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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Experimental NMRD Profiles for Some Low-Symmetry Ni(II) Complexes (S = 1) in Solution and Their Interpretation Using Slow-Motion Theory
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Experimental NMRD Profiles for Some Low-Symmetry Ni(II) Complexes (S = 1) in Solution and Their Interpretation Using Slow-Motion Theory

机译：溶液中一些低对称Ni（II）配合物（S = 1）的实验NMRD谱及其使用慢运动理论的解释

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摘要

Experimental NMRD profiles for four Ni(II) complexes (S = 1) in solution have been interpreted using slow-motion theory. Rhombicity in the zero-field splitting (ZFS) and noncoinciding static ZFS and dipole-dipole (DD) tensors are included in the model, which improves the physical picture in terms of the electronic structure and deformability of the complexes. In a previous study from our laboratory, Ni(dpm)_2(aniline-d_5)_2~(2+) data were reported and analyzed using a model that assumed axially symmetric ZFS and coinciding static ZFS and DD tensors. These data are reinterpreted in the present article, which provides a nearly axially symmetric static ZFS. New experimental data on three aqueous solutions containing tetraaza complexes are also reported and interpreted. One of the systems, Ni([15]aneN_4)(H_2O)_2~(2+), gives best-fit parameter values similar to those of Ni(dpm)_2(aniline-d_5)_2~(2+). These two systems have the two solvent molecules coordinated in axial positions. The second complex, Ni([12]aneN_4)(H_2O)_2~(2+), differs substantially in that the water molecules are coordinated in the cis configuration and that the best fit was obtained using a highly rhombic ZFS. The third complex, Ni(tmc)(H_2O)~(2+), is five-coordinated, which results in a rather large rhombicity. In all cases, the best-fit parameters are clearly outside of the Redfield limit, which means that simpler theories are of limited use. We have also found that the latter two systems differ very much from the two former systems in terms of electron-spin dynamics. The main reason lies in the difference in the relative magnitudes of the static and the fluctuating transient parts of the ZFS, and this feature has a great impact on the rhombicity effect.
机译：使用慢动作理论解释了溶液中四种Ni（II）配合物（S = 1）的实验NMRD曲线。该模型包括零场分裂（ZFS）和非一致静态ZFS和偶极子-偶极子（DD）张量中的菱形，这从电子结构和配合物的可变形性方面改善了物理图景。在我们实验室的先前研究中，报告了Ni（dpm）_2（苯胺-d_5）_2〜（2+）数据，并使用假设轴向对称ZFS和重合静态ZFS和DD张量的模型进行了分析。这些数据在本文中得到了重新解释，该文章提供了几乎轴向对称的静态ZFS。还报道和解释了关于含四氮杂配合物的三种水溶液的新实验数据。系统之一Ni（[15] aneN_4）（H_2O）_2〜（2+）提供的最佳拟合参数值类似于Ni（dpm）_2（苯胺-d_5）_2〜（2+）。这两个系统在轴向位置上配设有两个溶剂分子。第二种配合物Ni（[12] aneN_4）（H_2O）_2〜（2+）的主要区别在于水分子呈顺式配位，并且使用高度菱形的ZFS可获得最佳拟合。第三个配合物Ni（tmc）（H_2O）〜（2+）是五配位的，导致菱形较大。在所有情况下，最佳拟合参数显然都超出了Redfield限制，这意味着较简单的理论用途有限。我们还发现，在电子自旋动力学方面，后两种系统与前两种系统有很大不同。主要原因是ZFS的静态部分和波动的瞬态部分的相对大小不同，并且此功能对菱形效果产生很大影响。

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