Journal of Physical Organic Chemistry最新文献_第4页

The Study on Synthesis and Characterization of Insensitive Energetic Materials Based on 5-(5-Nitro-1H-1,2,4-Triazol-3-yl)-1H-Tetrazole 基于5-（5-硝基- 1h -1,2,4-三唑-3-基）- 1h -四唑的不敏感含能材料的合成与表征研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-15 DOI: 10.1002/poc.4667

Chenchen Lin, Pingping Yi, Xiaoyi Yi, Tingwei Wang, Jianguo Zhang, Piao He

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The Cleavage of RNA Model Compounds: The Interplay Between the Nucleophile and the Leaving Group RNA 模型化合物的裂解：亲核剂与离去基团之间的相互作用

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-10-09 DOI: 10.1002/poc.4664

Jasmin I. Koski, Emilia Poijärvi, Anne Tulisalo, Heidi Korhonen, Satu Mikkola

{"title":"The Cleavage of RNA Model Compounds: The Interplay Between the Nucleophile and the Leaving Group","authors":"Jasmin I. Koski, Emilia Poijärvi, Anne Tulisalo, Heidi Korhonen, Satu Mikkola","doi":"10.1002/poc.4664","DOIUrl":"https://doi.org/10.1002/poc.4664","url":null,"abstract":"Hydrolytic reactions of phosphodiester bonds of RNA have been extensively studied over several decades. Information on the factors that affect the reactivity of phosphodiester bonds in biomolecules is important for the development of new nucleic acid-related therapeutics. Furthermore, the development of artificial nucleases requires efficient catalytic entities, and rational design of catalysts requires detailed understanding of the catalytic mechanisms. In the present article, we concentrate on the interplay between the nucleophile and leaving group both in the absence and in the presence of metal ion catalysts. The effect of the nucleophile on the reactivity of RNA model compounds has been studied with 2-hydroxypropyl and uridine 3′-aryl phosphates as well as with bis-(p-nitrophenyl)phosphate as substrates. pH-rate profiles for three different 2-hydroxypropyl arylphosphates were compared with those obtained with a uridine 3′-alkyl and aryl phosphates. The observations are discussed in terms of the relative goodness/poorness of the nucleophile and the leaving group. Metal complex-dependent reactions were studied in the presence of well-known and robust CuTerPy and CuBiPy complexes. The results show that CuTerPy and CuBiPy favour different types of phosphodiesters as substrates, depending on the properties of the nucleophile and leaving group, and suggest that the complexes utilize different catalysis mechanisms, which may depend also on the structure of the substrate. The results obtained further the understanding on the basic principles of metal complex-promoted cleavage of RNA and model compounds, help to assess the relevance of data obtained with model compounds and support the design of artificial enzymes for phosphodiester cleavage.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4664","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142868334","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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Computational Justification Towards Detection of Dual Anions on a Single Molecular Platform: The Role of Solvent in Decoration of Dual Channels 单分子平台上双阴离子检测的计算论证：溶剂在双通道修饰中的作用

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 基于叠氮基/硝基/硝基/氟基咪唑骨架的含能材料理论研究

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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Deciphering the Importance of Weak CH…O and CH…π Interactions in S-Propyl (E)-2-(1,1-Dioxido-2-Propylbenzo[d]Isothiazol-3(2H)-ylidene)-1-Propylhydrazine-1-Carbothioate: An Experimental and Theoretical Approach

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-09-27 DOI: 10.1002/poc.4660

Muhammad Naeem Ahmed, Humaira Kashif, Muhammad Nawaz Tahir, Mohammad Shahidul Islam, Tahani Mazyad Almutairi, Mahmoud A. A. Ibrahim, Muhammad Adnan Bashir, Hiram Pérez, Diego M. Gil

{"title":"Deciphering the Importance of Weak CH…O and CH…π Interactions in S-Propyl (E)-2-(1,1-Dioxido-2-Propylbenzo[d]Isothiazol-3(2H)-ylidene)-1-Propylhydrazine-1-Carbothioate: An Experimental and Theoretical Approach","authors":"Muhammad Naeem Ahmed, Humaira Kashif, Muhammad Nawaz Tahir, Mohammad Shahidul Islam, Tahani Mazyad Almutairi, Mahmoud A. A. Ibrahim, Muhammad Adnan Bashir, Hiram Pérez, Diego M. Gil","doi":"10.1002/poc.4660","DOIUrl":"https://doi.org/10.1002/poc.4660","url":null,"abstract":"<div>\u0000 \u0000 The title compound, C17H25N3O3S2, hereafter 1, has been prepared and fully characterized by FTIR, 1H NMR and 13C NMR. Its crystal structure was determined by single-crystal X-ray diffraction. The crystal packing is stabilized by weak CH···O and CH···π interactions. The CLP-Pixel method was used to quantify the energetically significant molecular dimers. The intermolecular contacts were identified and quantified using Hirshfeld surfaces (HS) and the corresponding fingerprint plots. The main contributions to the HS of 1 come from HH, OH/HO and CH/HC contacts, which cover about 93% of the total HS surface. The enrichment ratios showed that the favorable contacts accountable for the crystal packing are consistent with their contributions to the HS. Interaction region indicator (IRI) analysis was used to visualize the location and type of intermolecular contacts, allowing identify the CH···O contacts as van der Waals interactions. To visualize the 3D topology of interactions in the crystal structure, interaction energy values were used to construct energy framework diagrams, which showed that the dispersion energy dominates over other interaction energies, as expected for crystal packing governed by weak interactions. Finally, a combination of MEP surface, QTAIM and NCIplot analysis energetically confirmed the existence of CH···O and O···O dichalcogen interactions.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 2","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143120219","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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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

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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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