caa a22 4500 605510903 CHVBK 20210128100648.0 cr unu---uuuuu 210128e20150601xx s 000 0 eng 10.1007/s00894-015-2697-y doi (NATIONALLICENCE)springer-10.1007/s00894-015-2697-y A comprehensive analysis of P···π pnicogen bonds: substitution effects and comparison with Br···π halogen bonds [Elektronische Daten] [Cuicui Liu, Yanli Zeng, Xiaoyan Li, Lingpeng Meng, Xueying Zhang] 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 in the electron donor leads to strengthening while the electron-withdrawing group leads to weakening of P···π interactions. The studied P···π and Br···π interactions are similar and are typically "closed-shell” non-covalent character in nature. Moreover, analyses of natural bond orbital and density difference of molecular formation indicated that charge transfer and polarization also play important roles in P···π interactions. The substituents have direct effects on the molecular electrostatic potential, and the charge transfer amount and extent of polarization of the P···π interaction are also specific to each substituent. Springer-Verlag Berlin Heidelberg, 2015 Pnicogen bond nationallicence Halogen bond nationallicence Substitution effect nationallicence Topological analysis of electron density nationallicence Liu Cuicui Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut Zeng Yanli Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut Li Xiaoyan Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut Meng Lingpeng Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut Zhang Xueying Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/6(2015-06-01), 1-12 1610-2940 21:6<1 2015 21 894 https://doi.org/10.1007/s00894-015-2697-y text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2697-y text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Liu Cuicui Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut NATIONALLICENCE 700 1- Zeng Yanli Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut NATIONALLICENCE 700 1- Li Xiaoyan Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut NATIONALLICENCE 700 1- Meng Lingpeng Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut NATIONALLICENCE 700 1- Zhang Xueying Institute of Computational Quantum Chemistry, College of Chemistry and Material Sciences, Hebei Normal University, 050024, Shijiazhuang, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/6(2015-06-01), 1-12 1610-2940 21:6<1 2015 21 894