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Molecular electrostatic potential and “atoms‐in‐molecules” analyses of the interplay between π‐hole and lone pair···π/X–H···π/metal···π interactions
Author(s) -
Bauzá Antonio,
Seth Saikat Kumar,
Frontera Antonio
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24869
Subject(s) - lone pair , ab initio , non covalent interactions , cooperativity , supramolecular chemistry , atoms in molecules , chemistry , electrostatics , molecule , ab initio quantum chemistry methods , density functional theory , chemical physics , computational chemistry , hydrogen bond , biochemistry , organic chemistry
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.