Journal of Physical Organic Chemistry最新文献

{"title":"Study on the synthesis mechanism of pyrazoles via [3+2] cycloaddition reaction of diazocarbonyl compounds with enones without leaving groups","authors":"Guipeng Feng,&nbsp;Jie Meng,&nbsp;Shaohong Xu,&nbsp;Chenqian Wang,&nbsp;Xubin Yao,&nbsp;Xinzi Nie","doi":"10.1002/poc.4591","DOIUrl":"10.1002/poc.4591","url":null,"abstract":"<p>On the basis of the density functional theory (DFT), the process of cycloaddition reaction of diazocarbonyl compounds with enones without leaving groups to obtain pyrazoles was proposed. First, the diazocarbonyl compounds reacted with enones to offer the intermediates by cycloaddition reaction, which was captured of hydrogen of the intermediate by the base to offer the nonaromatic pyrazole intermediate, which then give the final product by oxidation and isomerization in the air. This protocol corrected the reaction mechanism that was proposed in the experimental section. The negative correlation between the yields of products with the charges of ADCH at the C1 position of enones was also founded, which was consistent with the experimental results. The protocol could provide theoretical guidance for designing more efficient cycloaddition reaction.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2023-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138542229","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}

{"title":"A comparative study on the cucurbit[7]uril-based indicator displacement assay for methyl Viologen. A theoretical and experimental perspective","authors":"Paulina Pavez,&nbsp;Angélica Fierro,&nbsp;Mabel Rojas,&nbsp;Luis García-Rio,&nbsp;Luis Dinamarca-Villarroel,&nbsp;Denis Fuentealba,&nbsp;Kevin Droguett,&nbsp;José G. Santos,&nbsp;Margarita E. Aliaga","doi":"10.1002/poc.4581","DOIUrl":"10.1002/poc.4581","url":null,"abstract":"<p>One colorimetric and one fluorescent-indicator displacement assay (IDA) were studied to assess their interaction with methyl viologen (MV), an herbicide commercially known as paraquat. The host–guest complexes formed by cucurbit[7]uril (CB[7]) and the 4-nitroaniline (NA) or Berberine (Be) dyes function as colorimetric- and fluorescent-IDA for MV, respectively. The CB[7]@NA and CB[7]@Be complexes were characterized by UV–vis, fluorescence spectroscopy, and dynamic simulations. Isothermal titration calorimetry (ITC) experiments and dynamic simulations were employed to obtain thermodynamic data for the formation of the 1:1 inclusion complexes. Finally, NA is proposed as a reference colorimetric dye for determining CB[7]-binding affinities using competitive host–guest titrations, and the fluorescent-IDA as the best assay proposed, as it exhibits a high binding constant, a good detection limit of 2.7 × 10⁻⁶ mol L^-1, good linearity in the range from 4 × 10⁻⁶ mol L^-1 to 3.5 × 10⁻⁵ mol L^-1, in aqueous solution.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 7","pages":""},"PeriodicalIF":1.9,"publicationDate":"2023-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138527712","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}

