Can non-polar hydrogen atoms accept hydrogen bonds?

Yang, Lixu; Hubbard, Thomas A.; Cockroft, Scott L.

doi:10.1039/c3cc46048g

Cited by 36 publications

(49 citation statements)

References 31 publications

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“…In neat HFIP the SiH resonances appear strongly up‐field (Δ δ SiH =−0.1 to −1.1 ppm) relative to their position in noncoordinating solvents ([D 6 ]benzene, [D 8 ]toluene, methylcyclohexane‐ d 14 ) or in neat silane even at room temperature (Table S3). That conforms the criteria of DHB formation and is in line with the up‐field chemical shift of ν SiH resonance by 0.2 ppm observed for ( n ‐Hex) 3 SiH:PFTB at a very high molar ratio (1:56) . We used 1 H NOE difference spectroscopy to get further NMR proofs of SiH⋅⋅⋅HO interaction.…”

Section: Resultssupporting

confidence: 78%

Comprehensive Insight into the Hydrogen Bonding of Silanes

Voronova

Golub

Павлов

et al. 2018

Chemistry An Asian Journal

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The interaction of a set of mono-, di- and trisubstituted silanes with OH proton donors of different strength was studied by variable temperature (VT) FTIR and NMR spectroscopies at 190-298 K. Two competing sites of proton donors coordination: SiH and π-density of phenyl rings-are revealed for phenyl-containing silanes. The hydrogen bonds SiH⋅⋅⋅HO and OH⋅⋅⋅π(Ph) are of similar strength, but can be distinguished in the ν range: the ν vibrations appear at lower frequencies while OH⋅⋅⋅π(Ph) complexes give Si-H vibrations shifted to higher frequency. The calculations showed the manifold picture of the noncovalent interactions in hydrogen-bonded complexes of phenylsilanes. As OH⋅⋅⋅HSi bonds are weak, the other noncovalent interactions compete in the stabilization of the intermolecular complexes. Still, the structural and electronic parameters of "pure" DHB complexes of phenylsilanes are similar to those of Et SiH.

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Section: Resultssupporting

confidence: 78%

Comprehensive Insight into the Hydrogen Bonding of Silanes

Voronova

Golub

Павлов

et al. 2018

Chemistry An Asian Journal

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“…[11] Once the temporal shift of ESA1 and ESA2 is complete,b oth bands decay in around 1.5 ns,a sin the aprotic solvents.M ore pronounced spectral dynamics were observed in the most protic solvents,t rifluoroethanol (TFE, a = 1.51), hexafluoroisopropanol (HFP, a = 1.96,) and perfluoro-tert-butanol (NFB), with perfluoro-tert-butanol being the strongest H-bond donating solvent known. [14] Both bands shift even further than in the less-protic solvents (Figure 2). Global analysis reveals that this large shift is in fact due to the decay of ESA1 and the concurrent rise of anew band, ESA3, located at lower frequency ( Figure S19).…”

Section: Angewandte Chemiementioning

confidence: 93%

“…These time constants are in good agreement with those of solvent relaxation reported in the literature. [14] Both bands shift even further than in the less-protic solvents (Figure 2). [14] Both bands shift even further than in the less-protic solvents (Figure 2).…”

mentioning

confidence: 99%

Symmetry‐Breaking Charge Transfer and Hydrogen Bonding: Toward Asymmetrical Photochemistry

et al. 2016

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Symmetry-breaking charge transfer upon photoexcitation of al inear A-p-D-p-A molecule (D and Ab eing electron donating and accepting groups) could be visualized using ultrafast time-resolved infrared spectroscopyb ym onitoring the CN stretching modes on the Aunits.W hereas in apolar solvents,the S 1 state remains symmetric and quadrupolar,s ymmetry breaking occurs within ca. 100 fs in polar solvents as shown by the presence of two CN bands,instead of one in apolar solvents,w ith as plitting that increases with polarity.I np rotic solvents,s ymmetry breaking is significantly amplified by H-bonding interactions,which are the strongest at the CN group with the highest basicity.I ns trongly protic solvents,the two CN bands transform in about 20 ps into new bands with al arger splitting,a nd the lifetime of the S 1 state is substantially reduced. This is attributed to the formation of an excited asymmetric tight H-bond complex.Scheme 1. Structure of ADA.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.

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“…Once the temporal shift of ESA1 and ESA2 is complete, both bands decay in around 1.5 ns, as in the aprotic solvents. More pronounced spectral dynamics were observed in the most protic solvents, trifluoroethanol (TFE, α =1.51), hexafluoroisopropanol (HFP, α =1.96,) and perfluoro‐ tert ‐butanol (NFB), with perfluoro‐ tert ‐butanol being the strongest H‐bond donating solvent known . Both bands shift even further than in the less‐protic solvents (Figure ).…”

Section: Methodsmentioning

confidence: 99%

Symmetry‐Breaking Charge Transfer and Hydrogen Bonding: Toward Asymmetrical Photochemistry

et al. 2016

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Symmetry-breaking charge transfer upon photoexcitation of a linear A-π-D-π-A molecule (D and A being electron donating and accepting groups) could be visualized using ultrafast time-resolved infrared spectroscopy by monitoring the CN stretching modes on the A units. Whereas in apolar solvents, the S state remains symmetric and quadrupolar, symmetry breaking occurs within ca. 100 fs in polar solvents as shown by the presence of two CN bands, instead of one in apolar solvents, with a splitting that increases with polarity. In protic solvents, symmetry breaking is significantly amplified by H-bonding interactions, which are the strongest at the CN group with the highest basicity. In strongly protic solvents, the two CN bands transform in about 20 ps into new bands with a larger splitting, and the lifetime of the S state is substantially reduced. This is attributed to the formation of an excited asymmetric tight H-bond complex.

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Can non-polar hydrogen atoms accept hydrogen bonds?

Cited by 36 publications

References 31 publications

Comprehensive Insight into the Hydrogen Bonding of Silanes

Comprehensive Insight into the Hydrogen Bonding of Silanes

Symmetry‐Breaking Charge Transfer and Hydrogen Bonding: Toward Asymmetrical Photochemistry

Symmetry‐Breaking Charge Transfer and Hydrogen Bonding: Toward Asymmetrical Photochemistry

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