A first principle study of Nitrogen/Carbon replacement in a set of β-aminoacrolein/β-thioaminoacrolein derivatives

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL Computational and Theoretical Chemistry Pub Date : 2025-02-01 Epub Date: 2024-12-22 DOI:10.1016/j.comptc.2024.115053

Malihe Shahraki, Alireza Nowroozi, Ebrahim Nakhaei

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Abstract

This study systematically investigates the impact of N/C substitution in β-aminoacrolein/β-thioaminoacrolein derivatives at various theoretical levels. Key electronic energy components, including electron configuration, nitrogen atom positioning, lone pair-lone pair (Lp-Lp) repulsion, and resonance-assisted hydrogen bonding (RAHB), are evaluated. Results reveal that electron configuration contributes the most stabilizing energy (∼-16 Hartree), while nitrogen positioning and Lp-Lp repulsions destabilizes structures, following the trend: N2 < N1 < N3. RAHB energies are strongly influenced by nitrogen count, with stability improving in the order: N1 (−0.0145) < N2 (−0.0273) < N3 (−0.0370) < N1N2 (−0.0418) < N1N3 (−0.0515) < N2N3 (−0.0643) < N1N2N3 (-0.0788H). Furthermore, energetic, structural, spectral, and topological descriptors support these findings. Interestingly, the aromaticity index indicates a slight reduction in π-electron delocalization (π-ED) with N/C substitution, challenging conventional RAHB theory.

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β-氨基丙烯醛/β-硫代氨基丙烯醛衍生物氮/碳置换的第一性原理研究

本研究在不同理论水平上系统考察了N/C取代对β-氨基丙烯醛/β-硫代氨基丙烯醛衍生物的影响。关键的电子能量成分，包括电子组态、氮原子定位、孤对-孤对（Lp-Lp）斥力和共振辅助氢键（RAHB），进行了评估。结果表明，电子组态贡献了最稳定的能量（~ -16 Hartree），而氮定位和Lp-Lp排斥力则破坏了结构的稳定。N1 & lt;N3。RAHB能量受氮计数的影响较大，稳定性依次提高：N1(−0.0145)<；N2(−0.0273)<；N3(−0.0370)<；N1N2(−0.0418)<；N1N3 (- 0.0515) <；N2N3(−0.0643)<；N1N2N3(-0.0788小时)。此外，能量、结构、光谱和拓扑描述符支持这些发现。有趣的是，芳香性指数表明，N/C取代后π-电子离域（π-ED）略有降低，挑战了传统的RAHB理论。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.