Journal of Physical Organic Chemistry最新文献_第7页

A Density Functional Theory Study of Ru-Catalyzed Self-Coupling Reaction of Secondary Alcohols 钌催化仲醇自偶联反应的密度泛函理论研究

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-01-21 DOI: 10.1002/poc.70068

Junjie Xiao, Yan Li, Zhiqiang Zhang

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Quantifying the Electrophilicity of 9(10H)-Phenanthrenone- and 1-Acenaphthenone-Derived α, β-Unsaturated Ketones 测定9(10H)-菲萘醌和1-阿萘醌衍生的α， β-不饱和酮的亲电性

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-01-09 DOI: 10.1002/poc.70061

Christoph Gross, Jan Brossette, Luc Schellmann, Peter Mayer, Hendrik Zipse, Armin R. Ofial

{"title":"Quantifying the Electrophilicity of 9(10H)-Phenanthrenone- and 1-Acenaphthenone-Derived α, β-Unsaturated Ketones","authors":"Christoph Gross, Jan Brossette, Luc Schellmann, Peter Mayer, Hendrik Zipse, Armin R. Ofial","doi":"10.1002/poc.70061","DOIUrl":"https://doi.org/10.1002/poc.70061","url":null,"abstract":"The dibenzo-annulated six-membered ring of 9(10H)-phenanthrenone- and the dibenzo-annulated five-membered ring in 1-acenaphthenone-derived α, β-unsaturated ketones were chosen to study the influence of the ring size on the reactivity of the exocyclic electron-deficient π-system. The kinetics of nucleophilic addition of carbanions to both Michael acceptors in DMSO at 20°C was monitored by UV-Vis spectroscopy to determine the second-order rate constants k2 of the carbon–carbon bond-forming reactions. The Mayr–Patz equation, lg k2 = sN(N + E), along with reported reactivity parameters (N and sN) of the carbanions were used to calculate the electrophilicity parameter E for both electrophiles. The higher electrophilicity of the phenanthrenone-derived Michael acceptor was further scrutinized by quantum chemical calculations, which showed a less advanced bond formation in the transition state and a greater thermodynamic driving force for adduct formation for the phenanthrenone (E = −15.93) than for the acenaphthenone-derived α, β-unsaturated ketone (E = −18.72). Thus, the phenanthrenone derivative is located on the electrophilicity scale in the reactivity range of structurally related ortho-quinone methides. The acenaphthenone derivative has similar electrophilicity as cyclic α, β-unsaturated lactones with an exocyclic methylene group. Further nucleophilic reaction partners for both studied electrophiles can now be systematically selected by using the Mayr reactivity scales.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70061","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145983408","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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A DFT Study of Electronic Inductive and Resonance Effects of Substituents on Concerted Two-Proton-Coupled Electron Transfer Between Catechol Derivatives and Superoxide 取代基对儿茶酚衍生物与超氧化物间双质子耦合电子转移的电子感应和共振效应的DFT研究

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-12-31 DOI: 10.1002/poc.70064

Tatsushi Nakayama

{"title":"A DFT Study of Electronic Inductive and Resonance Effects of Substituents on Concerted Two-Proton-Coupled Electron Transfer Between Catechol Derivatives and Superoxide","authors":"Tatsushi Nakayama","doi":"10.1002/poc.70064","DOIUrl":"https://doi.org/10.1002/poc.70064","url":null,"abstract":"<div>\u0000 \u0000 The development of biomimetic electron transfer catalysts based on proton-coupled electron transfer (PCET), which is characterized by quinone–hydroquinone π-conjugation, represents a promising approach for achieving highly efficient artificial energy conversion. Herein, I report a density functional theory (DFT)-based analysis of the electronic inductive (I) and resonance (R) effects of substituents on concerted two-proton-coupled electron transfer (2PCET) between benzene-1,2-diol (catechol) derivatives and the superoxide radical anion (O2•−). In this study, I investigated the relationship between the type and number of substituents and their effects on 2PCET using 12 catechol derivatives. Four types of substituents—methyl (+I, +R), chloro (−I, +R), methoxy (−I, +R), and cyano (−I, −R)—were selected in mono-, di-, tri-, and tetra-substituted forms to isolate and analyze their electronic effects without additional functionalities. My DFT results confirmed that substituent effects selectively enhance either proton or electron transfer along a sequential PCET pathway. Further analysis revealed that the R effect is the primary driving force for concerted 2PCET, where an increasing number of methyl or chloro substituents promotes the reaction, whereas cyano substituents suppress it. The I and R effects influence the electronic properties of the catechol molecule in proportion to the number of substituents. However, free energy calculations indicated kinetic and thermodynamic deviations, suggesting that the substituents directly affected the two hydroxyl groups—the reaction sites of 2PCET—as well as their solvation environment.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145887970","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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Enhanced Mobility of Electrons via the Peripheral and Spacer Moieties Into Perylene Diimide-Based Compounds Lead to Promising Photovoltaic Properties: A DFT/TD-DFT Insight 通过外围和间隔基团增强电子迁移率进入苝二酰亚胺基化合物导致有前途的光伏性质：DFT/TD-DFT洞察

