Journal of Physical Organic Chemistry最新文献

Tetra(4-hexylphenyl) [3]- and [5]Cumulenes

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-04-14 DOI: 10.1002/poc.70015

Bozheng Sun, Stefano Pecorario, Elda Sala, Mario Caironi, Michael J. Ferguson, Carlo S. Casari, Rik R. Tykwinski

引用次数: 0

Mechanistic and Curtin–Hammett Studies of the 1O2 Oxidation of a Prenyl Phenol and Phenolate Anion

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-03-25 DOI: 10.1002/poc.70014

Akshaya Iyer, Lloyd Lapoot, Alexander Greer

{"title":"Mechanistic and Curtin–Hammett Studies of the 1O2 Oxidation of a Prenyl Phenol and Phenolate Anion","authors":"Akshaya Iyer, Lloyd Lapoot, Alexander Greer","doi":"10.1002/poc.70014","DOIUrl":"https://doi.org/10.1002/poc.70014","url":null,"abstract":"<div>\u0000 \u0000 The Curtin–Hammett principle, widely recognized in thermal reactions, has been extended to photosensitization processes in this study, providing new insights into the reactivity of photogenerated singlet oxygen (1O2) with phenol and phenolate anion species. Here, we explore mechanistic and Curtin–Hammett studies of the equilibrium between the phenol and phenolate anion forms of a prenylated natural product, prenylphloroglucinol. This study uses density functional theory (DFT) to examine phenol and phenolate anion-quenching pathways of 1O2 showing distinct pathways for each form. In the phenolate anion, 1O2 is quenched to form a peroxy anion. In contrast, in the phenol form, 1O2 leads to a potent epoxidizing agent in a seemingly pro-oxidant path. An iso-hydroperoxyhydrofuran intermediate is proposed to be key in the epoxidation. Meanwhile, the phenolate anion cyclizes and protonates forming a comparatively benign hydroperoxyhydrofuran species. The phloroglucinol is next to the C-prenyated group directs the reaction pathway towards the formation of a dihydrobenzofuran, deviating from the conventional 1O2 “ene” reaction mechanism and the production of allylic hydroperoxides typically observed in trisubstituted alkenes.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 5","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698891","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 Influence of Homoring Competition Effect of Substituents on the Nonclassical Hydrogen Bonding Properties in Diarylnitroketone

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-03-24 DOI: 10.1002/poc.70013

Hua Luo, Chao-Tun Cao, Chenzhong Cao

{"title":"The Influence of Homoring Competition Effect of Substituents on the Nonclassical Hydrogen Bonding Properties in Diarylnitroketone","authors":"Hua Luo, Chao-Tun Cao, Chenzhong Cao","doi":"10.1002/poc.70013","DOIUrl":"https://doi.org/10.1002/poc.70013","url":null,"abstract":"<div>\u0000 \u0000 Nonclassical hydrogen bond (NCHB) as a weak interaction force not only plays an important role in organic conversion and catalysis but also has significant implications for understanding and predicting the properties of compounds. At present, the influence of homoring competition effect of substituents on the intramolecular properties of NCHB has not been studied. In this work, 51 diphenylnitroketone XArCH=N(O)ArY (XPNY) compounds containing different substituents were chosen as model molecules, the bond energy (EHB) in CH⋯O and aromaticity of quasi-aromatic ring (PDIQ) were computed, and the chemical shifts δH(CH⋯O) of 1H NMR in CH⋯O were collected or measured. This work focuses on analyzing the NCHB CH⋯O hydrogen bond in compounds XPNY and explored the influence of homoring competition effect of substituents on the energy EHB of CH⋯O and chemical shift value δH(CH⋯O). The results show that (1) the chemical shift values δH(CH⋯O) of CH⋯O in XPNY are abnormally large, and the values of EHB are 14.15–15.51 kJ/mol, lower than 16.74 kJ/mol, which is consistent with the characteristics of intramolecular NCHB. Therefore, it can be considered that the CH⋯O hydrogen bonds are NCHB in XPNY. (2) The substituent X in compound XPNY exhibits the homoring competition effect. (3) The aromaticity of quasi-aromatic ring Q is the main factor affecting the EHB. The substituent X affects the EHB and δH(CH⋯O) along different paths. This study can help understanding the impact of substituent effects on NCHB in depth.\u0000 </div>","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":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143689968","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

Calculation of the Energy of Intramolecular Hydrogen Bonds Using the Clipping Method: The Case of ω-X-1-Alkanols, X(CH2)nOH

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-03-24 DOI: 10.1002/poc.70011

Robert E. Rosenberg

{"title":"Calculation of the Energy of Intramolecular Hydrogen Bonds Using the Clipping Method: The Case of ω-X-1-Alkanols, X(CH2)nOH","authors":"Robert E. Rosenberg","doi":"10.1002/poc.70011","DOIUrl":"https://doi.org/10.1002/poc.70011","url":null,"abstract":"<div>\u0000 \u0000 Although the energies of intermolecular hydrogen bonds, EHB, can be ascertained by a variety of approaches, there is not a general method to accurately determine the energies for intramolecular hydrogen bonds, EIMHB. Structures for compounds X(CH2)nOH {X = F, OH, NH2, Cl, Br, SH; n = 4–5} are calculated and then “clipped” to form complexes CH3CH2X•CH3CH2OH such that the critical geometric, spectroscopic, and electron density features are preserved. The EIMHB of the parent molecule is assumed to equal the EHB of the complex. Of the previous methods of determining EIMHB, the molecular tailoring approach (MTA) comes closest to the values from this work with the differences due to incomplete cancellation of conformational effects in the MTA. In general, parametric methods fare poorly, only being effective for groups of similar molecules. The cis–trans and isodesmic approaches are of limited value for longer carbon chains due to conformational strain.\u0000 </div>","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":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143690122","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

Polybenzenoid Hydrocarbons in the S1 State: Simple Structural Motifs Predict Electronic Properties and (Anti)aromaticity

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":"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 cata-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.","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

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 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 trans to the α-fluorine substitution is energetically favor over that giving the cis 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 cis-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.\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

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 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 CO2 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–CO2 and citrate–bmim (1-butyl-3-methylimidazolium) ion pair (IP)–CO2 interactions have been theoretically explored via carboxylation reactions and various electronic structure calculations. The results indicate favorable citrate–CO2 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 CO2 absorptions. This system should thus serve as a pathway for enhanced CO2 capture and better desorption by reducing the formation of carbene–CO2 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 CO2 while other available O sites may weakly bind CO2 (physisorption).\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

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 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.\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

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