Experimental evidence of O–H—S hydrogen bonding in supersonic jet

Abstract

Experimental evidence is presented for the O-H-S hydrogen bonding in the complexes of simple model compounds of methionine (dimethyl sulphide) and tyrosine (phenol, p-cresol, and 2-naphthol). The complexes were formed in the supersonic jet and were detected using resonantly enhanced multiphoton ionization spectroscopy. In all the complexes, the band origins for the S(1)-S(0) electronic transition were redshifted relative to that of their respective monomers. The resonant ion depletion IR spectra of all the complexes show redshifts of 123-140 cm(-1) in the O-H stretching frequency, indicating that the OH group acts as the hydrogen bond donor and sulfur as an acceptor. The density functional theory calculations also predict the stable structures in support of this and predict the redshifted O-H stretching frequency in the complex. The atoms-in-molecules and natural bond orbital calculations confirm the O-H-S hydrogen bonding interaction. The significant finding of this study is that the magnitudes of redshifts in the O-H stretch in the O-H-S hydrogen bonded complexes reported here are comparable to those reported for the O-H-O hydrogen bonded complexes where H(2)O acts as the H-bond acceptor, which suggests that the OH-S interaction is perhaps as strong as the OH-O interaction. To the best of our knowledge, this is the first such report on the O-H-S hydrogen bonded complexes.

OH···X (X = O, S) hydrogen bonding in thetrahydrofuran and tetrahydrothiophene

“…This has also been reported earlier for the other sulfur centered HB acceptors. 3,4,6,7 These observations indicate that the correlation that exists in the case of the first row H-bond acceptor may not hold across the rows of the periodic table. The main reasons for this could be (i) the large electronegativity difference between the oxygen or nitrogen and sulfur atom as HB acceptors, (ii) the large contribution of the dispersion energy in case of O-H···S H-bonded complexes whereas the electrostatic and charge transfer are the two major energy components for the O-H···O H-bonded systems.…”

“…We have recently initiated investigations of the hydrogen bonded complexes involving divalent sulfur acceptor in our laboratory using several laser spectroscopic techniques and computational methods. [3][4][5][6][7] In all the investigations, a comparative study of the O-H···O versus O-H···S hydrogen bonding interaction has enabled us to explore the differences/similarities in the nature of interaction and the directionality of the Hbond in these two systems. Briefly, the hydrogen bonding interaction between p-cresol (p-CR) and a series of S centered H-bond acceptors was investigated.…”

Absorptive Desulfurization of Model Biogas Stream Using Choline Chloride-Based Deep Eutectic Solvents

“…All characteristic bands that can be attributed to DMDS (2909.32 cm −1 -δs (CH) stretch, 1411.73 cm −1 -δas (CH 3 ) def., 1302.68 cm −1 -δs (CH 3 ) def., 692.82 cm −1 -C-S stretch, 540.96 cm −1 -S-S stretch) are visible in the ChCl:Ph-DMDS spectrum [56], which indicates the creation of the DES-DMDS complex (Figure 3a). Theoretically, in the absorptive DMDS removal process, both sulfur atoms can act as a donor in S-H···π and as an acceptor in O-H···S and C-H···S interactions [57][58][59]. However, on the FT-IR spectra, there are no shifts corresponding to this type of interaction.…”

Improved Description of Sulfur Charge Anisotropy in OPLS Force Fields: Model Development and Parameterization

“…7,10–15 In many compounds, the electrostatic potential around sulfur has both positive and negative regions, which allows it to act as hydrogen and halogen bond acceptors in lone-pair directions, and chalcogen bond donors along the extension of covalent bonds with sulfur. In a series of spectroscopic studies from Biswal and coworkers, 11,16,17,18 large red-shifts of the N-H and O-H stretching frequencies were observed for N-H⋯S and O-H⋯S hydrogen bonds in analogues of tryptophan-methionine and tyrosine-methionine complexes. The magnitudes of the red-shifts were comparable to the N/O-H⋯O counterparts, indicating similar hydrogen-bonding strength.…”