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<p>A theoretical investigation at the MP2/aug-cc-pVDZ level was done to elucidate the role of intramolecular hydrogen bonds (IMHBs) and –OH substituent implantation in modulating intermolecular hydrogen-bonded (HB) interactions of hydroxybenzenes (phenol, resorcinol, catechol, and pyrogallol) with ethers (dimethyl ether and diethyl ether). The calculations reveal that the primary IMHB enhances the intermolecular O–H···O interaction whereas the contribution of a second IMHB is negligible, as evident from the nearly identical binding energies of Cat-1, Pyg-1, and Pyg-2 with both the ethers. Additional -OH substituents that neither participate in HB nor form IMHBs exert minimal influence on overall stability. The binding energy values are found to strongly correlate with deprotonation enthalpy (DPE), electron density <i>ρ(r</i><sub><i>c</i></sub><i>)</i>, charge transfer (CT), hyperconjugation energy, and red shifted ν(O–H) frequencies. Strong correlation of ΔE<sub>elst</sub> and ΔE<sub>ind</sub> term with ν(O–H) red shifts of the complexes, contrasted with the poor correlation with ΔE<sub>disp</sub> energy term, illustrates the limitations of Badger-Bauer relationship when the overall interaction energy is considered rather than its individual components.</p>

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Hydroxybenzene-ether complexes: interplay of intra- and intermolecular hydrogen bonds and the limitation of Badger-Bauer relationship

  • 期刊论文

  • 发表日期：

    2026年3月14日

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  • Sanskruti Ramprasad Mishra,
  • Dipankar Sutradhar

摘要

A theoretical investigation at the MP2/aug-cc-pVDZ level was done to elucidate the role of intramolecular hydrogen bonds (IMHBs) and –OH substituent implantation in modulating intermolecular hydrogen-bonded (HB) interactions of hydroxybenzenes (phenol, resorcinol, catechol, and pyrogallol) with ethers (dimethyl ether and diethyl ether). The calculations reveal that the primary IMHB enhances the intermolecular O–H···O interaction whereas the contribution of a second IMHB is negligible, as evident from the nearly identical binding energies of Cat-1, Pyg-1, and Pyg-2 with both the ethers. Additional -OH substituents that neither participate in HB nor form IMHBs exert minimal influence on overall stability. The binding energy values are found to strongly correlate with deprotonation enthalpy (DPE), electron density ρ(rc), charge transfer (CT), hyperconjugation energy, and red shifted ν(O–H) frequencies. Strong correlation of ΔEelst and ΔEind term with ν(O–H) red shifts of the complexes, contrasted with the poor correlation with ΔEdisp energy term, illustrates the limitations of Badger-Bauer relationship when the overall interaction energy is considered rather than its individual components.