Synergetic effects of inter- and intramolecular hydrogen bonding interactions in XC₅H₃HC = Y···HO···H₂O₂ complexes (X = N, P, As and Sb; Y = O, S and NH): the role of aromaticity and exchange interactions

ABSTRACT

Intramolecular hydrogen bonding (IHB) interactions were considered in XC₅H₃HC = Y···HO molecules which include OH···Y unit (Y = O, S and NH) and heteroatom X (X = N, P, As and Sb). Alteration of heteroatoms X in para position causes a change of properties of electron charge densities on these molecules and influences on strength of the IHB interactions. The aromaticity of the ring A (involving IHB interaction) and ring B (involving heteroatoms X) of XC₅H₃HC = Y···HO molecules was calculated using para-delocalisation index (PDI). Results reveal that the change of X from N to Sb is followed by the decrease in aromaticity of the mentioned rings. However, the strength of the IHB interactions increases during the change of X. Moreover, IHB energies were estimated using some computational methods and a viewpoint based on the properties of ring critical points (RCPs). The IHB energies obtained using a viewpoint based on the properties of RCPs have a better relationship with hydrogen bonding descriptors. Also, intermolecular hydrogen bond (HB) interactions of hydrogen peroxide with the close and open forms of the XC₅H₃HC = Y···HO molecules were considered. Cooperative effects of the HB and IHB interactions are revealed. Moreover, energy decomposition analysis (EDA) highlights the role of exchange interactions on the stability of the XC₅H₃HC = Y···HO···H₂O₂ complexes.

KEYWORDS:

• Intramolecular hydrogen bonding
• aromaticity
• QTAIM
• NBO
• EDA

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

We thank the University of Zabol and the University of Sistan and Baluchistan for all their support. The Grant number of this work is IR-UOZ-GR-9923.