Journal of Computational Chemistry最新文献

{"title":"A DFT Study of an Organocatalytic Enantioselective Mannich Reaction Under the Sway of Noncovalent Interactions","authors":"Andrus Metsala,&nbsp;Kadri Kriis,&nbsp;Tõnis Kanger","doi":"10.1002/jcc.70159","DOIUrl":"https://doi.org/10.1002/jcc.70159","url":null,"abstract":"<div>\u0000 \u0000 <p>Density functional theory (DFT) calculations were performed for an asymmetric Mannich reaction between iminophosphorane and malononitrile catalyzed by a multifunctional organocatalyst. A quantum chemical modeling of the C<span></span>C bond-forming reaction coordinate, proton transfer reaction coordinate, and torsional reaction coordinate was investigated with the help of M06-2X DFT calculations with a def2-SVP basis set. It was found that the rate-determining and enantiodetermining step (transition state) was neither associated with the C<span></span>C bond-forming reaction coordinate nor with the proton transfer coordinate. The enantiodetermining step was associated with the torsional degrees of freedom and influenced by the network of non-covalent interactions.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 17","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144339657","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Three-Dimensional Metallic Boron Carbide: Stability and Properties","authors":"Kashif Hussain,&nbsp;Qiang Liu,&nbsp;Bin Chen,&nbsp;Maryam Sarwar,&nbsp;Fatima Munir,&nbsp;Ying Teng,&nbsp;Heping Xie,&nbsp;Suling Shen,&nbsp;Zhengbiao Ouyang","doi":"10.1002/jcc.70168","DOIUrl":"https://doi.org/10.1002/jcc.70168","url":null,"abstract":"<div>\u0000 \u0000 <p>The design of novel materials through the strategic modification of their structural building blocks represents a powerful approach to achieving significant advancements in materials science. This study thoroughly examines the structural, mechanical, electronic, acoustic, and thermodynamic properties of a three-dimensional monoclinic boron carbide (3D <i>m</i>-B₈C₈) structure using first-principles methods based on density functional theory (DFT). We introduce a unique cage-based 3D monoclinic boron carbide structure, constructed from 4-, 5-, and 6-membered rings, which demonstrates remarkable dynamic, thermal, and mechanical stability. Our advanced first-principles calculations reveal that this architecture exhibits metallic characteristics, as confirmed by both GGA-PBE and HSE06 hybrid functionals. In contrast to the ductile and low Vickers hardness 3D-B₆C₆, the 3D <i>m</i>-B₈C₈ displays significant brittleness, a high Vickers hardness of 45.40 GPa (32.36 GPa), a low Poisson's ratio of 0.188, and a universal anisotropic index of 0.903. When compared to established thermal coating (TBC) materials such as yttria-stabilized zirconia (YSZ), which has a fracture toughness range of 2.0 to 2.3 MPa m^1/2 and a minimum thermal conductivity of 2.20 W m⁻¹ K⁻¹, the 3D <i>m</i>-B₈C₈ demonstrates superior fracture toughness of 5.336 MPa m^1/2 and a minimum thermal conductivity of 3.773 W m⁻¹ K⁻¹. These exceptional characteristics suggest that 3D <i>m</i>-B₈C₈ could serve as a compelling candidate for applications in environmental protection, thermal barriers, and oxygen-resistant coatings. The material exhibits a Debye temperature of 1524.15 K, an acoustic Grüneisen constant of 1.240, and a phonon thermal conductivity of 85.52 W m⁻¹ K⁻¹ at 300 K. Its melting temperature is 3311.94 K, with a thermal expansion coefficient of 7.337 μK⁻¹ and notable phonon inelastic scattering. These findings expand the range of boron carbide materials with new properties, presenting exciting prospects for advanced engineering applications and encouraging further experimental synthesis efforts.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 17","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144367489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Study on the Aggregation and Dehydration Behavior of Aqueous Boric Acid Solutions Confined in Carbon Nanotubes","authors":"Yanan Wu,&nbsp;Fayan Zhu,&nbsp;Ruirui Liu,&nbsp;Xu Zhao,&nbsp;Yifa Du,&nbsp;Yongquan Zhou,&nbsp;Chunlei Wang,&nbsp;Yongming Zhang","doi":"10.1002/jcc.70156","DOIUrl":"https://doi.org/10.1002/jcc.70156","url":null,"abstract":"<div>\u0000 \u0000 <p>The properties and structure of boric acid aqueous solutions confined in different carbon nanotubes (CNTs) with pore sizes are investigated using multiscale simulations. The study shows that a CNT pore size of 2.56 nm is a critical value for the properties and structure