{"title":"Density functional theory for exploration of chemical reactivity: Successes and limitations","authors":"Tanmoy Chakraborty,&nbsp;Pratim K. Chattaraj","doi":"10.1002/poc.4589","DOIUrl":"https://doi.org/10.1002/poc.4589","url":null,"abstract":"&lt;p&gt;Computational modeling of molecules and their reactions are now essential components of the scientific research in chemistry.&lt;/p&gt;&lt;p&gt;Density functional theory (DFT) is among the most prominent and effective quantum mechanical theories of molecules and materials. Presently, it is commonly employed in calculations of band configuration of solids and binding energies of substances. It appears that these are the initial applications that are pertinent to sciences like biology and minerals, which are typically regarded as being further removed from quantum mechanics. DFT has been used to examine superconducting properties, particles at the forefront of intense laser impulses, relativistic influences in heavy molecules and nuclei of atoms, conventional fluids, and the magnetic characteristics of composites. DFT's adaptability is due to the flexibility of its basic principles and the range of possibilities with which they can be used. Despite this adaptability and applicability, the logical foundation of DFT is relatively inflexible.&lt;span&gt;&lt;sup&gt;1&lt;/sup&gt;&lt;/span&gt;&lt;/p&gt;&lt;p&gt;Through years of debating the many-body challenge, numerous effective strategies to address Schrödinger's equation have been created. For instance, the schematic perturbation concept, which relies on Feynman models and Green's functions, is utilized in physics, whereas configuration interaction (CI) approaches, which depend on methodical development in Slater determinants, are commonly employed in chemistry. There are also a variety of more specialized techniques. These approaches have a drawback in that they exert an enormous demand on computational resources, making it difficult to use them effectively on enormous and intricate systems. Here, DFT offers a strong substitute that may be less precise but is far more adaptable.&lt;span&gt;&lt;sup&gt;2&lt;/sup&gt;&lt;/span&gt; The 1998 award for the Nobel Prize in Chemistry, given to Walter Kohn,&lt;span&gt;&lt;sup&gt;3&lt;/sup&gt;&lt;/span&gt; the creator of DFT, and John Pople,&lt;span&gt;&lt;sup&gt;4&lt;/sup&gt;&lt;/span&gt; who played a key role in integrating DFT with computational chemistry, is indicative of the level to which DFT has made an impact on the scientific community of computational chemistry and physics. It has been utilized to determine a large portion of the information that is understood concerning the electronic, magnetic, and structural characteristics of substances.&lt;span&gt;&lt;sup&gt;5, 6&lt;/sup&gt;&lt;/span&gt;&lt;/p&gt;&lt;p&gt;A computational achievement was subsequently made possible by involving orbital parameters in the framework, as was done in the Kohn–Sham paradigm&lt;span&gt;&lt;sup&gt;7, 8&lt;/sup&gt;&lt;/span&gt; and in the beginning of 1995, DFT through the Kohn–Sham approaches in Pople's GAUSSIAN software tool&lt;span&gt;&lt;sup&gt;9&lt;/sup&gt;&lt;/span&gt; become the favored wave function computing package at those times as well as currently. In the end of 1970s and beginning of 1980s, eminent scientist R. G. Parr has established another form of DFT known as “conceptual DFT.”&lt;span&gt;&lt;sup&gt;10&lt;/sup&gt;&lt;/span&gt; In accordance with the notion that the density of el","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"36 12","pages":""},"PeriodicalIF":1.8,"publicationDate":"2023-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4589","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138468642","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}

{"title":"Rational design of promising candidates for photoactive layer in polymer solar cells: Insights from computation","authors":"Renato P. Orenha,&nbsp;Salvador B. Ramos,&nbsp;Maria L. L. Natal,&nbsp;Márcio H. A. Gomes,&nbsp;Alvaro Muñoz-Castro,&nbsp;Letícia M. P. Madureira,&nbsp;Giovanni F. Caramori,&nbsp;Maurício J. Piotrowski,&nbsp;Renato L. T. Parreira","doi":"10.1002/poc.4586","DOIUrl":"10.1002/poc.4586","url":null,"abstract":"<p>The design of organic solar cells, OSCs, requests a more efficient configuration of photoactive layers composed of p-type (quinoxaline, Qx) and n-type (naphthalene diimide, NDI) semiconductors that enable light harvesting along with a high-power conversion efficiency. Here, Qx-(phenyl or Ph) and NDI structures have been modulated using both electron withdrawing (EWG) and electron donating (EDG) groups such as −F, −NHCOCH₃, −OCH₃, −OH, −CHO, −COOCH₃, −COOH, −CN, −SO₃H, and −NO₂, aiming to design an effective photoactive p-n layer. The HOMO-LUMO gap of Qx-Ph can be tuned to the visible light spectrum by the addition of EWG in the Qx ring (decreasing the LUMO energy) and by EDG in the Ph ring (increasing the HOMO energy). The analyzed complexes show key electronic properties in organic solar cells with large power conversion efficiency. Descriptive data analysis suggests that the magnitude of the non-covalent interactions in donor\u0000<span></span><math>\u0000 <mi>…</mi></math> acceptor (D\u0000<span></span><math>\u0000 <mi>…</mi></math> A) complexes is expected to play a role in the efficiency of OSCs. The results will contribute to a more effective design of the photoactive layer in OSCs.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 7","pages":""},"PeriodicalIF":1.9,"publicationDate":"2023-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138527682","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}

{"title":"Insight into acrolein activation by P/B intramolecular frustrated Lewis pairs","authors":"Swapan Sinha,&nbsp;Subhra Das,&nbsp;Santanab Giri","doi":"10.1002/poc.4588","DOIUrl":"10.1002/poc.4588","url":null,"abstract":"<p>The study investigates the reactivity of a cyclic five-membered intramolecular P/B frustrated Lewis pair towards acrolein through a cycloaddition reaction. Intrinsic reaction coordinate (IRC) calculations suggest the single-step mechanism. It has been observed that the cycloaddition reaction occurs through a concerted mechanism in both the presence and absence of the catalyst. Analysis of reaction force and reaction electronic flux provides valuable information about the total work required and electronic activity along the IRC. Additionally, natural bonding orbital (NBO) analyses enrich the understanding of the mechanism in terms of the electron transfer process during the chemical reaction.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2023-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138527674","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}

