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首页> 外文期刊>Chemistry: A European journal >Discrepancy between the Spin Distribution and the Magnetic Ground State for a Triaminoxyl Substituted Triphenylphosphine Oxide Derivative
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Discrepancy between the Spin Distribution and the Magnetic Ground State for a Triaminoxyl Substituted Triphenylphosphine Oxide Derivative

机译：三氨基甲氧基取代的三苯膦氧化物衍生物的自旋分布与磁性基态之间的差异

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摘要

The magnetic interaction and spin transfer via phosphorus have been investigated for the tri-ferf-butylami-noxyl para-substituted triphenylphos-phine oxide.For this radical unit,the conjugation existing between the it* orbital of the NO group and the phenyl ji orbitals leads to an efficient delocaliza-tion of the spin from the radical to the neighboring aromatic ring.This has been confirmed by using fluid solution high-resolution EPR and solid state MAS NMR spectroscopy.The spin densities located on the atoms of the molecule could be probed since ~1H,~13C,~14N,and ~3IP are nuclei active in NMR and EPR,and lead to a precise spin distribution map for the triradical.The experimental investigations were completed by a DFT computational study.These techniques established in particular that spin density is located at the phosphorus(p=-15xl0~(-3)au),that its sign is in line with the sign alternation principle and that its magnitude is in the order of that found on the aromatic C atoms of the molecule.Surprisingly,whereas the spin distribution scheme supports ferromagnetic interactions among the radical units,the magnetic behavior found for this molecule revealed a low-spin ground state characterized by an intramolecular exchange parameter of J=-7.55cm~(-1)as revealed by solid state susceptibility studies and low temperature EPR.The X-ray crystal structures solved at 293 and 30 K show the occurrence of a crystallographic transition resulting in an ordering of the molecular units at low temperature.
机译：研究了三-铁-丁基-氨基-芳氧基对位取代的三苯基膦-膦氧化物的磁性相互作用和自旋转移。对于该自由基单元，NO *的it *轨道与苯基ji轨道之间存在共轭导致自旋从自由基有效地离域到相邻的芳环，这已经通过使用流体溶液高分辨率EPR和固态MAS NMR光谱得到了证实，位于分子原子上的自旋密度可以是自〜1H，〜13C，〜14N和〜3IP探测到的核在NMR和EPR中具有核活性，并产生了精确的三自由基自旋分布图。通过DFT计算研究完成了实验研究，这些技术特别确立了自旋密度位于磷（p = -15xl0〜（-3）au）处，其符号与符号交替原理一致，并且其大小与在芳族C原子上发现的顺序相同出乎意料的是，尽管自旋分布方案支持自由基单元之间的铁磁相互作用，但是该分子的磁行为揭示了低自旋的基态，其特征在于分子内交换参数为J = -7.55cm〜（-1）。通过固态磁化率研究和低温EPR。在293和30 K下解析的X射线晶体结构显示出晶体学转变的发生，导致低温下分子单元的排序。

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