Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies

Kannan, P.; Karthick, N.; Mahendraprabu, A.; Shanmugam, Ramasamy; Elangovan, A.; Arivazhagan, G.

doi:10.1016/j.molstruc.2017.03.036

Cited by 53 publications

(18 citation statements)

References 35 publications

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“…Blue-shifting H-bonding due to its contrasting characteristics, vis-à-vis conventional red-shifting H-bonding, has been the subject of intense research over the past decade or so. − Conventional H-bonding (X–H···Y) is normally characterized by weak interaction involving a proton donor, X, a hydrogen atom, and a proton acceptor, Y . The interaction is predominantly electrostatic, and the electronegative Y attracts the hydrogen toward itself which lengthens the X–H bond, leading to red-shifting of the X–H stretching frequency. , This was understood by the community well until the work of Budesinsky et al, where they reported a 7 cm –1 blue shift of the C–H stretching frequency of chloroform when triformylethane was added to it in solution.…”

Section: Introductionmentioning

confidence: 99%

Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR′CO···DCCl₃ and RR′S···DCCl₃ Complexes

Behera

Das

2018

J. Phys. Chem. A

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Blue-shifting H-bonded (C-D···O) complexes between CDCl and CHHCO, (CH)CO, and CH(CH)CO, and red-shifting H-bonded (C-D···S) complexes between CDCl with (CH)S and (CH)S have been identified by Fourier transform infrared spectroscopy in the gas phase at room temperature. With increasing partial pressure of the components, a new band appears in the C-D stretching region of the vibrational spectra. The intensity of this band decreases with an increase in temperature at constant pressure, which provides the basis for identification of the H-bonded bands in the spectrum. The C-D stretching frequency of CDCl is blue-shifted by +7.1, +4, and +3.2 cm upon complexation with CHHCO, (CH)CO, and CH(CH)CO, respectively, and red-shifted by -14 and -19.2 cm upon complexation with (CH)S and (CH)S, respectively. By using quantum chemical calculations at the MP2/6-311++G** level, we predict the geometry, electronic structural parameters, binding energy, and spectral shift of H-bonded complexes between CDCl and two series of compounds named RCOR' (HCO, CHHCO, (CH)CO, and CH(CH)CO) and RSR' (HS, CHHS, (CH)S, and (CH)S) series. The calculated and observed spectral shifts follow the same trends. With an increase in basicity of the H-bond acceptor, the C-D bond length increases, force constant decreases, and the frequency shifts to the red from the blue. The potential energy scans of the above complexes are done, which show that electrostatic attraction between electropositive D and electron-rich O/S causes bond elongation and red shift, and the electronic and nuclear repulsions lead to bond contraction and blue shifts. The dominance of the two opposing forces at the equilibrium geometry of the complex determines the nature of the shift, which changes both in magnitude and in direction with the basicity of the hydrogen-bond acceptor.

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Section: Introductionmentioning

confidence: 99%

Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR′CO···DCCl₃ and RR′S···DCCl₃ Complexes

Behera

Das

2018

J. Phys. Chem. A

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“…Molecules 2021, 26, x 11 of 17 hydrogen bonding, presence of water molecule in the chemical structure, and dipole-dipole interactions [45,46]. Our analysis showed the presence of Na and Ca ions in the plant exudates.…”

Section: Fourier-transform Infrared Spectroscopy (Ftir) Analysismentioning

confidence: 82%

“…The figure shows these three peaks in plant exudates with a slight shift in position. Several studies have shown that the FTIR peak shift can occur for various reasons, including specific molecular interactions, such as hydrogen bonding, presence of water molecule in the chemical structure, and dipole–dipole interactions [ 45 , 46 ]. Our analysis showed the presence of Na and Ca ions in the plant exudates.…”

