Group 14 Central Atoms and Halogen Bonding in Different Dielectric Environments: How Germanium Outperforms Silicon
Group 14 Central Atoms and Halogen Bonding in Different Dielectric Environments: How Germanium Outperforms Silicon
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DOI：
10.1002/cplu.202100294
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发表时间：
2021-08-31
期刊：
影响因子：
3.4
通讯作者：
Wilson, Kaitlin
中科院分区：
文献类型：
--
作者：
Donald, Kelling J.;Prasad, Supreeth;Wilson, Kaitlin
卤素键合在不同介电条件下的性质仍然未被探索，特别是对于无机体系。模型卤素键合配合物（R=H和F，和M=C，Si，和Ge的R3 M-I-NH3）的结构和能量性质的计算检查1和109之间的相对结晶度使用隐式溶剂模型。我们确认和评估异常高的最大电位在西格玛孔上的I（V-S，V-max）在F3 Ge-I相对于的情况下，其中M=C或Si。特别是，Ge在介导诱导效应方面远远优于Si。在V-s、V-max、R3 M-I中I上的全部点电荷和相互作用能以及复合物中的优化I-N距离之间确定了线性关系，通常R-2 >0.97。一个异常的趋势被确定，其中，对于每个M，F3 M-I-NH3变得不太稳定，因为在不同的电介质环境中，优化的I-N距离变得更短;这是使用F-I-NH3复合物作为参考来解释的。
The nature of halogen bonding under different dielectric conditions remains underexplored, especially for inorganic systems. The structural and energetic properties of model halogen bonded complexes (R3M-I-NH3 for R=H and F, and M=C, Si, and Ge) are examined computationally for relative permittivities between 1 and 109 using an implicit solvent model. We confirm and assess the exceptionally high maximum potentials at the sigma hole on I (V-s,V-max) in F3Ge-I relative to cases where M=C or Si. In particular, Ge far outperforms Si in mediating inductive effects. Linear relationships, typically with R-2 >0.97, are identified between V-s,V-max, the full point charge on I in R3M-I, and the interaction energy, and optimized I-N distance in the complexes. An anomalous trend is identified in which, for each M, F3M-I-NH3 becomes less stable as the optimized I-N distance gets shorter in different dielectric environments; it is explained using the F-I-NH3 complex as a reference.