Journal of Physical Organic Chemistry最新文献_第3页

Polybenzenoid Hydrocarbons in the S1 State: Simple Structural Motifs Predict Electronic Properties and (Anti)aromaticity S1态的多苯烃：简单结构基序预测电子性质和（反）芳构性

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-03-24 DOI: 10.1002/poc.70012

Fatimah Khaleel, Sabyasachi Chakraborty, Renana Gershoni-Poranne

{"title":"Polybenzenoid Hydrocarbons in the S1 State: Simple Structural Motifs Predict Electronic Properties and (Anti)aromaticity","authors":"Fatimah Khaleel, Sabyasachi Chakraborty, Renana Gershoni-Poranne","doi":"10.1002/poc.70012","DOIUrl":"https://doi.org/10.1002/poc.70012","url":null,"abstract":"<p>Polybenzenoid hydrocarbons (PBHs) are widely studied for their semiconductive properties and potential applications in organic electronics and photochemistry. Understanding their behavior in excited states is crucial for optimizing their performance in these applications. Here, we computationally investigate a dataset of 43 unbranched <i>cata</i>-condensed PBHs in their first singlet excited state (S₁), revealing clear correlations between molecular structure and electronic properties. By analyzing these molecules through their annulation patterns—specifically the arrangement of linear (L) and angular (A) tricyclic subunits and tetracyclic zigzag (Z) and curve (C) motifs—we establish a predictive hierarchy (L > Z > C > A) for the location of unpaired electrons and Baird-antiaromaticity. This structural approach enables semiquantitative prediction of key properties, including excitation energies, magnetic response, and singlet fission capability. Notably, we find that singlet fission propensity is dependent on both the length of the Longest L sequence and the position of the L motifs within the sequence. These insights, derived from the analysis of small tri- and tetracyclic components and validated on larger systems, provide a practical framework for understanding and designing PBH-based materials.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 5","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70012","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143689966","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanism and Diastereoselectivity of the Photo-/NHC Cocatalyzed Fluoroacylation of Benzofurans: A Theoretical View 光/NHC共催化苯并呋喃氟酰化反应机理及非对映选择性：理论观点

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-03-12 DOI: 10.1002/poc.70007

Zehua Li, Jiying Liu, Jiabin Liu, Panpan Bao, Huixian Jing, Hui Chen, Wenjing Zhang

{"title":"Mechanism and Diastereoselectivity of the Photo-/NHC Cocatalyzed Fluoroacylation of Benzofurans: A Theoretical View","authors":"Zehua Li, Jiying Liu, Jiabin Liu, Panpan Bao, Huixian Jing, Hui Chen, Wenjing Zhang","doi":"10.1002/poc.70007","DOIUrl":"https://doi.org/10.1002/poc.70007","url":null,"abstract":"<div>\u0000 \u0000 <p>The NHC/photoredox cocatalysis proposes an alternative to conventional methods for acylation of the unsaturated bonds. But it is still a great challenge to effectively control the stereoselectivities stemming from couplings of the ketyl radicals and the alkyl radicals. In this work, we have selected the photo-/NHC cocatalyzed fluoroaroylation of benzofurans as the computational model for density functional theory (DFT) studies, intending to unveil mechanisms of the fluorine-induced diastereoselectivities and thus to provide guidance to future rational design of promising catalytic reactions with high stereoselectivities. The computational results reveal that a fluorine-bearing zwitterion intermediate is yielded after nucleophilic addition of the NHC catalyst to the acyl fluorides, because fluorine anion is a poor leaving group. The cross-coupling of the ketyl radical and the tertiary carbon radical is the diastereoselectivity-determining step, and the configuration with the bulky NHC-stabilized ketyl radical bonded <i>trans</i> to the α-fluorine substitution is energetically favor over that giving the <i>cis</i> configuration. The distortion–interaction energy calculations combined with the geometry analysis indicate that the repulsion of the α-fluorine atom on the neighboring carbon results in significant distortions of the two coupling partners in the <i>cis</i>-configuration transition state and therefore leads to high diastereoselectivities. In addition, it is unveiled that the nucleophilicity of the carbene atom could be substantially influenced by electron delocalization. Moreover, the steric hindrance arose from the N(2)-phenyl group warrants attention as it may reduce remarkable geometry distortions with approach of the acyl fluoride compound.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 4","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143612576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Citrate-Based Ionic Liquids for CO2 Capture—A Computational Approach Toward Environmentally Benign Ionic Liquid Anions 基于柠檬酸盐的离子液体用于二氧化碳捕获——一种环境友好型离子液体阴离子的计算方法

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-03-04 DOI: 10.1002/poc.70009

