Journal of Physical Organic Chemistry最新文献_第2页

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 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.\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}

引用次数: 0

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

引用次数: 0

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":"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.","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}

引用次数: 0

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

DFT Insights Into Non-Catalytic Aminolysis of Polycarbonates DFT对聚碳酸酯非催化氨解的见解

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-01-28 DOI: 10.1002/poc.70001

Alexander Y. Samuilov, Amran Abdullah Ghilan Ali, Yakov D. Samuilov

{"title":"DFT Insights Into Non-Catalytic Aminolysis of Polycarbonates","authors":"Alexander Y. Samuilov, Amran Abdullah Ghilan Ali, Yakov D. Samuilov","doi":"10.1002/poc.70001","DOIUrl":"https://doi.org/10.1002/poc.70001","url":null,"abstract":"<div>\u0000 \u0000 The problem of environmental pollution by plastic is becoming more and more obvious. In this study, the non-catalytic reaction of diphenyl carbonate with methylamine as a model reaction for the depolymerization of polycarbonate was studied at the B3LYP/6-31++G(d,p) and M062X/6-31++G(d,p) levels. The reaction can proceed by the nucleophilic substitution and by the “addition–elimination” pathways. Calculations at the B3LYP/6-31++G(d,p) level indicate that the reaction of diphenyl carbonate with methylamine monomer leading to the formation of N-methyl-O-phenylcarbamate via the nucleophilic substitution pathway at 298 K is characterized by activation and reaction free energies equal to 174.0 and −57.1 kJ·mol−1. The same reaction with methylamine dimer is characterized by activation and reaction free energies equal to 147.1 and −77.7 kJ·mol−1, respectively. Thermodynamic and kinetic preference is also observed in the reaction of N-methyl-O-phenylcarbamate with the monomer and dimer of methylamine. Reactions with the formation of tetrahedral intermediates are unlikely. Their formation is endothermic and occurs with a decrease in entropy. This leads to small values of equilibrium constants. The equilibrium constant of the reaction of diphenyl carbonate with methylamine monomer to form a tetrahedral intermediate is 1.64·10−16 at 298 K and 1.20·10−14 at 423 K. The same trends are observed in the reactions of N-methyl-O-phenylcarbamate. The reactions of diphenyl carbonate, N-methyl-O-phenylcarbamate with methylamine dimer via the “addition–elimination” pathway are also characterized by small values of equilibrium constants. In all cases, interactions involving the methylamine dimer are more favorable than reactions involving the methylamine monomer.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 3","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143120056","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

Rigidity Analysis of Hydride Tunneling-Ready States From Secondary Kinetic Isotope Effects and Hammett Correlations: Relating to the Temperature Dependence of Kinetic Isotope Effects 从二次动力学同位素效应和Hammett关联分析氢化物隧穿就绪态的刚度：与动力学同位素效应的温度依赖性有关

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-01-28 DOI: 10.1002/poc.70002

Mingxuan Bai, Grishma Singh, Yun Lu

{"title":"Rigidity Analysis of Hydride Tunneling-Ready States From Secondary Kinetic Isotope Effects and Hammett Correlations: Relating to the Temperature Dependence of Kinetic Isotope Effects","authors":"Mingxuan Bai, Grishma Singh, Yun Lu","doi":"10.1002/poc.70002","DOIUrl":"https://doi.org/10.1002/poc.70002","url":null,"abstract":"<div>\u0000 \u0000 Recent study on the effects of enzyme mutations on the primary kinetic isotope effects (1° KIEs) of H-tunneling reactions revealed that a more rigid system results in a weaker temperature dependence of KIEs, indicated by a smaller isotopic activation energy difference (∆Ea = EaD − EaH). In literature, a more rigid system has been defined by the presence of shorter, more densely populated hydrogen donor-acceptor distances (DADs) in both the productive reactant complexes (PRCs) and the tunneling-ready states (TRSs). Studying the relationship between DADPRC/DADTRS and ∆Ea can help validate existing H-tunneling models or guide the development of new theories. In a previous publication, we employed Hammett correlations on hydride acceptors (NAD+ analogues) to propose TRS electronic structures for qualitative analysis of DADTRS order. In this paper, we selected a pair of such systems and used secondary (2°) KIEs on the hydride donor (NADH analogue) to obtain quantitative DADTRS information at the molecular level. TRS structures were computed, and the corresponding 2° KIEs were calculated and fitted to the observed values to extract DADTRS data. PRC structures were also computed. The DADPRC/DADTRS information aligns with the rigidity order derived from Hammett correlation analysis, and the correlation between DADPRC/DADTRS and ∆Ea is consistent with observations in enzyme systems.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 3","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143120013","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

Machine Learning Enabling the Prediction of Activation Energies of SPAAC 利用机器学习预测SPAAC的活化能

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-01-17 DOI: 10.1002/poc.4679

Jason D. Josephson, John Paul Pezacki, Masaya Nakajima

引用次数: 0

Theoretical Study on ESIPT for NHBQ-NO2 and NHBQ-NH2: A DFT/TDDFT Study NHBQ-NO2和NHBQ-NH2的ESIPT理论研究：DFT/TDDFT研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-01-03 DOI: 10.1002/poc.4680

Wen Zeng, Wenlong Shao, Jinfeng Zhao, Jiahe Chen

引用次数: 0