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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Steric Heavy Atom Effect on Magnetic Anisotropy of Triplet Tribromophenyl Nitrenes
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Steric Heavy Atom Effect on Magnetic Anisotropy of Triplet Tribromophenyl Nitrenes

机译：三重素三溴苯苯基磁各向异性的空间重原子效应

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摘要

Previously unknown the steric heavy atom effect on magnetic anisotropy parameters of triplet phenyl nitrenes is reported. 1.4 The heavy bromine atom effect is revealed by W-band EPR and theoretical investigations of triplet 2,4,6-tribromophenyl nitrenes bearing different substituents in positions 3 and S of the phenyl ring (1a, H/H; 1b, CN/CN; 1c, N-3/F; 1d, N-3/N-3; 1e, Cl/Cl; 1f, Br/Br). The zero-field splitting parameters of nitrenes 1a (D = 0.9930 cm (-1) , E = 0.0261 cm (-1) ), 1c (D = 1.244 cm(-1), E = 0.030 cm(-1)), and 1d (D = 1.369 cm(-1), E = 0.093 cm(-1)), generated by the photolysis of the corresponding azides in frozen methylcyclohexane solution at 5 K, were determined from the W-band EPR spectra. To clarify the origin of considerable differences in the experimental D values of nitrenes 1a, 1c, and 1d, extensive DFT and CASSCF calculations of these nitrenes as well as of model nitrenes 1b, 1e, and if were performed. The calculations show that all nitrenes have nearly the same magnitudes of the spin-spin interactions (D-SS similar to cm(-1)), but drastically differ in the spin-orbit coupling parameter (from D-SOC = 0.087 cm(-1) for la to D-SOC = 0.765 cm(-1) for 1f). Comprehensive analysis of various computational data showed that the magnitude of D-SOC of nitrenes 1a-f is the function of the N-Br distance between the nitrene nitrogen and the neighboring bromine atoms. The more bulky substituents are located in positions 3 and 5 of nitrenes 1a-1f, the smaller the N--Br distance and the larger D-SOC. These features indicate that the heavy atom effect on magnetic anisotropy of triplet phenyl nitrenes originates from the through-space rather than through-bond electronic interactions between the bromine atoms and the nitrene unit.
机译：以前未知，报道了对三重素苯基Nitrenes的磁各向异性参数的空间重原子效应。 1.4重溴原子效应是通过W波段EPR和亚苯基环（1A，H / H; 1B，CN / CN的S中的不同取代基的三元油2,4,6-三溴苯苯基NITREN的理论研究。（1A，H / H; 1B，CN / CN ; 1c，n-3 / f; 1d，n-3 / n-3; 1e，cl / cl; 1f，br / br）。 Nitrenes 1a的零场分裂参数（d = 0.9930cm（-1），e = 0.0261cm（-1）），1c（d = 1.244cm（-1），e = 0.030cm（-1）），通过在5K处的冷冻甲基环己烷溶液中的相应叠氮化物的光解产生的1D（D = 1.369cm（-1），e = 0.093cm（-1））由W波段EPR光谱测定。为了阐明Nitren1a，1c和1d的实验性D值，广泛的DFT和Casscf计算的实验性D值以及模型1b，1e和If的模型的起源。计算结果表明，所有1nrenes都具有几乎与旋转自旋相互作用的几乎相同的幅度（类似于cm（-1）的d-ss），但在旋转轨道耦合参数（来自d-soc = 0.087cm（ - 1）对于La至D-SoC = 0.765cm（-1）为1F）。各种计算数据的综合分析表明，Nitren1a-F的D-SoC的大小是硝化氮和相邻溴原子之间的N-Br距离的功能。更庞大的取代基位于1A-1F的位置3和5中，N - BR距离越小，D-SoC越小。这些特征表明重型原子对三重酚苯NITREN的磁各向异性的影响来自溴原子和硝基单元之间的通孔而不是通过键合电子相互作用。

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