Journal of Physical Organic Chemistry最新文献

{"title":"The Great Escape? Investigations of Tunneling Contributions to the Valence Tautomerizations of Benzene Chalcogenides and Heteroepins","authors":"Liam Tsou,&nbsp;Muhammad Dilawar Danish,&nbsp;Daniel P. Miller,&nbsp;Tim Schleif","doi":"10.1002/poc.70097","DOIUrl":"https://doi.org/10.1002/poc.70097","url":null,"abstract":"<div>\u0000 \u0000 <p>Valence tautomerizations are prototypical pericyclic rearrangements with broad relevance in (bio)organic chemistry that can exhibit significant contributions from quantum mechanical tunneling (QMT), as demonstrated previously e.g., for the oxepin—benzene oxide equilibrium. Such contributions were evaluated computationally for the valence tautomerizations of heteroepins C₆H₆X (X = S, Se, and Te) and thiepin oxides (X = SO or SO₂). Ring contraction of the heteroepins becomes increasingly exothermic from X = O to X = Te; however, as an exception to the Bell–Evans–Polanyi principle, the associated activation barriers also increase. Analysis of the intrinsic reaction coordinates reveals that the critical C1–C6 distance in the heteroepins strongly widens within this series, resulting in increasingly wider and higher barriers despite the growing thermodynamic driving force. Consequently, estimated tunneling probabilities decrease dramatically across the series, ruling out tunneling as a significant contributor to the experimentally observed instability of thiepin, selenepin, and tellurepin. In contrast, the valence tautomerizations of thiepin-<i>S</i>-oxide and thiepin-<i>S,S</i>-dioxide follow conventional Bell–Evans–Polanyi behavior. The equatorial conformer of thiepin-<i>S</i>-oxide is expected to not exhibit any appreciable tunneling reactivity, while its axial conformer is projected to undergo rapid ring contraction by heavy-atom tunneling. The bicyclic tautomer of C₆H₆SO₂ is predicted to ring-expand to the less strained thiepin-<i>S,S</i>-dioxide with a half-life suitable for matrix isolation spectroscopy experiments. Overall, this study of the potential role of QMT in the valence tautomerizations of heteroepins and thiepin oxides provides broader insights into how characteristic molecular features influence the intrinsic barrier width of a reaction.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148848946","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":"Assembly and Properties of Donor/Acceptor–Functionalized 2,6-Bisethynylpyridines; Investigations of Through-Bond and Through-Space Charge Transfer Behavior","authors":"Jarod T. Sjoquist,&nbsp;Noah A. Grinde,&nbsp;Maggie A. Schultz,&nbsp;Olivia J. Schwarz,&nbsp;John T. Nabors,&nbsp;Nathaniel P. Litts,&nbsp;Joseph D. Scanlon,&nbsp;Eric Bosch,&nbsp;Nathan P. Bowling","doi":"10.1002/poc.70100","DOIUrl":"https://doi.org/10.1002/poc.70100","url":null,"abstract":"<p>Introduction of Ag(I) cations to 2,6-bisethynylpyridine units decorated with electron-donating (<i>N</i>,<i>N</i>-dimethylaniline) and electron-accepting (1,3-dinitrobenzene) groups yields electronic changes consistent with the formation of distinct metal-organic complexes. Although the formation of these complexes is dynamic—allowing for the possibility of contributors with several different ligand:metal stoichiometries—¹H NMR titration data point to significant contributions from a 2:1 ligand:metal complex. Mutual shielding of the donor and acceptor arms in the 2:1 complex leads to sharp decreases in ¹H NMR chemical shifts of hydrogens on these rings. Though the changes in electronic properties and evidence of mutual shielding infer formation of a complex with a close spatial relationship of donor and acceptor units, the electronic effects that would be expected for through-space charge transfer are not clearly distinguishable from through-bond electronic effects. Protonation of the central pyridines illuminates how through-bond interactions of the <i>N</i>,<i>N</i>-dimethylaniline arms with a positively charged central pyridine tend to dominate the electronic profile of each ligand. X-ray crystallographic studies of an Ag(I) complex of a donor-acceptor system illustrate notable contacts between <i>N</i>,<i>N</i>-dimethylaniline and 1,3-dinitrobenzene units.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70100","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148848947","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":"Density Functional Theory Insights Into Ruthenium-Catalyzed Alkene–Alkyne Cross-Coupling: Mechanism, Regioselectivity, and Catalyst Effects","authors":"Hongtai Chen,&nbsp;Guixian Liu,&nbsp;Wei Zhou,&nbsp;Xiangtai Meng,&nbsp;Lei Zhang","doi":"10.1002/poc.70102","DOIUrl":"https://doi.org/10.1002/poc.70102","url":null,"abstract":"<div>\u0000 \u0000 <p>Direct cyclometalation of two unsaturated bonds at a transition metal center constitutes a highly efficient strategy for carbon–carbon cross-coupling. In this work, density functional theory calculations were performed to delineate the detailed reaction mechanism of ruthenium-catalyzed direct alkene–alkyne coupling for diene synthesis. Computational results reveal that the reaction proceeds