子片段的电子密度对锰（β）-β-二酮锰配合物性能的意义：XPS和DFT研究

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摘要

DFT and XPS studies were conducted on a series of nine manganese(III) complexes of the general formula [Mn(β-diketonato)3], with the ligand β-diketonato = dipivaloylmethanato (1), acetylacetonato (2), benzoylacetonato (3), dibenzoylmethanato (4), trifluoroacetylacetonato (5), trifluorothenoylacetonato (6), trifluorofuroylacetonato (7), trifluorobenzoylacetonato (8) and hexafluoroacetylacetonato (9). The binding energy position of the main and satellite structures of the Mn 2p3/2 photoelectron line, as well as the spin–orbit splitting, gave insight into the electronic structure of these manganese(III) complexes. DFT calculations showed that an experimental sample of the d4 [Mn(β-diketonato)3] complex can contain a mixture of different bond stretch isomers and different electronic states, in dynamic equilibrium with one other. The presence of more than one isomer in the experimental sample, as well as interaction between an unpaired 2p electron (originating after photoemission) and an unpaired 3d electron, which aligned anti-parallel to the unpaired 2p electron, caused broadening of the Mn 2p photoelectron lines. Multiplet splitting simulations of these photoelectron lines, similar to those calculated by Gupta and Sen for the free Mn(III) ion, gave good fits with the observed Mn 2p3/2 photoelectron lines. The XPS spectra of complexes with unsymmetrical β-diketonato ligands were simulated with two sets of multiplet splitting peaks, representing both the mer and fac isomers. The satellite structures obtained in both the Mn 2p3/2 photoelectron line (shake-up peaks) and the ligand F 1s photoelectron line (shake-down peaks), are representative of the ligand-to-metal charge transfer during photoionisation. The binding energies of the Mn 2p, F 1s and S 2p electrons, as well as the amount of charge transfer from ligand-to-metal, are both dependent on the electronegativity of the different groups attached to the β-diketonato ligand.
机译：DFT和XPS研究了一系列9种通式为[Mn（β-diketonato） 3 ]的锰（ III ）配合物。 ，其配体为β-二酮=复戊酰基甲酰基（1），乙酰丙酮基（2），苯甲酰基丙酮基（3），二苯甲酰基甲烷基（4），三氟乙酰丙酮基（5），三氟噻吩基乙酰基（6），三氟呋喃基乙酰基（7），三氟苯甲酰基乙酰基（8）和9）。 Mn 2p 3/2 光电子线的主结构和卫星结构的结合能位置，以及自旋轨道分裂，使我们深入了解了这些锰（ III ）配合物。 DFT计算表明，d 4 [Mn（β-diketonato） 3 ]配合物的实验样品可以包含不同键拉伸异构体和不同电子态的混合物，彼此动态平衡。实验样品中存在不止一种异构体，以及未配对的2p电子（起源于光发射）和未配对的3d电子之间的相互作用（与未配对的2p电子反平行排列）导致Mn 2p光电子变宽线。这些光电子谱线的多重分裂模拟，类似于由Gupta和Sen计算的游离Mn（ III ）离子的模拟，与观察到的Mn 2p 3/2 < / sub> 光电子线。用两组多重分裂峰（代表 mer 和 fac 异构体）模拟了具有不对称β-二酮基配体的配合物的XPS谱。在Mn 2p 3/2 光电子谱线（摇动峰）和配体F 1s光电子谱线（摇动峰）中获得的卫星结构都具有代表性。离子化过程中配体向金属的电荷转移Mn 2p，F 1s和S 2p电子的结合能以及从配体到金属的电荷转移量均取决于与β-二酮基配体相连的不同基团的电负性。

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