{"title":"Theoretical study on oxidation mechanism of fluorescent probe, coumarin-7-pinacolboronate by various reactive oxygen species","authors":"Yujie Guo,&nbsp;Yan Leng,&nbsp;Hongbo Liu,&nbsp;Chun-Gang Min,&nbsp;Ai-Min Ren,&nbsp;Qinhong Yin","doi":"10.1002/poc.4585","DOIUrl":"10.1002/poc.4585","url":null,"abstract":"<p>Hydrogen peroxide (H₂O₂) as relatively stable reactive oxygen species gains considerable attention because it can regulate physiological and pathological processes. In order to better detect H₂O₂, fluorescent probes were widely applied. Over the past 20 years, a great deal of boronate-based fluorescent molecular probes appeared due to relatively simple oxidation reaction. However, the reaction mechanisms that boronate derivatives were converted into fluorescent product by H₂O₂ are poorly studied. In this paper, taking coumarin-7-pinacolboronate (CBU) as an example, the oxidation mechanism of boronate-based probes by various reactive oxygen species was studied by theoretical calculations. The results found that (1) the chemical reaction mechanisms are nearly identical for the reactions of CBU with hydrogen peroxide, hypochlorous acid, peroxynitrite, and tyrosine hydroperoxide, respectively. (2) There is not radical intermediate during the reaction. (3) The different reactive oxygen species has a strong influence on rate limiting step and reaction rate.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2023-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138527672","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}

{"title":"A new method for determining the intrinsic resistance energy of H-atom transfer reaction and structure–activity relationship of H-donating ability","authors":"Yan-Hua Fu,&nbsp;Fang Wang,&nbsp;Zhongyuan Zhou,&nbsp;Liguo Yang,&nbsp;Guang-Bin Shen,&nbsp;Xiao-Qing Zhu","doi":"10.1002/poc.4584","DOIUrl":"10.1002/poc.4584","url":null,"abstract":"<p>The intrinsic resistance energy Δ<i>G</i>^≠_XH/X of H-donor XH in hydrogen atom transfer (HAT) reaction is usually used to evaluate the kinetic H-donating ability. In this article, a new method for determining Δ<i>G</i>^≠_XH/X of H-donor in HAT reaction was proposed by the definition of thermo-kinetic parameter Δ<i>G</i>^≠o (XH) = 1/2[Δ<i>G</i>^≠_XH/X + Δ<i>G</i>^o (XH)]. Δ<i>G</i>^≠o (XH) is the characteristic physical parameter of XH to describe the H-donating ability in a chemical reaction during a certain reaction time, Δ<i>G</i>^o (XH) is the bond dissociation free energy. The kinetic studies of HATs between 20 alcohols, ethers, alkanes and amines (XH) with cumyloxyl radical [PhC (CH₃)₂O^•, CumO^•] were researched, and Δ<i>G</i>^o (XH), Δ<i>G</i>^≠_XH/X, and Δ<i>G</i>^≠o (XH) were used to investigate the H-donating abilities of the studied substrates in thermodynamics, kinetics, and HAT reaction. The effect of structures of XH on these three parameters, the structure–activity relationship, such as the influence of electronic, steric, polar and stereoelectronic effects of substituents, heteroatoms insertion in cycloalkanes, and <i>cis–trans</i> configurational isomerism on the H-donating abilities were discussed in detail. This study not only provides a new method for determining Δ<i>G</i>^≠_XH/X but also systematically studies the factors affecting the H-donating ability, laying a foundation for the selection, design, and synthesis of more efficient antioxidants.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2023-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138527673","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}

{"title":"Electronegativity effect on the ESIPT process of 4′-N,N-dimethylamino-3-hydroxyflavone (DMA3HF) and its derivatives","authors":"Zhiqiang Liu,&nbsp;Ligang Han,&nbsp;Xiali Wang,&nbsp;Yi Wang,&nbsp;Yingmin Hou","doi":"10.1002/poc.4583","DOIUrl":"10.1002/poc.4583","url":null,"abstract":"<p>4′-N,N-dimethylamino-3-hydroxyflavone (DMA3HF) has antioxidant activity and excited state proton transfer (ESIPT) property. In this study, the influence of electronegativity on the ESIPT process has been studied by DFT/TD-DFT methods. Except DMA3HF, the substitutes of S and Se have been designed. The analysis of main bond parameters, infrared vibration spectra, and reduced density gradient function shows that the reduction of atomic electronegativity could promote the ESIPT process. Dihedral angle, frontier molecular orbitals and hole-electron analysis indicate that the twisted intramolecular charge transfer (TICT) process has been enhanced by the decreasing electronegativity. The results show that the decrease of atomic electronegativity is beneficial to TICT and ESIPT processess.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2023-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138527683","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}

{"title":"Effect of N, S atoms on the mechanisms of H-transfer for five-membered nitrogen-containing heterocycles","authors":"Yan-Hua Fu,&nbsp;Kai Wang,&nbsp;Liguo Yang,&nbsp;Guang-Bin Shen,&nbsp;Xiao-Qing Zhu","doi":"10.1002/poc.4582","DOIUrl":"10.1002/poc.4582","url":null,"abstract":"<p>As the mechanisms of the hydride transfer reaction between 7,8-dihydro-9-methylcaffeine (CAFH) with <i>N</i>-methylacridinium (AcrH⁺ClO₄^-) and hydrogen atom transfer (HAT) reaction between 2,3-dihydrobenzo-imidazoles (BIH) with 2,2-diphenyl-1-picrylhydrazyl radical (DPPH^•) were researched to both be induced by electron transfer, the reaction mechanisms of 2,3-dihydrobenzo-thiazoles (BTH) with these two substrates were studied. The thermodynamic analysis platforms were used to judge the mechanisms, and the mechanisms of these two reactions were not the same with CAFH and BIH as the <i>E</i>_ox (BTH) value was more positive than CAFH and BIH. A new method for inferring the reaction mechanism was proposed using the kinetic equation Δ<i>G</i>^≠_XH/Y = Δ<i>G</i>^≠o (XH) + Δ<i>G</i>^≠o(Y) and thermo-kinetic parameter Δ<i>G</i>^≠o. The HAT reaction mechanisms between BTH with DPPH^• and ^tBu₃PhO^• were researched by Δ<i>G</i>^≠o_HD. As the Δ<i>G</i>^≠o (BTH) values in these two reactions were similar; hence, the rate determining steps of them were both HATs as the Δ<i>G</i>^≠o_HD(Y) values of DPPH^• and ^tBu₃PhO^• used for determining Δ<i>G</i>^≠o (BTH) were both in HAT reactions. The HAT reaction mechanisms between BIH with ^tBu₃PhO^• were also researched by thermodynamic analysis platform and kinetic isotope effect (KIE = 3.99), which confirmed that the rate determining step of BIH/^tBu₃PhO^• was indeed HAT. The H-donating ability of BIH and BTH was compared by Δ<i>G</i>^≠o_HD. From BIH to BTH, the substitution of <i>N</i> by <i>S</i> not only greatly reduces the thermodynamic electron donating and H-donating capacity of the compound but also increases the H-donating ability in kinetics and HAT reaction.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2023-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138527696","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}

{"title":"Cooperativity and topological hydrogen bonding in aromatic diol complexes","authors":"Robert E. Rosenberg,&nbsp;John S. Lomas","doi":"10.1002/poc.4578","DOIUrl":"10.1002/poc.4578","url":null,"abstract":"<p>Complexes of three aromatic diols, catechol, naphthalene-1,8-diol, and fluorene-4,5-diol, with a series of hydrogen bond acceptors (HBAs) that have oxygen, nitrogen, and sulfur acceptor atoms, have been studied by density functional theory (DFT) at the B3LYP/6-311+G(d,p) level. Binding energies, geometries, infrared spectroscopic (IR) frequencies, nuclear magnetic resonance (NMR) shifts, and measures of the electron density distribution from the Quantum Theory of Atoms in Molecules (QTAIM) are evaluated and compared with data for the corresponding monohydroxy compounds (monols), phenol, naphth-1-ol, and fluorene-4-ol, in order to assess the importance of cooperativity between intramolecular and intermolecular hydrogen bonding. All measures for all complexes show positive cooperativity whereby both the intermolecular and intramolecular hydrogen bonds are strengthened upon complexation. Cooperativity is weak for catechol and strong for the other two diols and, for all diols, increases with the hydrogen bond basicity of the acceptor. Correlations of IR and NMR metrics against binding energies for a single HBA and all six monols and diols are excellent, but attempts to correlate the same metrics for all HBAs and a single donor are frustrated by differences in intermolecular hydrogen bonding, depending notably on the identity of the acceptor atom in the HBA. Atom–atom interaction energies, calculated by the Interacting Quantum Atoms approach, are used to discuss the covalency of both types of hydrogen bond.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2023-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136262613","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}