via three elementary steps: concerted cyclometalation, β-hydride elimination, and reductive elimination, with the initial cyclometalation step serving as both the rate-determining and regioselectivity-controlling step. Under standard reaction conditions, the branched diene is the major product, whereas the more stable linear diene is a minor isomer; however, this regioselectivity is significantly modulated by ligand architecture and substrate substituent effects. Calculations demonstrate that replacing the pentamethylcyclopentadienyl ligand with the unsubstituted cyclopentadienyl ligand, or introducing alkyl substituents on the alkene substrate, can invert the selectivity, switching the major product from branched to linear diene. Furthermore, investigations into catalyst structure–reactivity relationships reveal that ligand structure plays a dominant role, because the presence of a cyclooctatetraene ligand results in a substantial reduction in catalytic activity, whereas the formal charge of the Ru center exerts only a secondary influence. The present computational findings not only rationalize existing experimental observations but also provide deeper mechanistic insights into the origins of regioselectivity and reactivity in this class of transformations.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148849170","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":"PyQuiverHS: A Web Tool for Computing Isotope Effects","authors":"Gianmarc Grazioli,&nbsp;Andrew Ly,&nbsp;Dianoosh Sabetnejad,&nbsp;Anvitha Mattapalli,&nbsp;Calvin T. Nguyen,&nbsp;Daniel J. O'Leary","doi":"10.1002/poc.70099","DOIUrl":"https://doi.org/10.1002/poc.70099","url":null,"abstract":"<p>Predicting isotope effects using electronic structure calculations is widely done, but current software options can present a barrier for some chemists, depending upon their needs and software/programming proficiency. Building upon existing code bases, we have developed PyQuiverHS as a free web tool (www.isotope-effects.com) to provide ready access to kinetic and equilibrium isotope effect (EIE) calculations employing the Bigeleisen–Mayer (B-M) and enthalpy–entropy (<i>H-S</i>) partition functions. A graphical user interface assists in setting up a configuration file, which contains scaling factor and isotope substitution information. After uploading the configuration file and Gaussian frequency jobs for the unlabeled system, users execute a kinetic isotope effect (KIE) or EIE calculation at a particular temperature or range of temperatures with a defined increment. Wigner and Bell tunneling corrections are provided for KIE calculations. Overall KIEs or EIEs and their contributing B-M and <i>H-S</i> terms are compiled in auto-downloaded comma-separated values (*.csv) and plain text files. Automating the process with PyQuiverHS is a significant gain in efficiency, as previous methods for these types of calculations have relied on spreadsheets, which require time-intensive data manipulation. We demonstrate the utility of PyQuiverHS by calculating temperature-dependent conformational KIEs in 9,10-dihydro-4,5-dimethylphenanthrene (<b>1</b>), a doubly bridged biphenyl derivative (<b>2</b>), [2.2]-metaparacyclophane (<b>3</b>), a secondary KIE for the S_N2 reaction of chloride with methyl bromide (<b>4</b>), and an EIE for the interconversion of chair conformations of 1,1,3,3-tetramethylcyclohexane (<b>6</b>).</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70099","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784521","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":"A Stable Hemicarceplex With an Encapsulated Cationic Guest","authors":"Casey Lee-Foss,&nbsp;Alex Lovstedt,&nbsp;Lewis Nguyen,&nbsp;Steven R. Kass","doi":"10.1002/poc.70098","DOIUrl":"https://doi.org/10.1002/poc.70098","url":null,"abstract":"<p>A hemicarcerand first reported by Quan and Cram in 1991 was prepared and characterized by X-ray crystallography. It incorporates CoCp₂⁺ PF₆⁻ with an equilibrium constant of ~220 M⁻¹ at 120°C and apparently is indefinitely stable at room temperature. This potential weakly coordinating cation's structure was also determined by X-ray analysis, and the cation is located on the inside and the counteranion on the outside of the cage through one of its four potential openings. Computations model these results and suggest that the imine linker needs to be modified to reduce the electrostatic attraction of the oppositely charged ions by physically separating them further.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70098","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784142","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":"Solvent Effects on the Reactivity of a Phenolate Betaine: Kinetics and Theoretical Calculations of Transition-State Solvation","authors":"Marcos Caroli Rezende,&nbsp;Carolina Mascayano,&nbsp;Sofia Cornejo,&nbsp;Miroslav Cabadaj","doi":"10.1002/poc.70095","DOIUrl":"https://doi.org/10.1002/poc.70095","url":null,"abstract":"<div>\u0000 \u0000 <p>The kinetics of the reaction of solvatochromic 4-(2,4,6-triphenylpyridinio)phenolate with methyl iodide was followed at 25.0°C in various solvents (chloroform, dichloromethane, acetone, acetonitrile, dimethyl sulfoxide, 2-octanol) and in six binary mixtures of variable composition. Rates in poorly acidic solvents correlated with the medium polarizability and dipolarity. Solvent effects in binary mixtures were rationalized by a non-ideality approach based on the preferential solvation of the transition state in these media. Correlations of reactivities with solvent properties found support with theoretical calculations of the transition state of the reaction in different solvents, simulated by a continuum model and by the explicit solvation of the TS by molecules of a hydroxylic solvent.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 9","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148616661","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 Physical Organic Odyssey: From the Ultrafast Dynamics of Carbenes and Nitrenes to Contemporary Chemical Biology and Drug Discovery","authors":"Bin Yang,&nbsp;Jin Wang","doi":"10.1002/poc.70094","DOIUrl":"https://doi.org/10.1002/poc.70094","url":null,"abstract":"<p>The field of photoaffinity labeling (PAL) stands as a testament to the enduring power of physical organic chemistry in driving biological discovery. For nearly five decades, Professor Matthew S. Platz has occupied a singular position at the intersection of reactive intermediate chemistry, ultrafast spectroscopy, and chemical biology—transforming our mechanistic understanding of carbenes, nitrenes, oxenium ions, and their excited-state precursors into actionable design principles for molecular probes. This review, dedicated to Professor Platz on the occasion of his 75th birthday, traces the arc of his scientific legacy: from foundational matrix-isolation and laser flash photolysis studies of phenylcarbene and phenylnitrene, through the transformative discovery of the fluorine effect in aryl azide photochemistry, to the rigorous mechanistic revision of widely used nucleotide-based PAL probes. A central section surveys the remarkable breadth of Platz's ultrafast spectroscopic program—encompassing diarylcarbenes, acyl and sulfonyl azides, Wolff rearrangements, oxenium ions, and heteroatom-containing reactive intermediates—establishing the quantitative kinetic framework that underpins rational probe design. We then connect these foundational insights to the contemporary chemoproteomics landscape of 2020–2025: the diazo problem in diazirine labeling, the rational design of PALBOX probes, the emergence of acyl silane photophores, photocatalytic proximity labeling platforms, and quantitative mass spectrometry workflows. Throughout, we argue that the recurring motif of Platz's career—that rigorous kinetic and mechanistic characterization of fleeting intermediates is the prerequisite for rational reagent design—remains as productive and necessary today as when he first turned a laser onto a solution of phenyl azide.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 9","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70094","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148616107","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":"Factors Affecting Nitrogen Atom Inversion in the Solid State","authors":"Jesus Daniel Loya,&nbsp;Abigail A. Moravek,&nbsp;Atropa Choi,&nbsp;Ren A. Wiscons","doi":"10.1002/poc.70093","DOIUrl":"https://doi.org/10.1002/poc.70093","url":null,"abstract":"<div>\u0000 \u0000 <p>The advancement of molecular ferroelectric materials for digital information storage requires systems that exhibit predictable polarization switching under ambient conditions. Recently, room-temperature polarization switching was observed from a single crystal of the nitrogen-centered triangulene, azangulene, revealing nitrogen inversion as a promising mechanism by which to achieve ferroelectricity. While an exciting addition to the library of organic molecular ferroelectrics, azangulene is limited by an irreversible single-crystal-to-single-crystal phase transition that kinetically traps the system in a nonpolar and nonferroelectric molecular conformation, necessitating subtle tuning of the conformational energy landscape to preserve room-temperature polarization switching, while eliminating (destabilizing) nonpolar conformers. Two triangulene design principles emerged from computational studies of azangulene derivatives focused on bridging atom selection and aryl functionalization. This work seeks to experimentally validate these computational design principles in the solid state, while identifying additional noteworthy factors that may impact the translatability of computational design principles to experimental solid-state systems. Using two model systems, nitrogen-containing 6/6/6 linear tricycles and bridged triphenylamine derivatives, four factors affecting nitrogen inversion are experimentally explored in the solid state: (i) size mismatch between the central and bridging atoms in triangulenes; (ii) the role of aryl functionalization on the central nitrogen and bridging atom geometries; (iii) (de)coupling between molecular bowl and nitrogen atom inversion; and (iv) the relative magnitude of intra- versus intermolecular factors on solid-state bowl conformation. From this work, we offer actionable strategies to tune nitrogen inversion in azangulene-based ferroelectric materials.