The spectroscopic determination of the energies of the hydrogen bonds in the complexes formed between several chlorosubstituted phenols and acetone and dimethylformamide

Perelygin, I. S.; Akhunov, T. F.

doi:10.1007/bf00604513

Cited by 2 publications

(1 citation statement)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…During the following decades, this correlation has been mentioned in literature as the “Badger‐Bauer rule” and has been used for numerous investigations 20–26 . However, in some works it was noted that the dependency ∆ H (∆ ν s ) is nonlinear, 27,28 while others reported the absence of a strict correlation between ∆ H and ∆ ν s at all 29–31 . The series of works was devoted to correlate the shift of ν s frequency with a hydrogen bond length 9,10,32,33 .…”

Section: Introductionmentioning

confidence: 99%

Estimations of FH···X hydrogen bond energies from IR intensities: Iogansen's rule revisited

et al. 2021

View full text Add to dashboard Cite

In this work the possibility of using the IR intensity of the stretching vibration νs of proton donor group for estimation of hydrogen bond strength was investigated. For a set of complexes with FH···X (X = F, N, O) hydrogen bonds in the wide range of energies (0.1–49.2 kcal/mol) vibrational frequencies νs and their intensities A were calculated (CCSD at complete basis set limit). The validity of the previously proposed linear proportionality between the intensification of the stretching vibration νs in IR spectra and hydrogen bond enthalpy –ΔH = 12.2 ∆A (A. V. Iogansen, Spectrochimica Acta A 1999) was examined. It is shown that for a range of similar hydrogen bond types with complexation energies ∆E <15 kcal/mol the ∆E(∆A) function remains similar to that proposed in the Iogansen's work, while upon strengthening this dependency becomes significantly nonlinear. We examined two other parameters (∆Aνs and ∆A∙mR) related to IR intensity as descriptors of hydrogen bond strength which are proportional to transition dipole moment matrix element and mass‐independent dipole moment derivative. It was found that the dependency ∆E(∆Aνs) stays linear in the whole studied range of complexation energies and it can be used for evaluation of ∆E from infrared spectral data with the accuracy about 2 kcal/mol. The mass‐independent product ∆A∙mR is an appropriate descriptor for sets of complexes with various hydrogen bond types. Simple equations proposed in this work can be used for estimations of hydrogen bond strength in various systems, where experimental thermodynamic methods or direct calculations are difficult or even impossible.

show abstract