Ibrahim Mahmoud A A, Mahmoud Asmaa M M, Saeed Rehab R A, Shehata Mohammed N I, Shoeib Tamer, Al-Fahemi Jabir H
Computational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University Minia 61519 Egypt
Department of Engineering, College of Engineering and Technology, University of Technology and Applied Sciences Nizwa 611 Sultanate of Oman.
RSC Adv. 2025 Aug 22;15(36):29811-29821. doi: 10.1039/d5ra04648c. eCollection 2025 Aug 18.
Interactions of hypervalent IF and XeFO molecules within the square pyramidal geometry σ-hole site with Lewis bases (LB = NH and NCH) and anions (X = F, Cl, Br, and I) were comparatively investigated using methods. The energetic features outlined remarkable interaction ( ) and binding ( ) energies for all complexes aligned from -5.65 to -91.02 kcal mol and from -5.53 to -65.89 kcal mol, respectively. More negative and values were demonstrated for XeFO⋯LB complexes, compared to IF⋯LB complexes, along with nominal deformation energies for all complexes. Turning to IF⋯ and XeFO⋯X complexes, demonstrated the proficiency of the latter complexes, which was in synchronic with the claims. On the contrary, IF⋯X complexes demonstrated higher negative values in comparison to XeFO⋯X complexes, which may be attributed to the considerable favorable deformation energies relevant to the former complexes rather than the latter candidates. Moreover, the and were disclosed to ameliorate in coincidence with the Lewis basicity strength as follows: IF/XeFO⋯NCH < ⋯NH < ⋯I < ⋯Br < ⋯Cl < ⋯F. Quantum theory of atoms in molecules/noncovalent interactions index observations affirmed that the interactions of IF/XeFO molecules σ-hole site with NH and NCH were characterized with open- and closed-shell nature, respectively, while the IF/XeFO⋯X complexes were characterized with the coordinative covalent nature. Symmetry-adapted perturbation theory results pinpointed the predominance of the inspected interactions with the electrostatic forces. The acquired results will be advantageous for the ubiquitous investigation of understanding the impact of geometrical deformation on the interactions of hypervalent molecules and their applications in diverse fields such as materials science and crystal engineering.
利用相关方法，对正方锥几何结构σ-空穴位点内的高价碘氟（IF）和氙氟氧（XeFO）分子与路易斯碱（LB = NH和NCH）以及阴离子（X = F、Cl、Br和I）之间的相互作用进行了比较研究。能量特征表明，所有配合物的显著相互作用能（）和结合能（）分别在-5.65至-91.02 kcal/mol和-5.53至-65.89 kcal/mol范围内。与IF⋯LB配合物相比，XeFO⋯LB配合物表现出更负的和值，同时所有配合物的标称变形能也如此。对于IF⋯和XeFO⋯X配合物，表明了后者配合物的优势，这与的说法一致。相反，IF⋯X配合物与XeFO⋯X配合物相比表现出更高的负值，这可能归因于与前者配合物相关的相当有利的变形能，而不是后者。此外，和被发现随着路易斯碱强度的增加而改善，顺序如下：IF/XeFO⋯NCH < ⋯NH < ⋯I < ⋯Br < ⋯Cl < ⋯F。分子中原子的量子理论/非共价相互作用指数观察证实，IF/XeFO分子的σ-空穴位点与NH和NCH的相互作用分别具有开壳层和闭壳层性质，而IF/XeFO⋯X配合物具有配位共价性质。对称适配微扰理论结果指出，所研究相互作用中静电力占主导。所获得的结果将有利于普遍研究理解几何变形对高价分子相互作用的影响及其在材料科学和晶体工程等不同领域的应用。