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-12-29 DOI: 10.1002/poc.70062

Mashal Khan, Muhammad Khalid, Muhammad Imran, Shahzad Murtaza, Ataualpa Albert Carmo Braga

{"title":"Enhanced Mobility of Electrons via the Peripheral and Spacer Moieties Into Perylene Diimide-Based Compounds Lead to Promising Photovoltaic Properties: A DFT/TD-DFT Insight","authors":"Mashal Khan, Muhammad Khalid, Muhammad Imran, Shahzad Murtaza, Ataualpa Albert Carmo Braga","doi":"10.1002/poc.70062","DOIUrl":"https://doi.org/10.1002/poc.70062","url":null,"abstract":"<div>\u0000 \u0000 The remarkable applications of the nonfullerene acceptors (NFAs) make them highly favorable for commercialization as the organic photovoltaic materials. Herein, new perylene diimide-based compounds (PDFD1–PDFD9) with A1–π–A2–π–A1 configuration were structurally designed by altering the π–bridges and end-capped acceptors for efficient perovskite materials for organic solar cells (OSCs). Density functional theory (DFT) and time-dependent DFT (TD-DFT) approach were employed to calculate the photophysical, optoelectronic and photovoltaic properties of the designed molecules. The results showed that these chromophores exhibited remarkably reduced Egap (2.36–3.05 eV) and red-shifted absorption (λmax) values, that is, 462–752 nm in the gas and 475–756 nm in the chloroform solvent phases. Moreover, the transition density matrix (TDM) plots along with the lower exciton binding energies (0.44–0.74 eV) showed efficient charge separation and recombination, which demonstrated significant charge transfer (CT). Furthermore, the donor: acceptor complex (PBDB-T:PDFD8) revealed prominent charge shift from the HOMO to LUMO. Among the proposed organic chromophores, the compound (PDFD8) showed the most promising results, that is, least Egap (2.36 eV) and highest λmax (756 nm). From the photovoltaic insights, significant results of the open-circuit voltage (Voc) were obtained for these compounds. Therefore, these compounds exhibited outperforming attributes due to which they can serve as suitable electron transport materials (ETMs) for solar cell applications.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145887816","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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Myths and Truths About Electrophilic Aromatic Substitution: The Particular Case of Fluorobenzene 亲电芳香取代的神话与真相：以氟苯为例

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-12-18 DOI: 10.1002/poc.70063

Francisco A. Martins, Matheus P. Freitas

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Paving the Way Toward New Push-Pull Superbases in the Gas Phase by an Effective DFT Approach: The Case of a New Structurally Complex Molecule, 5-Aminopyrrole-2-Amidine 用有效的DFT方法为气相中新的推拉式超碱铺平道路——以结构复杂的新分子5-氨基吡咯-2-氨基为例

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-12-10 DOI: 10.1002/poc.70047

