硼基杂环中抗芳性促进的自由基稳定性及其在二氮活化中的应用:DFT和机器学习的结合研究。

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL
Shijie Pan, Wenhao Wang and Jun Zhu*, 
{"title":"硼基杂环中抗芳性促进的自由基稳定性及其在二氮活化中的应用:DFT和机器学习的结合研究。","authors":"Shijie Pan,&nbsp;Wenhao Wang and Jun Zhu*,&nbsp;","doi":"10.1021/acs.jpca.5c03944","DOIUrl":null,"url":null,"abstract":"<p >Aromaticity is one of the fundamental concepts in chemistry and generally brings additional thermodynamic stability to a compound. On the other hand, boron radicals have attracted increasing interest from both theoretical and experimental chemists due to their various applications. Here, we carry out density functional theory (DFT) calculations to explore the relationship between the (anti)aromaticity and stability of boron-centered radicals. It is found that stronger antiaromaticity of the parent heterocyclics leads to higher thermodynamic stability of the corresponding radicals, which is in sharp contrast to the general knowledge that antiaromaticity brings compounds’ thermodynamic instabilities. In addition, the boryl radicals derived from aromatic precursors are predicated to be favorable both thermodynamically and kinetically for dinitrogen activation. Furthermore, through principal component analysis (PCA), one of the most commonly used unsupervised machine learning algorithms, we have identified that aromaticity, the HOMO–LUMO gap, and spin density collectively contribute to the reaction barrier of dinitrogen activation.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 32","pages":"7390–7400"},"PeriodicalIF":2.8000,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Antiaromaticity-Promoted Radical Stability in Boryl Heterocyclics and Its Application to Dinitrogen Activation: A Combined DFT and Machine Learning Study\",\"authors\":\"Shijie Pan,&nbsp;Wenhao Wang and Jun Zhu*,&nbsp;\",\"doi\":\"10.1021/acs.jpca.5c03944\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Aromaticity is one of the fundamental concepts in chemistry and generally brings additional thermodynamic stability to a compound. On the other hand, boron radicals have attracted increasing interest from both theoretical and experimental chemists due to their various applications. Here, we carry out density functional theory (DFT) calculations to explore the relationship between the (anti)aromaticity and stability of boron-centered radicals. It is found that stronger antiaromaticity of the parent heterocyclics leads to higher thermodynamic stability of the corresponding radicals, which is in sharp contrast to the general knowledge that antiaromaticity brings compounds’ thermodynamic instabilities. In addition, the boryl radicals derived from aromatic precursors are predicated to be favorable both thermodynamically and kinetically for dinitrogen activation. Furthermore, through principal component analysis (PCA), one of the most commonly used unsupervised machine learning algorithms, we have identified that aromaticity, the HOMO–LUMO gap, and spin density collectively contribute to the reaction barrier of dinitrogen activation.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":\"129 32\",\"pages\":\"7390–7400\"},\"PeriodicalIF\":2.8000,\"publicationDate\":\"2025-08-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jpca.5c03944\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpca.5c03944","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

摘要

芳香性是化学中的一个基本概念,通常会给化合物带来额外的热力学稳定性。另一方面,硼自由基由于其广泛的应用,引起了理论和实验化学家越来越多的兴趣。在这里,我们进行密度泛函理论(DFT)计算来探索(反)芳香性和硼中心自由基稳定性之间的关系。研究发现,母体杂环的抗芳性越强,相应自由基的热力学稳定性越高,这与一般认为抗芳性会导致化合物的热力学不稳定性形成鲜明对比。此外,从热力学和动力学上预测芳香前驱体衍生的硼基自由基有利于二氮活化。此外,通过主成分分析(PCA),一种最常用的无监督机器学习算法,我们已经确定芳香性,HOMO-LUMO间隙和自旋密度共同有助于二氮活化的反应势垒。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Antiaromaticity-Promoted Radical Stability in Boryl Heterocyclics and Its Application to Dinitrogen Activation: A Combined DFT and Machine Learning Study

Antiaromaticity-Promoted Radical Stability in Boryl Heterocyclics and Its Application to Dinitrogen Activation: A Combined DFT and Machine Learning Study

Aromaticity is one of the fundamental concepts in chemistry and generally brings additional thermodynamic stability to a compound. On the other hand, boron radicals have attracted increasing interest from both theoretical and experimental chemists due to their various applications. Here, we carry out density functional theory (DFT) calculations to explore the relationship between the (anti)aromaticity and stability of boron-centered radicals. It is found that stronger antiaromaticity of the parent heterocyclics leads to higher thermodynamic stability of the corresponding radicals, which is in sharp contrast to the general knowledge that antiaromaticity brings compounds’ thermodynamic instabilities. In addition, the boryl radicals derived from aromatic precursors are predicated to be favorable both thermodynamically and kinetically for dinitrogen activation. Furthermore, through principal component analysis (PCA), one of the most commonly used unsupervised machine learning algorithms, we have identified that aromaticity, the HOMO–LUMO gap, and spin density collectively contribute to the reaction barrier of dinitrogen activation.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
The Journal of Physical Chemistry A
The Journal of Physical Chemistry A 化学-物理:原子、分子和化学物理
CiteScore
5.20
自引率
10.30%
发文量
922
审稿时长
1.3 months
期刊介绍: The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信