{"title":"探索双(4-硝基苯基)方酰胺与卤化阴离子的主客体相互作用:气相和溶液中的计算研究","authors":"Yasin Gholiee","doi":"10.1007/s00214-024-03137-6","DOIUrl":null,"url":null,"abstract":"<p>A computational study on the host–guest complexes of neutral bis(4-nitrophenyl)squaramide (SQ) and halide anions is reported. In the gas-phase, the calculated interaction and stabilization energies indicates a diminishing intrinsic affinity of SQ for anions from fluoride to iodide. The nature of interactions is investigated using Natural Bond Orbital (NBO), Quantum Theory of Atoms in Molecules (QTAIM) along with Energy Decomposition Analysis-Natural Orbitals for Chemical Valence (EDA-NOCV). While electrostatic interactions account for roughly 60% of the total, EDA-NOCV analysis demonstrated increasing contributions of orbital interactions from <span>\\(\\left[ {{\\text{SQ}} \\cdots {\\text{I}}} \\right]^{ - }\\)</span> to <span>\\(\\left[ {{\\text{SQ}} \\cdots {\\text{F}}} \\right]^{ - }\\)</span> complexes. In solution, thermodynamic cycle analyses and Gibbs free energy calculations reveal a propensity towards the formation of <span>\\(\\left[ {{\\text{SQ}} \\cdots {\\text{F}}} \\right]^{ - }\\)</span>, taking into account the influence of solvation energies on the overall stability. The consistent trend observed in selectivity both in the gas phase and in solution suggests that changes in solvation energy do not significantly impact the stability of complexes. The findings were additionally supported by a significant correlation observed between the computed and experimental formation constants.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"66 1","pages":""},"PeriodicalIF":1.6000,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Exploring host–guest interactions of bis(4-nitrophenyl)squaramide with halide anions: a computational investigation in the gas-phase and solution\",\"authors\":\"Yasin Gholiee\",\"doi\":\"10.1007/s00214-024-03137-6\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>A computational study on the host–guest complexes of neutral bis(4-nitrophenyl)squaramide (SQ) and halide anions is reported. In the gas-phase, the calculated interaction and stabilization energies indicates a diminishing intrinsic affinity of SQ for anions from fluoride to iodide. The nature of interactions is investigated using Natural Bond Orbital (NBO), Quantum Theory of Atoms in Molecules (QTAIM) along with Energy Decomposition Analysis-Natural Orbitals for Chemical Valence (EDA-NOCV). While electrostatic interactions account for roughly 60% of the total, EDA-NOCV analysis demonstrated increasing contributions of orbital interactions from <span>\\\\(\\\\left[ {{\\\\text{SQ}} \\\\cdots {\\\\text{I}}} \\\\right]^{ - }\\\\)</span> to <span>\\\\(\\\\left[ {{\\\\text{SQ}} \\\\cdots {\\\\text{F}}} \\\\right]^{ - }\\\\)</span> complexes. In solution, thermodynamic cycle analyses and Gibbs free energy calculations reveal a propensity towards the formation of <span>\\\\(\\\\left[ {{\\\\text{SQ}} \\\\cdots {\\\\text{F}}} \\\\right]^{ - }\\\\)</span>, taking into account the influence of solvation energies on the overall stability. The consistent trend observed in selectivity both in the gas phase and in solution suggests that changes in solvation energy do not significantly impact the stability of complexes. The findings were additionally supported by a significant correlation observed between the computed and experimental formation constants.</p>\",\"PeriodicalId\":23045,\"journal\":{\"name\":\"Theoretical Chemistry Accounts\",\"volume\":\"66 1\",\"pages\":\"\"},\"PeriodicalIF\":1.6000,\"publicationDate\":\"2024-07-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Theoretical Chemistry Accounts\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1007/s00214-024-03137-6\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Theoretical Chemistry Accounts","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s00214-024-03137-6","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Exploring host–guest interactions of bis(4-nitrophenyl)squaramide with halide anions: a computational investigation in the gas-phase and solution
A computational study on the host–guest complexes of neutral bis(4-nitrophenyl)squaramide (SQ) and halide anions is reported. In the gas-phase, the calculated interaction and stabilization energies indicates a diminishing intrinsic affinity of SQ for anions from fluoride to iodide. The nature of interactions is investigated using Natural Bond Orbital (NBO), Quantum Theory of Atoms in Molecules (QTAIM) along with Energy Decomposition Analysis-Natural Orbitals for Chemical Valence (EDA-NOCV). While electrostatic interactions account for roughly 60% of the total, EDA-NOCV analysis demonstrated increasing contributions of orbital interactions from \(\left[ {{\text{SQ}} \cdots {\text{I}}} \right]^{ - }\) to \(\left[ {{\text{SQ}} \cdots {\text{F}}} \right]^{ - }\) complexes. In solution, thermodynamic cycle analyses and Gibbs free energy calculations reveal a propensity towards the formation of \(\left[ {{\text{SQ}} \cdots {\text{F}}} \right]^{ - }\), taking into account the influence of solvation energies on the overall stability. The consistent trend observed in selectivity both in the gas phase and in solution suggests that changes in solvation energy do not significantly impact the stability of complexes. The findings were additionally supported by a significant correlation observed between the computed and experimental formation constants.
期刊介绍:
TCA publishes papers in all fields of theoretical chemistry, computational chemistry, and modeling. Fundamental studies as well as applications are included in the scope. In many cases, theorists and computational chemists have special concerns which reach either across the vertical borders of the special disciplines in chemistry or else across the horizontal borders of structure, spectra, synthesis, and dynamics. TCA is especially interested in papers that impact upon multiple chemical disciplines.