Uttama Mukherjee

{"title":"Citrate-Based Ionic Liquids for CO2 Capture—A Computational Approach Toward Environmentally Benign Ionic Liquid Anions","authors":"Uttama Mukherjee","doi":"10.1002/poc.70009","DOIUrl":"https://doi.org/10.1002/poc.70009","url":null,"abstract":"<div>\u0000 \u0000 <p>This work aims to explore and characterize citrate as an anion of nontoxic and biocompatible origin, which is a crucial step to developing a sustainable CO<sub>2</sub> capture process through ionic liquids (ILs). Citrate ILs have recently been synthesized and utilized as solvents and catalysts for various synthetic purposes in the industry. These are found to be easily recycled, nonpolluting, less corrosive, and easy to synthesize. In this work, citrate–CO<sub>2</sub> and citrate–bmim (1-butyl-3-methylimidazolium) ion pair (IP)–CO<sub>2</sub> interactions have been theoretically explored via carboxylation reactions and various electronic structure calculations. The results indicate favorable citrate–CO<sub>2</sub> interactions in the gas as well as the aqueous phase resulting in monocarboxylates, dicarboxylates, and tricarboxylates of citrates owing to the availability of its three carboxylate O atoms. Even as citrate is paired with bmim, it shows the possibility of multiple site CO<sub>2</sub> absorptions. This system should thus serve as a pathway for enhanced CO<sub>2</sub> capture and better desorption by reducing the formation of carbene–CO<sub>2</sub> complex (reduced basicity of the anion and enhanced steric hindrance of the cation). The study reveals that in the IP, at least one of the citrate O atoms can form a covalent carboxylate (chemisorption) with CO<sub>2</sub> while other available O sites may weakly bind CO<sub>2</sub> (physisorption).</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 4","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143554656","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unexpected the Mechanistic Pathway of the Hydrogen Evolution Reaction in the Presence of N-Substituted Hydro-Derivatives of Ortho-Bipyridines 邻联吡啶n取代氢衍生物存在下析氢反应的机理研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-28 DOI: 10.1002/poc.70010

A. V. Dolganov, A. D. Yudina, L. A. Klimaeva, O. Yu. Ganz, Yu. V. Ulyakina, A. A. Burmistrova, T. O. Karpunina, A. A. Kuzmicheva, S. G. Kostryukov

{"title":"Unexpected the Mechanistic Pathway of the Hydrogen Evolution Reaction in the Presence of N-Substituted Hydro-Derivatives of Ortho-Bipyridines","authors":"A. V. Dolganov, A. D. Yudina, L. A. Klimaeva, O. Yu. Ganz, Yu. V. Ulyakina, A. A. Burmistrova, T. O. Karpunina, A. A. Kuzmicheva, S. G. Kostryukov","doi":"10.1002/poc.70010","DOIUrl":"https://doi.org/10.1002/poc.70010","url":null,"abstract":"<div>\u0000 \u0000 <p>Using cyclic voltammetry, the electrochemical properties and electrocatalytic activity in the reaction of molecular hydrogen formation in the presence of 2,2′-bipyridinium-1,1′-diium and 2,2′-bipyridinium-1-ium perchlorates were studied. The electrochemical reduction product of 2,2′-bipyridinium-1,1′-diium perchlorate decomposes to form molecular hydrogen, but in the case of 2,2′-bipyridinium-1-ium perchlorate, a two-electron reduction product is formed −(E)-1H,1′H-2,2′-bipyridinylidene. It has been shown that the hydrogen evolution reaction (HER) in the presence of 2,2′-bipyridinium-1,1′-diium and 2,2′-bipyridinium-1-ium perchlorates occurs at the same potentials but through different mechanisms. In both cases, the potential is −0.85 V according to the CECE mechanism, but at a potential of −1.25 V according to the ECEC mechanism. In both cases, the key intermediate, through which both mechanisms are realized, is (E)-1H,1′H-2,2′-bipyridinylidene.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 4","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143521828","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The Importance of Strain on the Relative Energies of Bridgehead Radicals 应变对桥头自由基相对能量的重要性

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-21 DOI: 10.1002/poc.70004

Gary W. Breton

引用次数: 0

The Position of ‘Proton Transfer’ Phenomena in Case of Fluoride Detection: A Minireview “质子转移”现象在氟化物检测中的地位

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-18 DOI: 10.1002/poc.70008

Atanu Mahata, Arabinda Mallick

引用次数: 0

A Computational Prediction: Enhancing Visible Light Harvesting Through Minor Modification of Donor Moiety in Triphenylamine-Based Dyes for DSSCs 计算预测：通过对三苯胺基染料中供体部分进行微小修饰来增强DSSCs的可见光捕获