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 9","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148533897","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":"Molecular Insights Into ESIPT-Controlled Photophysics of Amazonian Xanthones: A DFT/TD-DFT Study for Photoactive Antioxidant Design","authors":"Murillo H. Queiroz,&nbsp;Roberto Rivelino,&nbsp;Kaline Coutinho,&nbsp;Sylvio Canuto,&nbsp;Rodrigo Gester","doi":"10.1002/poc.70092","DOIUrl":"https://doi.org/10.1002/poc.70092","url":null,"abstract":"<div>\u0000 \u0000 <p>Xanthones are a prominent class of natural products with diverse biological activities, often modulated by their photophysical properties. Here, we present a theoretical investigation of the photoemission of five Amazonian xanthones (XAN1–5) in aqueous environment using Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT), combined with QTAIM and Voronoi Deformation Density (VDD) analyses. Our results show that all derivatives form stable intramolecular O–H···O hydrogen bonds in the ground state, with interaction energies ranging from −10.3 to −11.8 kcal/mol. Excitation leads to a direct ESIPT transformation only for XAN 2, XAN 3, and XAN 4, whereas XAN 1 and XAN 5 remain stabilized in the enolic form during the first excited-state relaxation. QTAIM topological parameters reveal that while ground-state H-bond strength is relatively similar across the series, VDD identifies a threshold of local charge polarization required for the proton mobility. This indicates that while ground-state H-bonding arrangement and local charge polarization are essential, they are not sufficient to induce ESIPT. Our analysis suggest that this process is governed by the specific electronic redistribution in the lowest excited state, which must enhance the acceptor basicity to trigger proton transfer. These findings provide molecular-level theoretical insights into the photophysics of Amazonian xanthones and offer a guide for the design of new photoactive antioxidant compounds.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 8","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148467290","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":"Molecular Crosstalk Between Catecholamine Neurotransmitters and Neurologically Active Ions (\u0000 \u0000 \u0000 \u0000 Na\u0000 +\u0000 \u0000 \u0000 $$ {Na}^{+} $$\u0000 , \u0000 \u0000 \u0000 \u0000 K\u0000 +\u0000 \u0000 \u0000 $$ {K}^{+} $$\u0000 and \u0000 \u0000 \u0000 \u0000 Cl\u0000 −\u0000 \u0000 \u0000 $$ {Cl}^{-} $$\u0000 ) and Ion-Induced Chemical Reactivity: A DFT Study","authors":"Kuppusamy Chandru,&nbsp;Tuhin Pradhan","doi":"10.1002/poc.70091","DOIUrl":"https://doi.org/10.1002/poc.70091","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;p&gt;Theoretical research on the intermolecular interactions (crosstalk) between catecholamine neurotransmitters (CATs) and neurologically active ions (NAIs) such as &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;Na&lt;/mi&gt;\u0000 &lt;mo&gt;+&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {Na}^{+} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;K&lt;/mi&gt;\u0000 &lt;mo&gt;+&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {K}^{+} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;Cl&lt;/mi&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {Cl}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; has been performed using the density functional B3LYP method with 6-311++G (d, p)+SDD basis set in aqueous phase. Complexation energy analysis predicts that average interaction energy between CATs and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;Na&lt;/mi&gt;\u0000 &lt;mo&gt;+&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {Na}^{+} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; ion in aqueous phase is ~−22.9 &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;kcal&lt;/mtext&gt;\u0000 &lt;mo&gt;⋅&lt;/mo&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;mol&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ kcalcdot {mol}^{-1} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, which is ~3 times higher (i.e., stronger) than the reported experimental interaction energy between dopamine and dopamine transporter (−7.4 &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;kcal&lt;/mtext&gt;\u0000 &lt;mo&gt;⋅&lt;/mo&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;mol&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ kcalcdot {mol}^{-1} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;). Interaction with anion (&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;Cl&lt;/mi&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {Cl}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;) is weaker than c","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 8","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148386263","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}