Rotational spectrum and intramolecular hydrogen bonding in 1,2-butanedithiol

Juanes, Marcos; Saragi, Rizalina Tama; Jin, Yan; Zingsheim, Oliver; Schlemmer, Stephan; Lesarri, Alberto

doi:10.1016/j.molstruc.2020.128080

Cited by 9 publications

(8 citation statements)

References 48 publications

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“…Thiol-alcohol gas-phase hydrogen bonds were also reported for the monohydrates of furfuryl 36 and thenyl 37 mercaptan ( r (S–H···O) = 2.22–2.44 Å; r (O–H···S) = 2.43–2.58 Å), but the experimental investigations of gas-phase hydrogen bonds between thiols are still scarce. 34 , 35 Protein crystal contacts between the cysteine thiol and the sulfur atom in methionine or cysteine have shorter average values of r (S–H···S) = 2.55(47) Å. 49 …”

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“… Here, we explore the replacement of oxygen in phenol by a heavier less-electronegative chalcogen atom like sulfur, proving that it maintains S–H···S hydrogen bonding while simultaneously resulting in a π-stacking homodimer. The work is extended also to the thiophenol trimer, complementing our view on sulfur hydrogen bonding − and allowing comparisons with the phenol and aniline trimers.…”

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Switching Hydrogen Bonding to π-Stacking: The Thiophenol Dimer and Trimer

Saragi

Juanes

Pérez

et al. 2021

J. Phys. Chem. Lett.

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We used jet-cooled broadband rotational spectroscopy to explore the balance between π-stacking and hydrogen-bonding interactions in the self-aggregation of thiophenol. Two different isomers were detected for the thiophenol dimer, revealing dispersion-controlled π-stacked structures anchored by a long S–H···S sulfur hydrogen bond. The weak intermolecular forces allow for noticeable internal dynamics in the dimers, as tunneling splittings are observed for the global minimum. The large-amplitude motion is ascribed to a concerted inversion motion between the two rings, exchanging the roles of the proton donor and acceptor in the thiol groups. The determined torsional barrier of B 2 = 250.3 cm –1 is consistent with theoretical predictions (290–502 cm –1 ) and the monomer barrier of 277.1(3) cm –1 . For the thiophenol trimer, a symmetric top structure was assigned in the spectrum. The results highlight the relevance of substituent effects to modulate π-stacking geometries and the role of the sulfur-centered hydrogen bonds.

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Switching Hydrogen Bonding to π-Stacking: The Thiophenol Dimer and Trimer

Saragi

Juanes

Pérez

et al. 2021

J. Phys. Chem. Lett.

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“…Armed with such an arsenal of techniques, our group carried out several gas-phase studies on model complexes − ,− and demonstrated, by considering the red shifts in vibrational frequencies of X–H oscillators, binding energies, geometrical parameters, and magnitude of donor–acceptor orbital overlap, that O–H···S and N–H···S/Se H-bonds have strengths comparable to those of conventional H-bonds. It was also concluded that those S/SeCHBs are a combination of electrostatic, charge-transfer, and dispersion forces. ,− The fascinating role of C–H···S/Se H-bonds in several biochemical systems, as well as in crystal structures, was noted. These H-bonds were earlier considered to be similar to van der Waals interactions .…”

Section: Hydrogen Bonds With Sulfur and Selenium: Changing Perceptionsmentioning

confidence: 97%

The Prodigious Hydrogen Bonds with Sulfur and Selenium in Molecular Assemblies, Structural Biology, and Functional Materials

et al. 2020

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Conspectus Hydrogen bonds (H-bonds) play important roles in imparting functionality to the basic molecules of life by stabilizing their structures and directing their interactions. Numerous studies have been devoted to understanding H-bonds involving highly electronegative atoms like nitrogen, oxygen, and halogens and consequences of those H-bonds in chemical reactions, catalysis, and structure and function of biomolecules; but the involvement of less electronegative atoms like sulfur and selenium in H-bond formation establishes the concept of noncanonical H-bonds. Initially belittled for the “weak” nature of their interactions, these perceptions have gradually evolved over time through dedicated efforts by several research groups. This has been facilitated by advancements in experimental methods for their detection through gas-phase laser spectroscopy and solution NMR spectroscopy, as well as through theoretical predictions from high level quantum chemical calculations. In this Account, we present insights into the versatility of the sulfur and selenium centered H-bonds (S/SeCHBs) by highlighting their multifarious applications in various fields from chemical reactions to optoelectronic properties to structural biology. Our group has highlighted the significance and strength of such H-bonds in natural and modified biomolecules. Here, we have reviewed several molecular assemblies, biomolecules, and functional materials, where the role of these H-bonds is pivotal in influencing biological functions. It is worth mentioning here that the precise experimental data obtained from gas-phase laser spectroscopy have contributed considerably to changing the existing perceptions toward S/SeCHBs. Thus, molecular beam experiments, though difficult to perform on smaller model thio- or seleno-substituted Molecules, etc. (amides, nucleobases, drug molecules), are inevitable to gather elementary knowledge and convincing concepts on S/SeCHBs that can be extended from a small four-atom sulfanyl dimer to a large 14 kDa iron–sulfur protein, ferredoxin. These H-bonds can also tailor a fascinating array of molecular frameworks and design supramolecular assemblies by inter- and intralinking of individual “molecular Lego-like” units. The discussion is indeed intriguing when it turns to the usage of S/SeCHBs in facile synthetic strategies like tuning regioselectivity in reactions, as well as invoking phenomena like dual phosphorescence and chemiluminescence. This is in addition to our investigations of the dispersive nature of the hydrogen bond between metal hydrides and sulfur or selenium as acceptor, which we anticipate would lead to progress in the areas of proton and hydride transfer, as well as force-field design. This Account demonstrates how ease of fabrication, enhanced efficiency, and alteration of physicochemical properties of several functional materials is facilitated owing to the presence of S/SeCHBs. Our efforts have been instrumental in the evaluation of various S/SeCHBs in flue gas capture, as well as design of organic ene...

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“…High-resolution rotationally-resolved 9,10 studies are still scarce, as illustrated by the hydrogen sulphide dimer, reported only in 2018. 11 To date, rotational spectroscopy has addressed several intra- 12,13,14 and intermolecular interactions in hydrogen sulfide dimers or sulfur-containing complexes, like O-H•••S, 15 18 and S-H•••. 19,20,21 The gas-phase information can thus complement previous molecular descriptions relying solely on crystal data 3 and theoretical calculations.…”

Section: Introductionmentioning

confidence: 99%