Ibrahim Mahmoud A A, Kamel Afnan A K, Soliman Mahmoud E S, Moustafa Mahmoud F, El-Mageed H R Abd, Taha Fouad, Mohamed Lamiaa A, Moussa Nayra A M
Computational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University, Minia 61519, Egypt.
Molecular Bio-computation and Drug Design Lab, School of Health Sciences, University of KwaZulu-Natal, Westville, Durban 4000, South Africa.
ACS Omega. 2021 Sep 22;6(39):25476-25485. doi: 10.1021/acsomega.1c03461. eCollection 2021 Oct 5.
A quantum chemical study was accomplished on the σ-hole interactions of the barely explored group IV elements, for the first time, in the absence and presence of the positively and negatively directed external electric field (EEF). The analyses of molecular electrostatic potential addressed the occurrence of the σ-hole on all the inspected tetrel atoms, confirming their salient versatility to engage in σ-hole interactions. MP2 energetic findings disclosed the occurrence of favorable σ-hole interactions within the tetrel bonding complexes. The tetrel bonding interactions became stronger in the order of C < Si < Ge < Sn for F-T-F···FH complexes with the largest interaction energy amounting to -19.43 kcal/mol for the optimized F-Sn-F···FH complex under the influence of +0.020 au EEF. The interaction energy conspicuously evolved by boosting the magnitude of the positively directed EEF value and declining the negatively directed EEF one. The decomposition analysis for the interaction energies was also executed in terms of symmetry-adapted perturbation theory, illuminating the dominant electrostatic contribution to all the studied complexes' interactions except carbon-based interactions controlled by dispersion forces. The outcomes that emerged from the current work reported significantly how the direction and strength of the EEF affect the tetrel-bonding interactions, leading to further improvements in the forthcoming studies of supramolecular chemistry and materials science.
首次在不存在和存在正负方向外部电场（EEF）的情况下，对研究较少的第IV族元素的σ-空穴相互作用进行了量子化学研究。分子静电势分析表明，在所有被检查的四价元素原子上都存在σ-空穴，证实了它们参与σ-空穴相互作用的显著通用性。MP2能量研究结果揭示了在四价元素键合配合物中存在有利的σ-空穴相互作用。对于F-T-F···FH配合物，四价元素键合相互作用按C < Si < Ge < Sn的顺序增强，在+0.020 au EEF影响下优化的F-Sn-F···FH配合物的最大相互作用能达到-19.43 kcal/mol。通过提高正方向EEF值的大小和降低负方向EEF值，相互作用能显著变化。还根据对称适配微扰理论对相互作用能进行了分解分析，揭示了除受色散力控制的碳基相互作用外，静电对所有研究配合物相互作用的主要贡献。当前工作得出的结果显著表明了EEF的方向和强度如何影响四价元素键合相互作用，这将在超分子化学和材料科学的后续研究中带来进一步的改进。