Ewa Daniela Raczyńska, Jean-Francois Gal, Pierre-Charles Maria

{"title":"Paving the Way Toward New Push-Pull Superbases in the Gas Phase by an Effective DFT Approach: The Case of a New Structurally Complex Molecule, 5-Aminopyrrole-2-Amidine","authors":"Ewa Daniela Raczyńska, Jean-Francois Gal, Pierre-Charles Maria","doi":"10.1002/poc.70047","DOIUrl":"https://doi.org/10.1002/poc.70047","url":null,"abstract":"Amidines, such as formamidines, acetamidines, and benzamidines {XYN–C(R)=NZ, R: H, Me, Ph}, belong to the family of Brønsted push-pull organic N-bases. Depending on substituents at N atoms (X, Y, and Z), they display gas-phase proton basicities considerably stronger than that of NH3, but weaker than that of the bicyclic guanidine MTBD (7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene). In our recent quantum-chemical studies on simple tautomeric superbases, we noticed that some of their tautomeric forms can be employed as scaffolds for putative superbases. We focus the present study on APA, a new amidine, containing the Y-conjugated aminopyrrole ring at the amidine functional C atom, a possible parent compound of a new series of 5-amino-1H-pyrrole-2-carboximidamides (or 5-aminopyrrole-2-amidines). For the analysis of its complex structure, tautomeric possibilities, and proton-transfer equilibria, the DFT (density functional theory) method turned out to be effective. This method allows calculating with sufficient precision the gas-phase energetic parameters for isomeric N-containing π-electron systems, comparable to those calculated at the ab initio Gn levels, and which can be used to pave the way for an extension of the experimental gas-phase basicity scale. Using DFT, the thermodynamics of all possible isomeric conversions was examined, and the energetically favored ones indicated. For selected isomers, the protonation sites, acid/base equilibria, micro- and macroscopic gas-phase basicities were investigated. The calculated macroscopic gas-phase basicity, which refers to the intrinsic strength of the investigated base, is very close to that of the superbasic bicyclic amidine DBN (1,5-diazabicyclo[4.3.0]non-5-ene), experimentally investigated earlier by FTICR (Fourier transform ion cyclotron resonance) mass spectrometry.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70047","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145739408","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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Electrochemical Approaches For Barbier-Like Carbon–Carbon Bond Formations: Cases of Allylations and Propargylations Barbier-Like碳-碳键形成的电化学方法：烯化和丙基化的案例

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-12-02 DOI: 10.1002/poc.70048

Bibhas Mondal, Debjit Das, Ujjal Kanti Roy

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Thallium(III) Complexes of a Chlorophyll-a Derivative Asymmetrically Coordinated With Single Axial Anionic Ligands 与单轴阴离子配体不对称配位的叶绿素-a衍生物铊配合物

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-11-26 DOI: 10.1002/poc.70046

Shin Ogasawara, Haruki Ishikawa, Yusuke Kinoshita, Hitoshi Tamiaki

{"title":"Thallium(III) Complexes of a Chlorophyll-a Derivative Asymmetrically Coordinated With Single Axial Anionic Ligands","authors":"Shin Ogasawara, Haruki Ishikawa, Yusuke Kinoshita, Hitoshi Tamiaki","doi":"10.1002/poc.70046","DOIUrl":"https://doi.org/10.1002/poc.70046","url":null,"abstract":"<div>\u0000 \u0000 Methyl pyropheophorbide-a, one of the chlorophyll-a derivatives, was reacted with thallium(III) trifluoroacetate in tetrahydrofuran at room temperature to yield the corresponding Tl(III) complex with trifluoroacetate as an axial ligand. The anionic trifluoroacetate ligand was readily exchanged for chloride by treatment with brine. The resulting five-coordinated complex with Cl− was fully characterized by 1H NMR and visible absorption spectroscopies as well as mass spectrometry. Notably, the meso-protons of trifluoroacetate and chloride complexes coupled strongly with the stable Tl isotopes (the nuclear spin quantum numbers = 1/2) through four bonds to give doublet peaks (the coupling constants = 40–58 Hz). Their 1H NMR spectra in deuterated chloroform indicated that the Tl(III) chlorins with an axial ligand were epimeric mixtures around the chiral central metal. Molecular model calculation proposed their absolute configurations at the asymmetric Tl(III) atom. The α-ligated complexes were estimated to be preferable over the β-ligated epimers. The epimeric ratios varying from 1.6 to 2.0 were dependent on the axial ligands. The obtained Tl(III) complex in dichloromethane efficiently absorbed violet and red lights but hardly emitted red-to-far-red light due to the heavy atom effect.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145619175","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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Halogen Bonding and Electron Transfer Between Diiodine and Aromatic (Di)amines 二碘和芳胺之间的卤素键和电子转移

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-11-24 DOI: 10.1002/poc.70044