of confined boric acid solutions. When the pore size of a CNT is less than 2.56 nm, the properties of boric acid solutions show a noticeable confinement effect, which gradually decreases with increasing pore size and approaches those of a bulk solution. In small-sized CNTs (0.82 and 0.96 nm), boric acid molecules do not polymerize with each other. With further increasing pore size, polymerization occurs between boric acid molecules in a bidentate manner. In small CNTs (0.82 and 0.96 nm), boric acid molecules undergo dehydration and transform into metaboric acid molecules. This study provides a theoretical basis for green enrichment, separation, and high-value utilization of boron resources.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 17","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144323714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revisiting the “Cluster-In-Solvent” Approach for Computational Spectroscopy: The Vibrational Circular Dichroism as a Test Case","authors":"Srilatha Arra,&nbsp;Isabella Daidone,&nbsp;Massimiliano Aschi","doi":"10.1002/jcc.70144","DOIUrl":"https://doi.org/10.1002/jcc.70144","url":null,"abstract":"<p>The cluster-in-solvent approach, that is, the use of the quantum-mechanical calculation of a spectral observable on a significant number of solute–solvent clusters extracted from semi-classical simulations, is widely used in computational spectroscopy. However, identifying relevant coordinates for cluster selection remains a challenge. We previously developed the Ellipsoid Method for Cluster-in-Solvent (EMCS), an automated strategy for unbiased identification and statistical weighting of clusters. Yet, for larger solutes, EMCS can yield overly large solvent clusters that hinder conformational analysis. Here, we introduce a simple extension of EMCS that reduces cluster size, enabling its application to medium-to-large solutes. The method is validated through the computation of Vibrational Circular Dichroism (VCD) spectra, which are highly sensitive to solute–solvent interactions. Test cases include aqueous L-alanine, aqueous dialanine, and (1S,2S)-trans-1-amino-2-indanol in DMSO. For L-alanine and trans-1-amino-2-indanol, computed spectra closely match experiment, with root-mean-square-deviation (RMSD) values of 10.3 and 8.0, respectively, consistent with previous benchmarks. For aqueous dialanine, the main spectral features were reproduced, though discrepancies in the fine structure remain, likely due to limitations in capturing subtle solvation effects. Overall, the refined EMCS protocol enables efficient and non-arbitrary sampling of solute–solvent clusters, offering a valuable tool for the structural analysis of solvation shells in complex molecular systems.</p>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 17","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70144","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144323720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ranking the Properties Important for Understanding Noncovalent Bond Strength","authors":"Steve Scheiner","doi":"10.1002/jcc.70163","DOIUrl":"https://doi.org/10.1002/jcc.70163","url":null,"abstract":"<div>\u0000 \u0000 <p>The interaction energies within noncovalent bonds can be partitioned into electrostatic, induction, and dispersive attractive elements. A set of complexes comprising halogen, chalcogen, pnicogen, and tetrel bonds, are studied by quantum chemical calculations to assess how each of these components can be understood on the basis of properties of the constituent monomers. The variation of the electrostatic term, which accounts for over half of the total attractive energy, can be approximated, but with only modest accuracy, by combination of the maximum and minimum of the electrostatic potential on the two subunits. Induction represents a smaller contribution to the total, but is well connected with the NBO interorbital transfer energy, as opposed to the reciprocal of the HOMO-LUMO gap which behaves quite differently than IND. Of the various AIM parameters, both the bond critical point density and energy density are closely related to the full interaction energy.