A comprehensive analysis of P···π pnicogen bonds: substitution effects and comparison with Br···π halogen bonds

Ab initio calculations were carried out in a systematic investigation of P···π pnicogen-bonded complexes XH2P···C2H2/C2H4 and FH2P···C2R2/C2R4 for X = H, CH3, OH, CN, Br, Cl, NO2, F, and R = F, CH3, as well as corresponding Br···π halogen-bonded complexes XBr···C2H2. Both the electron-withdrawing and electron-donating substituents in the electron acceptor have enhancing effects on the strength of P···π interactions. The electron-donating group...