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

Computational Justification Towards Detection of Dual Anions on a Single Molecular Platform: The Role of Solvent in Decoration of Dual Channels

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-06 DOI: 10.1002/poc.4666

Suvendu Paul

{"title":"Computational Justification Towards Detection of Dual Anions on a Single Molecular Platform: The Role of Solvent in Decoration of Dual Channels","authors":"Suvendu Paul","doi":"10.1002/poc.4666","DOIUrl":"https://doi.org/10.1002/poc.4666","url":null,"abstract":"<div>\u0000 \u0000 Ratiometric optical detection of analytes is a convenient strategy as the technique is devoid of relative error and background correction. Herein, solvent-guided ratiometric optical recognition of fluoride and bisulfate anions by a low-cost, “off-the-shelf” bioactive molecule, harmane (HRH) is thoroughly explored. Interestingly, solvent plays a dynamic role in the selective recognition of the dual anions via the dual channels of HRH in an intelligent manner. The probe displays high-fidelity recognition behavior towards fluoride ion in an aprotic solvent (acetonitrile) and towards bisulfate ion in a protic environment (acetonitrile/water; 5:1; v/v). Both the channels of HRH are very selective for a particular anion (F−/HSO4−) in a specific solvent. Organized and comprehensive theoretical calculation denotes that hydrogen bonding between the acidic pyrrolic proton of HRH and fluoride for the first channel and the acidic proton of bisulfate and the pyridinic nitrogen for the second channel of HRH led to the formation of a hydrogen-bonded ion pair (HBIP). Consequently, significant optical changes are observed in the visible region, which is convenient for real-life detection of F− and HSO4− independently. The essential role of solvent in tuning the dual channels of HRH is an important artifact in the literature of fundamental photochemistry.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867908","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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Theoretical Investigation of Energetic Materials Based on Imidazole Framework Featuring Azido/Nitro/Nitrato/Fluoro Groups

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-01 DOI: 10.1002/poc.4661

Anjali Sharma, Kshetrimayum Dhruba Singh, Mridula Guin

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Exploring Spectral and Electrochemical Behavior of Hydroxy-N-Benzylideneanilines by Integrated Theoretical and Experimental Approaches 通过综合理论和实验方法探索羟基-N-苄叉苯胺的光谱和电化学行为

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-09-23 DOI: 10.1002/poc.4659

Prabhudatta Hota, Supriya Priyambada Biswal, Manas Ranjan Dash, Bijnyan Ranjan Das, Pramila Kumari Misra

{"title":"Exploring Spectral and Electrochemical Behavior of Hydroxy-N-Benzylideneanilines by Integrated Theoretical and Experimental Approaches","authors":"Prabhudatta Hota, Supriya Priyambada Biswal, Manas Ranjan Dash, Bijnyan Ranjan Das, Pramila Kumari Misra","doi":"10.1002/poc.4659","DOIUrl":"https://doi.org/10.1002/poc.4659","url":null,"abstract":"<div>\u0000 \u0000 The present work explored the effect of –OH group substitution (o/p) on the spectral and electrochemical behavior of N-benzylideneaniline. The geometry optimization of unsubstituted and (o/p)-OH-substituted analogs revealed the coplanarity of the molecules. The vibrational spectra of the compounds were computed using density functional theory (DFT) and compared with the experimental data. The observed bands were assigned based on total energy distribution (TED). Predicted electronic absorption spectra from time-dependent density functional theory (TD-DFT) calculation were compared with the UV–visible spectra of the molecules. The analysis of the lowest spin-allowed (singlet-singlet) excited states divulged possible electronic transition. The o-substituted benzylideneaniline possessed the lowest highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gap among the substituted and unsubstituted analogs. The intramolecular contacts were interpreted using natural bond orbital and localized molecular orbital analysis. The –CH=N– linkage was investigated as a bridge for the electron delocalization from the donor to acceptor moieties. The manifestation of a reduction peak in the cyclic voltammetric studies confirmed the electrochemical behavior in the –OH-substituted molecule, which was diffusion-controlled. The discrepancy in the electrochemical property concerning the position of the –OH substituent of the candidate molecules was put forward.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642381","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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Correlating Chemical Structure and Charge Carrier Dynamics in Phenanthrocarbazole-Based Hole Transporting Materials for Efficient Perovskite Solar Cells 关联菲罗咔唑基空穴传输材料中的化学结构和电荷载流子动力学以实现高效的过氧化物太阳能电池

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-09-23 DOI: 10.1002/poc.4662

Muzammil Hussain, Muhammad Adnan, Zobia Irshad, Riaz Hussain, Hany W. Darwish, Jongchul Lim