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 17","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144308870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multi-Task Learning in Homogeneous Catalysis: A Case Study for Predicting the Catalytic Performance in Ethylene Polymerization","authors":"Zubair Sadiq,&nbsp;Wenhong Yang,&nbsp;Weisheng Yang,&nbsp;Wen-Hua Sun","doi":"10.1002/jcc.70157","DOIUrl":"10.1002/jcc.70157","url":null,"abstract":"<div>\u0000 \u0000 <p>This study focuses on training a multi-task learning (MTL) type machine learning (ML) model to predict diverse catalytic performance of 195 bis(imino)pyridine transition metal complexes toward ethylene polymerization, with comparison to their single-task learning (STL) counterparts. The <i>CatBoost</i> MTL model outperforms all other models, showing predictions and generalization errors for the properties of catalytic activity (<i>R</i>_<i>t</i>²=0.741, <i>R</i>² = 0.985, <i>Q</i>² = 0.600), molecular weight (<i>R</i>_<i>t</i>²=0.873, <i>R</i>² = 0.997, <i>Q</i>² = 0.846), molecular weight distribution (<i>R</i>_<i>t</i>²=0.831, <i>R</i>² = 0.999, <i>Q</i>² = 0.839), and melting temperature (<i>R</i>_<i>t</i>²=0.813, <i>R</i>² = 0.992, Q² = 0.625) of the produced polymer. The interpretation of the model reveals that complexes with electron-donating groups, simple alkyl groups (such as methyl groups etc.), and a higher degree of unsaturation (presence of double or triple bonds) positively influence the predicted properties. Subsequently, providing insights into the underlying mechanisms of variation in catalytic performance, new complexes are designed with superior catalytic performances.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 17","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305546","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Virtual Bonding Enhanced Graph Self-Supervised Learning for Molecular Property Prediction","authors":"Yongna Yuan,&nbsp;Zitian Lu,&nbsp;Yuhan Li","doi":"10.1002/jcc.70147","DOIUrl":"https://doi.org/10.1002/jcc.70147","url":null,"abstract":"<div>\u0000 \u0000 <p>Accurate prediction of molecular properties is essential for modern drug design and discovery. Self-supervised learning (SSL) and Graph Neural Networks (GNNs) have been widely used in this field to learn molecular representations and predict molecular properties. However, previous graph-based deep learning methods have overlooked the important weak interaction, that is, long-range interatomic interaction, which is crucial in determining the molecular properties. This study presents a novel self-supervised learning framework, Virtual Bonding Enhanced Molecular Property Prediction (VIBE-MPP), to address the limitations of existing methods by incorporating weak interactions and 3D spatial information into the molecular representations. VIBE-MPP utilizes a Virtual Bonding Graph Neural Network (VBGNN) to construct a virtual bonding enhanced graph that encodes molecules, and a Dual-level Self-supervised Boosted Pretraining (DSBP) approach to enhance representation learning through four designed pretext tasks. The framework introduces virtual bonds to represent atom interactions within a radius of 10 Å, enabling an atom to engage in message passing with multiple other neighboring atoms simultaneously. The model is evaluated on 10 benchmark datasets, demonstrating superior performance over state-of-the-art methods in both classification and regression tasks. On average, it improves upon the best baseline models by 3.20% and achieves optimal performance on four regression datasets. Additionally, visualizations of the learned molecular representations in downstream datasets show that VIBE-MPP effectively captures molecular properties and semantic information.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 16","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281574","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of a New AMBER Force Field for Cysteine and Histidine Cadmium-Binding Proteins and Its Validation Through QM/MM MD Simulations","authors":"Matteo Orlandi,&nbsp;Marina Macchiagodena,&nbsp;Piero Procacci,&nbsp;Fabrizio Carta,&nbsp;Claudiu T. Supuran,&nbsp;Marco Pagliai","doi":"10.1002/jcc.70154","DOIUrl":"https://doi.org/10.1002/jcc.70154","url":null,"abstract":"<p>We developed and validated a novel force field in the context of the AMBER parameterization for the simulation of cadmium(II)-binding proteins. The proposed force field takes into account the polarization effect produced by the central ion on its surroundings. The new polarized atomic charges for cysteine and histidine residues were derived based on the available structures of cadmium-bearing proteins using QM calculations and QM/MM simulations. The developed force field was validated by performing molecular dynamics simulations on several cadmium(II)-binding proteins. Our model preserves the tetra-coordination of the metal site with remarkable stability, yielding mean distances between <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msup>\u0000 <mi>Cd</mi>\u0000 <mrow>\u0000 <mn>2</mn>\u0000 <mo>+</mo>\u0000 </mrow>\u0000 </msup>\u0000 </mrow>\u0000 <annotation>$$ {mathrm{Cd}}^{2+} $$</annotation>\u0000 </semantics></math> ion and S or N atoms of the binding residues in close agreement with experimental data.