Investigating Unusual Homonuclear Intermolecular "Through-Space" J Couplings in Organochalcogen Systems
Investigating Unusual Homonuclear Intermolecular "Through-Space" J Couplings in Organochalcogen Systems
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DOI：
10.1021/acs.inorgchem.6b01121
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发表时间：
2016-11-07
影响因子：
4.6
通讯作者：
Ashbrook, Sharon E.
中科院分区：
文献类型：
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作者：
Camacho, Paula Sanz;McKay, David;Ashbrook, Sharon E.
虽然电子介导的自旋自旋或J耦合通常被视为通过共价键传递，但已经报道了未正式键合但非常接近的原子之间的J耦合（称为“通过空间”J耦合）的例子。在这项工作中，我们研究了homopolymer P-31 J耦合在有机硫族杂环，这发生在P-31之间的两个单独的分子，毫无疑问地证实了他们通过空间的性质。这种相互作用的存在对于一种化合物来说甚至更令人惊讶，其中它发生在晶体学上等同的物种之间。虽然晶体学上等效的物种不需要磁等效的固态，由于各向异性相互作用的存在下，我们证明，它不是屏蔽各向异性，电梯磁等效，在这种情况下，但存在的异质耦合到Se-77。我们支持我们的实验观察周期性标量相对论密度泛函理论计算和耦合密度变形图可视化这些有趣的相互作用的机制。
Although the electron-mediated spin spin or J coupling is conventionally viewed as transmitted via covalent bonds, examples of J couplings between atoms that are not formally bonded but are in close proximity (termed "through space" J couplings) have been reported. In this work, we investigate the observation of homonuclear P-31 J couplings in organochalcogen heterocycles, which occur between P-31 in two separate molecules, confirming without doubt their through space nature. The presence of this interaction is even more surprising for one compound, where it occurs between crystallographically equivalent species. Although crystallographically equivalent species need not be magnetically equivalent in the solid state, owing to the presence of anisotropic interactions, we demonstrate that it is not the shielding anisotropy that lifts magnetic equivalence, in this case, but the presence of heteronuclear couplings to Se-77. We support our experimental observations with periodic scalar-relativistic density functional theory calculations and coupling density deformation plots to visualize the mechanism of these interesting interactions.