Isaac Sarfo, Emmanuel Adeniyi, Jun You, Matthias Zeller, Sergiy V. Rosokha

{"title":"Halogen Bonding and Electron Transfer Between Diiodine and Aromatic (Di)amines","authors":"Isaac Sarfo, Emmanuel Adeniyi, Jun You, Matthias Zeller, Sergiy V. Rosokha","doi":"10.1002/poc.70044","DOIUrl":"https://doi.org/10.1002/poc.70044","url":null,"abstract":"<div>\u0000 \u0000 UV–Vis and X-ray crystallographic measurements, together with the analysis of the potential energy surfaces, demonstrated a critical role of halogen-bonded (HaB) complexes in the electron transfer (ET) reactions between diiodine and aromatic amines. Specifically, UV–Vis spectral studies showed that the addition of I2 to solutions of tetramethyl-p-phenylenediamine (TMPD) or various N,N-dimethylanilines resulted in the immediate formation of HaB complexes. In systems with TMPD, this was followed by rapid ET—even at −85°C—resulting in the formation of persistent TMPD+• cation radicals (which were crystallized as salts with iodide counterions). The formation of HaB complexes upon mixing I2 with dimethylanilines was followed by the generation of I3−, indicating the occurrence of redox processes. Subsequent chemical reactions led to the crystallization of triiodide salts of protonated m-methoxy-N,N-dimethylaniline, p-iodo-N,N-dimethylaniline (from the reaction with N,N-dimethylamine), or, surprisingly, 4,4′-bis(dimethylamino)benzhydrylium cations (from the reaction of I2 with p-bromo-N,N-dimethylaniline). Most notably, the rates of the redox processes in all these systems were many orders of magnitude faster than those predicted by the classical Marcus (outer-sphere) ET theory. These high rates were accounted for by considering the donor–acceptor electronic coupling in the HaB precursor complexes, which drastically lowers the activation barriers for inner-sphere ET. These results confirm that HaB complexes are vital intermediates in the ET reactions of halogenated electrophiles, and their role should be taken into account when analyzing potential ET steps in chemical transformations involving such molecules.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145619124","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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Insights Into Intramolecular Charge Transfer in a Benzoxazole-Substituted TAPP Derivative: Solvent Effects and DFT Analysis 苯并恶唑取代TAPP衍生物的分子内电荷转移：溶剂效应和DFT分析

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-11-24 DOI: 10.1002/poc.70045

Sultan Funda Ekti, Güler Yağız Erdemir

{"title":"Insights Into Intramolecular Charge Transfer in a Benzoxazole-Substituted TAPP Derivative: Solvent Effects and DFT Analysis","authors":"Sultan Funda Ekti, Güler Yağız Erdemir","doi":"10.1002/poc.70045","DOIUrl":"https://doi.org/10.1002/poc.70045","url":null,"abstract":"<div>\u0000 \u0000 In this study, synthesis, characterization, photophysical properties, and DFT calculations of a new tetraaryl-1,4-dihydropyrrolo[3,2-b]pyrrole (TAPP) derivative molecule of A-π-D-π-A type containing benzoxazole as an acceptor group at 1,4-positions have been carried out. The target A-D-A type molecule was synthesized using 4-(benzo[d]oxazol-2-yl)aniline by the method known in the literature, and it was aimed to obtain the classical TAPP structure in an iron-catalyzed environment. No product was obtained with the first method; therefore, the reaction conditions were optimized. The reaction time and temperature were varied in a controlled manner; the optimum conditions were determined with a reaction time of 7 h at 60°C. The photophysical behavior of the synthesized benzoxazole-substituted TAPP derivative was investigated by UV–vis and fluorescence spectroscopy depending on different solvent polarities. In the absorption spectra, the maximum absorption band observed around 330 nm in low polarity solvents shifted to 340 nm in polar solvents. Similarly, fluorescence emissions systematically red-shifted from hexane to DCM (470–550 nm), and quantum yields decreased significantly (0.41 in hexane and 0.03 in DCM). This bathochromic shift and decrease in intensity indicate that the molecule has high polarity in the excited state whereas the intrinsic charge transfer (ICT) and twisted ICT (TICT) states stabilize with increasing solvent polarity. At the same time, nonluminescent transition channels such as loss of planarity, oxygen-induced quenching, and internal conversion in the solvent-excited state also decrease the fluorescence intensity. The findings reveal that this TAPP derivative forms a strong donor-acceptor system and exhibits high sensitivity to solvent environment.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145581322","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