Articles written in Journal of Chemical Sciences
Volume 127 Issue 10 October 2015 pp 1729-1738
Theoretical exploration of pnicogen bond noncovalent interactions in HCHO· · · PH2X (X=CH3, H, C6H5, F, Cl, Br, and NO2) complexes
Yan-Zhi Liu Kun Yuan Zhao Yuan Yuan-Cheng Zhu Xiang Zhao
Pnicogen bond (ZB) is a new kind of intermolecular weak interaction, which would be an important strategy for the construction of supramolecular materials. In this paper, ab initio MP2/aug-cc-pvDZ calculations have been carried out to characterize the X-P ⋯ O ZB interactions between HCHO and PH2X (X=CH3, H, C6H5, F, Cl, Br, and NO2). The calculated interaction energies with basis set super-position error (BSSE) corrections in seven ZB complexes are between −7.51 and −20.36 kJ·mol−1. The relative stabilities of the seven complexes increase in the order: HCHO⋯ PH2CH3 < HCHO⋯ PH3 < HCHO⋯ PH2 C6H5 < HCHO⋯ PH2 Br < HCHO⋯ PH2 Cl < HCHO⋯ PH2F < HCHO⋯ PH2NO2. The natural bond orbital (NBO) and natural resonance theory (NRT) analysis were employed to investigate the electron behavior and nature of the ZBs. The natural bond orbital interactions in the ZBs are mainly LP1,2 (O) → 𝜎* (P-X). The P-X (X= Br, Cl, F and NO2) are more suitable for acting as ZB donors than the P-X (X=H, CH3 and C6H5) groups. The electron density topology properties based on atoms-inmolecules (AIM) theory showed that the ZB interactions in the HCHO⋯ PH2X (X=Br, Cl, F and NO2) are stronger than those of HCHO⋯ PH2 X(X=CH3 , H and C6H5) complexes, indicating that the electron withdrawing of X benefits for the stability of ZB structure.
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