{"title":"Correlating Chemical Structure and Charge Carrier Dynamics in Phenanthrocarbazole-Based Hole Transporting Materials for Efficient Perovskite Solar Cells","authors":"Muzammil Hussain, Muhammad Adnan, Zobia Irshad, Riaz Hussain, Hany W. Darwish, Jongchul Lim","doi":"10.1002/poc.4662","DOIUrl":"https://doi.org/10.1002/poc.4662","url":null,"abstract":"<div>\u0000 \u0000 Polymeric hole transport materials (HTMs) have emerged because of their potential to produce dopant-free, efficient, and stable perovskite solar cells (PSCs). Therefore, we engineered 10 novel donor materials (SMH1–SMH10) containing phenanthrocarbazole-based polymeric structures for organic and PSCs. These molecules underwent bridging-core modifications using different spacers, such as furan (N1), pyrrole (N2), benzene (N3), pyrazine (N4), dioxane (N5), isoxazole (N6), isoindole (N7), indolizine (N8), double bond (N9), and pyrimidine (N10), in comparison to reference molecule R. The study examined the structure–property relationship and the impact of these modifications on the optical, photovoltaic, photophysical, and optoelectronic characteristics of the newly designed SMH1–SMH10 series. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were conducted to analyze frontier molecular orbitals, density of states, reorganization energies, open-circuit voltage, transition density matrix, and charge transfer processes. Results show that the newly designed molecules (SMH1–SMH10) exhibited superior optoelectronics characteristics compared to the R molecule. Among these, SMH4 is the most promising candidate, with a small band gap (2.79 eV), low electron and hole mobility (λe 0.0028 eV, λh 0.0020 eV), lower binding energy (Eb 0.58 eV), high λmax values (656.42 nm in gas, 573.34 nm in chlorobenzene), and a high Voc of 1.30 V. Therefore, this study demonstrated that bridging-core modifications offer a simple and effective strategy for designing desirable characteristics molecules for photovoltaic applications.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642405","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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A Theoretical Perspective on the Stereochemistry of Benzoanellated Aroyl-X,N-Ketene Acetal Derivatives 苯甲酰-X,N-酮醛衍生物立体化学的理论视角

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-09-22 DOI: 10.1002/poc.4658

Francisco A. Martins, Matheus P. Freitas

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Enhanced Hyperpolarizabilities Through p-Phenylene Bridges: Computational Studies on Metamerism and Functional Molecular Properties of Pyridinium–Dicyanomethanide-Based Zwitterions 通过对苯桥增强超极化能力：关于吡啶鎓-二氰基甲烷基偶聚物的同素异形体和功能分子特性的计算研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-09-10 DOI: 10.1002/poc.4657

Sanyasi Sitha

{"title":"Enhanced Hyperpolarizabilities Through p-Phenylene Bridges: Computational Studies on Metamerism and Functional Molecular Properties of Pyridinium–Dicyanomethanide-Based Zwitterions","authors":"Sanyasi Sitha","doi":"10.1002/poc.4657","DOIUrl":"10.1002/poc.4657","url":null,"abstract":"Para-phenylene-bridged pyridinium (acceptor)–dicyanomethanide (donor)-based zwitterions were computationally investigated and are reported here. Reichardt's metamer was found to be twisted and Brooker's metamer in near-planar conformation. Natural bond orbital (NBO) analysis showed that mesomeric resonance is helping Brooker's metamer but found to be not helpful for Reichardt's metamer. To assess the impacts of metamerism and aromatic bridges, fundamental molecular properties like dipole moments (μ), polarizabilities (α), hyperpolarizabilities (β), and adiabatic absorptions of these two molecules were analyzed and then directly compared with their counterpart zwitterions without any bridges (previously reported). Results of impact of metamerism: Reichardt's metamer showed around three times enhanced hyperpolarizabilities (ωB97xD: β = 1577.1 × 10−30 esu) than the Brooker's metamer (ωB97xD: β = 532.5 × 10−30 esu). Impacts of p-phenylene bridges: Compared to their respective D–A directly connected zwitterions reported previously (in ωB97xD methodology, Reichardt's: β = 257.2 × 10−30 esu and Brooker's: β = 67.2 × 10−30 esu), respective p-phenylene-bridged zwitterions showed five to eight times enhanced hyperpolarizabilities. This report highlights the better efficiencies of Reichardt's metamer over Brooker's metamer and aromatically bridged over the directly connected zwitterions. Current findings may be helpful in the designing of efficient functional molecular chromophores, and aromatic bridge combined with zwitterions can be solutions to nonlinear transparency trade-off problem.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4657","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191271","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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In Memoriam: The Life and Scientific Accomplishments of Frank A. L. Anet (1926–2024) 悼念弗兰克-阿奈特（1926-2024）的生平与科学成就

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-08-26 DOI: 10.1002/poc.4656

Darón I. Freedberg, Nicholas V. Hud, Max Kopelevich, Daniel J. O'Leary, Jane Strouse

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Exploring Conformational Preferences in XC(W)ZY Molecules With X, Y = F, Cl, Br and W, Z = O, S, Se: Unraveling the Influence of Conjugative and Anomeric Interactions 探索 XC(W)ZY 分子中的构象偏好，其中 X、Y = F、Cl、Br 和 W、Z = O、S、Se：揭示共轭和同分异构相互作用的影响

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-08-12 DOI: 10.1002/poc.4654

Michelle T. Custodio Castro, Carlos O. Della Védova, Rosana M. Romano

{"title":"Exploring Conformational Preferences in XC(W)ZY Molecules With X, Y = F, Cl, Br and W, Z = O, S, Se: Unraveling the Influence of Conjugative and Anomeric Interactions","authors":"Michelle T. Custodio Castro, Carlos O. Della Védova, Rosana M. Romano","doi":"10.1002/poc.4654","DOIUrl":"10.1002/poc.4654","url":null,"abstract":"<div>\u0000 \u0000 The relative stabilities of the syn- and anti-conformers of 72 molecules belonging to the XC(W)ZY type, with X, Y = F, Cl, Br and W, Z = O, S, Se, have been computed using the B3LYP/aug-cc-pVDZ approximation. The conformational preferences, represented by the energy differences between the two rotamers, exhibit a systematic trend in relation to both the halogen atoms and the chalcogen atoms. These computational predictions are in agreement with available experimental results. The NBO formalism was employed to assess the influence of both the conjugative and anomeric interactions on the relative energy of the conformers. It has been determined that the conjugative interaction provides a satisfactory explanation for the energy differences between rotamers. In contrast, the anomeric interactions favors the syn-conformation in all cases. The relative stabilities between XC(W)ZY/YC(W)ZX and XC(W)ZY/XC(Z)WY constitutional isomers have also been computed and correlated with the experimental data.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191280","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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Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO2 Into Valuable Chemicals 由氨基硼酸衍生的新型三官能团分子内受托路易斯对，可将二氧化碳转化为有价值的化学品

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-08-12 DOI: 10.1002/poc.4655

Mohmmad Faizan, Guntupalli Santhosh, Madhumita Chakraborty, Ravinder Pawar

{"title":"Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO2 Into Valuable Chemicals","authors":"Mohmmad Faizan, Guntupalli Santhosh, Madhumita Chakraborty, Ravinder Pawar","doi":"10.1002/poc.4655","DOIUrl":"10.1002/poc.4655","url":null,"abstract":"<div>\u0000 \u0000 The conversion of CO2 into valuable chemicals remains a significant challenge for achieving environmental sustainability, primarily due to the stability of the CO2 molecule. This necessitates the development of efficient and ecofriendly catalysts. In recent years, frustrated Lewis pairs (FLPs) have shown promise for CO2 utilization. In this study, we introduce α-aminodiboronic acid (DBA), a novel trifunctional aminoboronic acid, as an intramolecular FLP for converting CO2 into cyclic carbonate and formic acid. Using density functional theory (DFT) calculations, we explored the reaction mechanism and investigated DBA's electronic structure through molecular electrostatic potential surface (MESP) and natural bond orbital (NBO) analyses. Our results reveal that one −B (OH)2 group induces an unusual state of frustration in the molecule due to charge transfer from the nitrogen atom's lone pair to the π* orbitals, enhancing catalytic performance. The additional −B (OH)2 group serves as an anchoring site for reactive species. The epoxide activation energy is reduced by approximately 27 kcal/mol compared to the uncatalyzed reaction, and the reduction of CO2 occurs with a requirement of 26 kcal/mol. The additional −B (OH)2 plays a crucial role in the catalytic mechanism and minimizes the energies of various structures observed in the reaction path. The reaction energetics align with structural analysis observations, marking this study as the first report on single-molecule trifunctional FLPs for transforming CO2 into valuable chemicals.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191319","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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Theoretical investigations on N2H5N5/PDO cocrystal via a first-principles study 通过第一原理研究对 N2H5N5/PDO 共晶体进行理论探索

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-08-11 DOI: 10.1002/poc.4653

Zhipeng Chen, Junqi Wang, Qingshan Xie, Chen Yang, Changlin Zhou

{"title":"Theoretical investigations on N2H5N5/PDO cocrystal via a first-principles study","authors":"Zhipeng Chen, Junqi Wang, Qingshan Xie, Chen Yang, Changlin Zhou","doi":"10.1002/poc.4653","DOIUrl":"10.1002/poc.4653","url":null,"abstract":"The exploration of cyclo-N5ˉ-based energetic cocrystals represents a noteworthy avenue within pentazolate chemistry, focusing on leveraging cocrystallization to enhance stability. Recently, a novel cocrystal explosive, N2H5N5/PDO, was developed by combining N2H5N5 with pyrazine 1,4-dioxide (PDO), exhibiting promising detonation characteristics and reduced sensitivity. This study endeavors to elucidate how the structure and noncovalent interactions impact the performance of N2H5N5/PDO through a first-principles investigation. The results indicate that the enhanced hydrogen bonding and wave-like crystal packing structure within the cocrystal effectively bolster its stability compared to N2H5N5. The N···H and O···H interactions, in conjunction with π–π interactions, emerge as critical elements driving cocrystal formation. Compared to the pure N2H5N5, the detonation performance of the cocrystal exhibits a slight decline, albeit with a noticeable reduction in sensitivity.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191320","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