DFT and IsoStar Analyses to Assess the Utility of σ- and π-Hole Interactions for Crystal Engineering.

ABSTRACT: The interpretation of 36 charge neutral 'contact pairs' from the IsoStar database was supported by DFT calculations of model molecules 1-12, and bimolecular adducts thereof. The 'central groups' are σ-hole donors (H₂ O and aromatic C-I), π-hole donors (R-C(O)Me, R-NO₂ and R-C₆ F₅ ) and for comparison R-C₆ H₅ (R=any group or atom). The 'contact groups' are hydrogen bond donors X-H (X=N, O, S, or R₂ C, or R₃ C) and lone-pair containing fragments (R₃ C-F, R-C≡N and R₂ C=O). Nearly all the IsoStar distributions follow expectations based on the electrostatic potential of the 'central-' and 'contact group'. Interaction energies (ΔE^BSSE ) are dominated by electrostatics (partic

SUBMITTER: Mooibroek TJ 

PROVIDER: S-EPMC7898519 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature