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 - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Molecules Année : 2020

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

Résumé

Positive electrostatic potential (V) 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 V. Further precious insights into such factors are obtained through a rigorous decomposition of the V values in atomic or atomic group contributions, a task here achieved by extending the Bader-Gatti source function (SF) for the electron density to V. 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 V values on electron density isosurfaces (V S) and by comparing and dissecting in atomic/atomic group contributions the V S maxima (V S,max) 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.
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Dates et versions

hal-02952772 , version 1 (29-09-2020)

Identifiants

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Carlo Gatti, Alessandro Dessì, Roberto Dallocchio, Victor Mamane, Sergio Cossu, et al.. 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, 2020, 25 (19), pp.4409. ⟨10.3390/molecules25194409⟩. ⟨hal-02952772⟩
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