Molecular electrostatic potential and "atoms‐in‐molecules" analyses of the interplay between π‐hole and lone pair···π/X–H···π/metal···π interactions. Issue 9 (30th June 2017)

• Record Type: Journal Article
• Authors: Bauzá, Antonio; Seth, Saikat Kumar; Frontera, Antonio
• Other Names: Gadre Shridhar R. guestEditor.; Suresh C. H. guestEditor.
• Is Part Of: Journal of computational chemistry. Volume 39:Issue 9(2018)
• Page Start: 458
• Page End: 463
• Publication Date: 2017-06-30
• Subjects: ab initio calculations -- cooperative effects -- noncovalent interactions -- supramolecular chemistry -- π‐hole interactions; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.24869
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract : Using ab initio calculations, we analyze the interplay between π‐hole interactions involving the nitro group of 1, 4‐dinitrobenzene and lone pair···π (lp···π), C–H···π or metal(M)···π noncovalent interactions. Moreover, we have also used 1, 4‐phenylenebis(phosphine dioxide) for comparison purposes. Interesting cooperativity effects are found when π‐hole (F···N, P) and lp···π/C–H···π/M···π interactions coexist in the same supramolecular assembly. These effects are studied theoretically in terms of energetic and geometric features of the complexes, which are computed by ab initio methods (RI‐MP2/def2‐TZVP). A charge density analysis using the Bader's theory of "atoms in molecules" is carried out to characterize the interactions and to analyze their strengthening or weakening depending on the variation of charge density at critical points. The importance of electrostatic effects on the mutual influence of the interaction is studied by means of molecular electrostatic potential calculations. By taking advantage of these computational tools, the present study examines interplay of these interactions. © 2017 Wiley Periodicals, Inc. Abstract : The interplay between π‐hole interactions involving the –PnO2 group (Pn = N, P) of 1, 4‐disubstituted benzene and lone pair···π (lp···π), C–H···π or metal(M)···π non covalent interactions was analyzed by means of ab initio calculations, molecular electrostatic potential surfaces and AIM analysis.