Reversal of the usual spectral shift of haloforms in some hydrogen-bonded complexes

Boldeskul, I. E.; Цымбал, И. Ф.; Ryl'tsev, E. V.; Latajka, Zdzisław; Barnes, Austin J.

doi:10.1016/s0022-2860(97)00137-3

Cited by 117 publications

(79 citation statements)

References 3 publications

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“…However, reading the literature carefully, we found a few studies [177][178][179] showing that the X-H...Y arrangement (which is attractive) can be also accompanied by an opposite geometrical and spectral manifestation. Instead of elongation of the X-H bond accompanied by a red shift of the X-H stretching vibration, the contraction of this bond and an associated blue shift of the respective stretching have also been detected.…”

Section: Hydrogen Bonding and Improper Hydrogen Bondingmentioning

confidence: 97%

The World of Non-Covalent Interactions: 2006

Hobza¹,

Zahradník²,

Müller‐Dethlefs³

2006

Collect. Czech. Chem. Commun.

241

235

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The review focusses on the fundamental importance of non-covalent interactions in nature by illustrating specific examples from chemistry, physics and the biosciences. Laser spectroscopic methods and both ab initio and molecular modelling procedures used for the study of non-covalent interactions in molecular clusters are briefly outlined. The role of structure and geometry, stabilization energy, potential and free energy surfaces for molecular clusters is extensively discussed in the light of the most advanced ab initio computational results for the CCSD(T) method, extrapolated to the CBS limit. The most important types of non-covalent complexes are classified and several small and medium size non-covalent systems, including H-bonded and improper H-bonded complexes, nucleic acid base pairs, and peptides and proteins are discussed with some detail. Finally, we evaluate the interpretation of experimental results in comparison with state of the art theoretical models: this is illustrated for phenol...Ar, the benzene dimer and nucleic acid base pairs. A review with 270 references.

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Section: Hydrogen Bonding and Improper Hydrogen Bondingmentioning

confidence: 97%

The World of Non-Covalent Interactions: 2006

Hobza¹,

Zahradník²,

Müller‐Dethlefs³

2006

Collect. Czech. Chem. Commun.

241

235

View full text Add to dashboard Cite

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“…To maximise this attraction, the O-H bond length shortens. Boldeskul et al explain this occurrence in chloroform-nitro systems as an increase in the s character of the C-H bond owing to molecular deformation caused by intermolecular forces [28]. Admittedly, this does not account for all systems involving improper blue shift hydrogen bonding, so additional terms are required to adequately explain this type of hydrogen bonding.…”

Section: Hydrogen Bondingmentioning

confidence: 99%

“…This might mean the nitrile groups are more likely to interact with each other in the swollen state of the polymer, and the adsorption of alcohols undermines this interaction. Because the red shift is correlated to the hydrogen bond strength [19,28,29], relative magnitudes of frequency shifts have been used to compare hydrogen bond strengths. The larger the red shift, the stronger the hydrogen bonding causing it.…”

Section: Hydrogen Bondingmentioning

confidence: 99%

Interaction of a Polymer of Intrinsic Microporosity (PIM-1) with Penetrants

Chaukura¹

2015

AJAC

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Abstract:The characterisation, solubility testing, and alcohol adsorption studies of PIM-1 are reported. Techniques used for characterisation are N 2 sorption and ATR-FTIR analysis. A number of solvents were tested for their ability to dissolve low molecular weight (~30 000 gmol -1 ), medium molecular weight (~60 000 gmol -1 ), and high molecular weight (~120 000 gmol -1 ) PIM-1.Results showed solubility of PIM-1 in these solvents to be dependent on molar mass. CHCl 3 , tetrahydrofuran (THF), CH 2 Cl 2 , dicholobenzene (DCB), 1,2,4-trichlorobenzene (TCB), and acetophenone were found to be good solvents at all molecular weights. Treatment of PIM-1 with nonsolvents, namely: small alcohols and water, followed by solvent removal, caused swelling, resulting in an increase in BET surface area of about 11 %, except for water, which reduced BET surface area by the same amount (11 %). Methanol (MeOH) treatment resulted in a new population of micropores around 0.6 nm. The change after ethanol (EtOH) and propanol (PrOH) treatment was not as significant. Hydrogen bonding between alcohols and PIM-1 was also investigated using shifts in the frequencies of FTIR peaks for the ether and the nitrile functional groups. Nitrile group frequencies for the alcohols were consistently blue-shifted, whereas the ether frequencies were red shifted. Both red-and blue-shifts were used as a measure of hydrogen bond strength.

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“…[1][2][3] The first systematic study showing that H-bonding could be connected with a completely opposite manifestation, that is, bond contraction and a blue-shift of the X-H stretch frequency, appeared in 1998 [4] and earlier experimental evidence supports this. [5][6][7][8] The literature on the blue-shifting H bonds up to the year 2000 was reviewed in ref. [9] and is growing rapidly now.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigations into the Blue‐Shifting Hydrogen Bond in Benzene Complexes

Špirko¹,

Hobza²

2006

ChemPhysChem

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The benzene...X complexes (X=benzene, antracene, ovalene) were optimised at the MP2/6-31G** level with the C2v symmetry of the complex and planarity of the proton acceptor being preserved. The resulting stabilisation energies amount to 1.2, 2.3 and 2.9 kcal mol(-1), and the C-H bond of the proton donor is contracted by 0.0035, 0.0052 and 0.0055 A, respectively. The contraction is connected with a blue-shift of the C-H stretch vibration frequency. A two-dimensional anharmonic vibration treatment based on a MP2/6-31G** potential energy surface yields the following blue shifts for the complexes studied: 28, 42 and 43 cm(-1). The dominant attraction in the complexes is London dispersion, while the attractive contribution from electrostatic quadrupole-quadrupole interactions is considerably smaller.

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Reversal of the usual spectral shift of haloforms in some hydrogen-bonded complexes

Cited by 117 publications

References 3 publications

The World of Non-Covalent Interactions: 2006

The World of Non-Covalent Interactions: 2006

Interaction of a Polymer of Intrinsic Microporosity (PIM-1) with Penetrants

Theoretical Investigations into the Blue‐Shifting Hydrogen Bond in Benzene Complexes

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