</p>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 16","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70154","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144273266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Xylopyranose Ring-Opening by Single and Double Proton Transfers Under Pyrolysis Conditions","authors":"Jacopo Lupi,&nbsp;Bernardo Ballotta,&nbsp;Leandro Ayarde-Henríquez,&nbsp;Stephen Dooley","doi":"10.1002/jcc.70151","DOIUrl":"https://doi.org/10.1002/jcc.70151","url":null,"abstract":"&lt;p&gt;This study unveils a new transition state (TS) leading to the acyclic product via synchronous double proton transfer by automatedly exploring the potential energy surface of &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;β&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ beta $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;-D-xylopyranose under pyrolysis conditions. Quantum chemistry methods with multi-path canonical variational transition state theory show that the standard activation enthalpy of the new TS (44.9 kcal &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mtext&gt;mol&lt;/mtext&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;$$ {mathrm{mol}}^{-1} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;) is 1.5 kcal &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mtext&gt;mol&lt;/mtext&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;$$ {mathrm{mol}}^{-1} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; lower than that of the well-established channel; however, the latter's rate constant (&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;4&lt;/mn&gt;\u0000 &lt;mo&gt;.&lt;/mo&gt;\u0000 &lt;mn&gt;36&lt;/mn&gt;\u0000 &lt;mo&gt;×&lt;/mo&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;msup&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;0&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ 4.36times 1{0}^{-2} $$&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;mn&gt;9&lt;/mn&gt;\u0000 &lt;mo&gt;.&lt;/mo&gt;\u0000 &lt;mn&gt;96&lt;/mn&gt;\u0000 &lt;mo&gt;×&lt;/mo&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;msup&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;0&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&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;$$ 9.96times 1{0}^1 $$&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;mtext&gt;s&lt;/mtext&gt;\u0000 ","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 16","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70151","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144273455","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Understanding the Mechanism of Triplet-Triplet Energy Transfer in the Photocatalytic [2 + 2] Cycloaddition: Insights From Quantum Chemical Modeling","authors":"Eunji Lee,&nbsp;Hyejin Moon,&nbsp;Jiyong Park,&nbsp;Mu-Hyun Baik","doi":"10.1002/jcc.70155","DOIUrl":"https://doi.org/10.1002/jcc.70155","url":null,"abstract":"<p>We investigate the mechanism of [2 + 2] photocycloaddition reaction of 3-(but-3-enyl)oxyquinolone using a chiral xanthone-containing triplet sensitizer. Quantum chemical computer models were utilized to examine the substrate-catalyst encounter complex structures, which were classified into <i>syn</i>- and <i>anti-</i>adducts. The photoactivation steps of the substrate were analyzed based on the Marcus equation of electron transfer, including intersystem crossings (ISC) and outer sphere triplet-triplet energy transfer (TTEnT). Our results show that the calculated rates of ISC are comparable for the two adducts, while the rates of TTEnT differ due to the orbital overlap between the donor and acceptor sites. After the TTEnT, a stereospecific cyclization occurs, completing the catalytic cycle. We propose a strategy to improve stereoselectivity by exploiting the intrinsic difference in TTEnT rates between the two encounter complex isomers.</p>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 16","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70155","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}