Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives
Positive electrostatic potential (<i>V</i>) values are often associated with σ- and π-holes, regions of lower electron density which can interact with electron-rich sites to form noncovalent interactions. Factors impacting σ- and π-holes may thus be monitored in terms of the shape and va...
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MDPI AG
2020-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/19/4409 |
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| author | Carlo Gatti Alessandro Dessì Roberto Dallocchio Victor Mamane Sergio Cossu Robin Weiss Patrick Pale Emmanuel Aubert Paola Peluso |
| author_facet | Carlo Gatti Alessandro Dessì Roberto Dallocchio Victor Mamane Sergio Cossu Robin Weiss Patrick Pale Emmanuel Aubert Paola Peluso |
| author_sort | Carlo Gatti |
| collection | DOAJ |
| description | Positive electrostatic potential (<i>V</i>) values are often associated with σ- and π-holes, regions of lower electron density which can interact with electron-rich sites to form noncovalent interactions. Factors impacting σ- and π-holes may thus be monitored in terms of the shape and values of the resulting <i>V</i>. Further precious insights into such factors are obtained through a rigorous decomposition of the <i>V</i> values in atomic or atomic group contributions, a task here achieved by extending the Bader–Gatti source function (SF) for the electron density to <i>V</i>. In this article, this general methodology is applied to a series of 4,4′-bipyridine derivatives containing atoms from Groups VI (S, Se) and VII (Cl, Br), and the pentafluorophenyl group acting as a π-hole. As these molecules are characterized by a certain degree of conformational freedom due to the possibility of rotation around the two C–Ch bonds, from two to four conformational motifs could be identified for each structure through conformational search. On this basis, the impact of chemical and conformational features on σ- and π-hole regions could be systematically evaluated by computing the <i>V</i> values on electron density isosurfaces (<i>V</i><sub>S</sub>) and by comparing and dissecting in atomic/atomic group contributions the <i>V</i><sub>S</sub> maxima (<i>V</i><sub>S,max</sub>) values calculated for different molecular patterns. The results of this study confirm that both chemical and conformational features may seriously impact σ- and π-hole regions and provide a clear analysis and a rationale of why and how this influence is realized. Hence, the proposed methodology might offer precious clues for designing changes in the σ- and π-hole regions, aimed at affecting their potential involvement in noncovalent interactions in a desired way. |
| first_indexed | 2024-03-10T16:02:59Z |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T16:02:59Z |
| publishDate | 2020-09-01 |
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| series | Molecules |
| spelling | doaj.art-a982e93c81e7429e860c40286b15045b2023-11-20T15:08:33ZengMDPI AGMolecules1420-30492020-09-012519440910.3390/molecules25194409Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine DerivativesCarlo Gatti0Alessandro Dessì1Roberto Dallocchio2Victor Mamane3Sergio Cossu4Robin Weiss5Patrick Pale6Emmanuel Aubert7Paola Peluso8CNR-SCITEC, Istituto di Scienze e Tecnologie Chimiche “Giulio Natta”, sezione di via Golgi, via C. Golgi 19, 20133 Milano, ItalyInstitute of Biomolecular Chemistry ICB, CNR, Secondary branch of Sassari, Traversa La Crucca 3, Regione Baldinca, Li Punti, 07100 Sassari, ItalyInstitute of Biomolecular Chemistry ICB, CNR, Secondary branch of Sassari, Traversa La Crucca 3, Regione Baldinca, Li Punti, 07100 Sassari, ItalyStrasbourg Institute of Chemistry, UMR CNRS 7177, Team LASYROC, 1 rue Blaise Pascal, University of Strasbourg, 67008 Strasbourg, FranceDepartment of Molecular Science and Nanosystems DSMN, Venice Ca’ Foscari University, Via Torino 155, 30172 Mestre Venezia, ItalyStrasbourg Institute of Chemistry, UMR CNRS 7177, Team LASYROC, 1 rue Blaise Pascal, University of Strasbourg, 67008 Strasbourg, FranceStrasbourg Institute of Chemistry, UMR CNRS 7177, Team LASYROC, 1 rue Blaise Pascal, University of Strasbourg, 67008 Strasbourg, FranceCrystallography, Magnetic Resonance and Modelling (CRM2), UMR CNRS 7036, University of Lorraine, Bd des Aiguillettes, 54506 Vandoeuvre-les-Nancy, FranceInstitute of Biomolecular Chemistry ICB, CNR, Secondary branch of Sassari, Traversa La Crucca 3, Regione Baldinca, Li Punti, 07100 Sassari, ItalyPositive electrostatic potential (<i>V</i>) values are often associated with σ- and π-holes, regions of lower electron density which can interact with electron-rich sites to form noncovalent interactions. Factors impacting σ- and π-holes may thus be monitored in terms of the shape and values of the resulting <i>V</i>. Further precious insights into such factors are obtained through a rigorous decomposition of the <i>V</i> values in atomic or atomic group contributions, a task here achieved by extending the Bader–Gatti source function (SF) for the electron density to <i>V</i>. In this article, this general methodology is applied to a series of 4,4′-bipyridine derivatives containing atoms from Groups VI (S, Se) and VII (Cl, Br), and the pentafluorophenyl group acting as a π-hole. As these molecules are characterized by a certain degree of conformational freedom due to the possibility of rotation around the two C–Ch bonds, from two to four conformational motifs could be identified for each structure through conformational search. On this basis, the impact of chemical and conformational features on σ- and π-hole regions could be systematically evaluated by computing the <i>V</i> values on electron density isosurfaces (<i>V</i><sub>S</sub>) and by comparing and dissecting in atomic/atomic group contributions the <i>V</i><sub>S</sub> maxima (<i>V</i><sub>S,max</sub>) values calculated for different molecular patterns. The results of this study confirm that both chemical and conformational features may seriously impact σ- and π-hole regions and provide a clear analysis and a rationale of why and how this influence is realized. Hence, the proposed methodology might offer precious clues for designing changes in the σ- and π-hole regions, aimed at affecting their potential involvement in noncovalent interactions in a desired way.https://www.mdpi.com/1420-3049/25/19/4409atomic group contributionsbipyridineschalcogen bondelectrostatic potentialhalogen bondσ-hole |
| spellingShingle | Carlo Gatti Alessandro Dessì Roberto Dallocchio Victor Mamane Sergio Cossu Robin Weiss Patrick Pale Emmanuel Aubert Paola Peluso Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives Molecules atomic group contributions bipyridines chalcogen bond electrostatic potential halogen bond σ-hole |
| title | Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives |
| title_full | Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives |
| title_fullStr | Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives |
| title_full_unstemmed | Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives |
| title_short | Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives |
| title_sort | factors impacting σ and π hole regions as revealed by the electrostatic potential and its source function reconstruction the case of 4 4 bipyridine derivatives |
| topic | atomic group contributions bipyridines chalcogen bond electrostatic potential halogen bond σ-hole |
| url | https://www.mdpi.com/1420-3049/25/19/4409 |
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