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-18 DOI: 10.1002/poc.70005

Morad M. El-Hendawy, Samar T. Hassan, Emad E. El-Katori, Mahmoud M. A. Mohamed

{"title":"A Computational Prediction: Enhancing Visible Light Harvesting Through Minor Modification of Donor Moiety in Triphenylamine-Based Dyes for DSSCs","authors":"Morad M. El-Hendawy, Samar T. Hassan, Emad E. El-Katori, Mahmoud M. A. Mohamed","doi":"10.1002/poc.70005","DOIUrl":"https://doi.org/10.1002/poc.70005","url":null,"abstract":"<div>\u0000 \u0000 <p>Five triphenylamine-based dyes were theoretically investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT) due to their structural configuration of (D–π–A) which has potential applications as sensitizers for dye-sensitized solar cells (DSSCs). One dye was sourced from the literature, (E)-2-cyano-3-(5-(6-(diphenylamino)-3,3-dimethyl-3H-indol-2-yl)thiophen-2-yl)acrylic acid, denoted as (I), and the remaining dyes (from II to V) are inspired by the former with minor structural change in the indole moiety of donor part. These molecular structures are composed of different diphenyl indole amine species (donor part), thiophene (π-bridge), and cyanoacrylic acid (acceptor part). This study focused on the effect of small structural change in the five-membered ring of the indole moiety on the geometric, electronic, and optical properties of the studied dyes as well as their potential applications as sensitizers for DSSCs. Due to this structural change, a twist in the molecular skeleton of the designed dyes was observed, resulting in a new band at a longer wavelength that spans the visible region. This band is attributed to the phenomenon of twisting intramolecular charge transfer (TICT). The findings reveal that the minor structural change in the indole moiety enhanced the harvesting character of designed dyes that makes them promising candidates for application in DSSCs.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 4","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431244","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Unexpected Inhibition of the Knoevenagel Condensation in Methanol by Iodonium Salt Served as Electrophilic Activator 碘盐作为亲电活化剂对甲醇中Knoevenagel缩合反应的抑制作用

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-14 DOI: 10.1002/poc.70006

Alexandra A. Sysoeva

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False Identification of (Anti)aromaticity in Polycyclic Molecules in Ground and Excited States Through Incorrect Use of NICS 不正确使用NICS对基态和激发态多环分子芳香性的错误识别

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-10 DOI: 10.1002/poc.70000

Péter J. Mayer, Henrik Ottosson

{"title":"False Identification of (Anti)aromaticity in Polycyclic Molecules in Ground and Excited States Through Incorrect Use of NICS","authors":"Péter J. Mayer, Henrik Ottosson","doi":"10.1002/poc.70000","DOIUrl":"https://doi.org/10.1002/poc.70000","url":null,"abstract":"<p>Aromaticity is a key concept in physical organic chemistry. However, as it cannot be measured directly, it is assessed indirectly via other properties (energetic, electronic, geometric and magnetic). Although these properties describe aromaticity, they are not solely related to aromaticity as the observed values also can stem from, for example, magnetically induced local currents at certain atoms or groups, or strain in the σ-skeleton. This can lead to misinterpretations. Here, we highlight a pitfall in the (anti)aromaticity assessment of polycyclic molecules when it is mainly based on nucleus independent chemical shifts (NICSs). The NICS index can be misinterpreted to indicate ‘aromaticity’ or ‘antiaromaticity’ in nonaromatic rings as a result of paratropic or diatropic ring currents in adjacent rings. We explore if such false indications by NICS are (i) stronger in Baird-aromatic or -antiaromatic excited states (mainly triplet and quintet, but also singlet) than in closed-shell singlet ground states, and (ii) if a paratropic ring current in an adjacent ring causes stronger or weaker false ‘aromaticity’ than a diatropic one causes false ‘antiaromaticity’. Based on our computations we conclude that larger aromatic rings in all types of states (e.g., a triplet state Baird-aromatic cyclooctatetraene ring) have greater influence than smaller ones, yet, we see no indication that the effect is stronger in excited states. Instead, annulene rings are more influential in their paratropic (antiaromatic) states, regardless if ground or excited states, than in their diatropic (aromatic) ones.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 3","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70000","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Periselectivity, Chemoselectivity, and Regioselectivity of the Cycloaddition Reaction of Aza-Oxyallyl Cations With Cinnamaldehyde: A Density Functional Theory Study 氮杂氧烯丙基阳离子与肉桂醛环加成反应的选择性、化学选择性和区域选择性：密度泛函理论研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-10 DOI: 10.1002/poc.70003

Godfred Boakye Adusei, Albert Aniagyei, Elliot Menkah, Caroline R. Kwawu, Gabriel Amankwah, Richmond Arhin, Hawa Osman, Evans Adei

引用次数: 0