Section: Resultsmentioning

confidence: 99%

Evidence for Phytoremediation and Phytoexcretion of NTO from Industrial Wastewater by Vetiver Grass

et al. 2020

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The use of insensitive munitions such as 3-nitro-1,2,4-triazol-5-one (NTO) is rapidly increasing and is expected to replace conventional munitions in the near future. Various NTO treatment technologies are being developed for the treatment of wastewater from industrial munition facilities. This is the first study to explore the potential phytoremediation of industrial NTO-wastewater using vetiver grass (Chrysopogon zizanioides L.). Here, we present evidence that vetiver can effectively remove NTO from wastewater, and also translocated NTO from root to shoot. NTO was phytotoxic and resulted in a loss of plant biomass and chlorophyll. The metabolomic analysis showed significant differences between treated and control samples, with the upregulation of specific pathways such as glycerophosphate metabolism and amino acid metabolism, providing a glimpse into the stress alleviation strategy of vetiver. One of the mechanisms of NTO stress reduction was the excretion of solid crystals. Scanning electron microscopy (SEM), electrospray ionization mass spectrometry (ESI-MS), and Fourier-transform infrared spectroscopy (FTIR) analysis confirmed the presence of NTO crystals in the plant exudates. Further characterization of the exudates is in progress to ascertain the purity of these crystals, and if vetiver could be used for phytomining NTO from industrial wastewater.

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“…The blue shifting H-bond has received a significant experimental and theoretical interest due to its contrasting characteristics from the conventional red shifting H-bond. − The conventional H-bond (X−H···Y) is formed when a covalently bonded H atom of a proton donor (X−H) interacts with a lone pair or an electron rich center of a proton acceptor (Y) . The interaction is primarily electrostatic in nature where the electronegative Y attracts H toward itself which lengthens the X−H bond, leading to a red shift of the X−H stretching frequency and an increase in intensity.…”

Section: Introductionmentioning

confidence: 99%

Blue-Shifted Hydrogen Bonding in the Gas Phase CH/D₃CN···HCCl₃ Complexes

Behera

Das

2019

J. Phys. Chem. A

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Blue-shifting H-bonded complexes between CHCl 3 and CH/D 3 CN have been identified by Fourier transform infrared spectroscopy in the gas phase at room temperature. The change in FTIR peak intensity of the mixture of the two components as a function of temperature and composition provides the basis for identification of the H-bonded band in the infrared spectrum. On complex formation with CH 3 CN and CD 3 CN, the C−H stretching frequency of CHCl 3 shifts to the blue by +8.7 and +8.6 cm −1 , respectively. The molecular electrostatic potential calculation at the MP2/6-311++G** level has been used to arrive at the geometry of the complex. It has been reported in the literature that CHCl 3 and CH/D 3 CN form red-shifting H-bonded complex in Ar matrix. The red shifting has been verified by doing ab initio calculations in the presence of Ar atoms, which has been attributed to the matrix effect at low temperature. The interaction of Ar with CH 3 CN makes the CH 3 CN more basic and as a result it becomes better hydrogen bond acceptor and causes red shift. The potential energy scans and NBO analysis of the Cl 3 CH•••NCCH 3 complex have been compared with those of F 3 CH•••NCCH 3 and Cl 3 CH•••NH 3 complexes. The change in electron density of the CHCl 3 as a function of C−H•••N distance shows that the approach of CH 3 CN to CHCl 3 induces a shift in electron density from the H atom to the Cl atoms of CHCl 3 which leads to C−H bond contraction and blue shifting of C−H stretching frequency. However, in the complex Cl 3 CH•••NH 3 , where frequency shift to the red is reported, charge transfer and electrostatic interaction dominate.

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Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies

Cited by 53 publications

References 35 publications

Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR′CO···DCCl₃ and RR′S···DCCl₃ Complexes

Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR′CO···DCCl₃ and RR′S···DCCl₃ Complexes

Evidence for Phytoremediation and Phytoexcretion of NTO from Industrial Wastewater by Vetiver Grass

Blue-Shifted Hydrogen Bonding in the Gas Phase CH/D₃CN···HCCl₃ Complexes

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Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies

Cited by 53 publications

References 35 publications

Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR′CO···DCCl3 and RR′S···DCCl3 Complexes

Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR′CO···DCCl3 and RR′S···DCCl3 Complexes

Evidence for Phytoremediation and Phytoexcretion of NTO from Industrial Wastewater by Vetiver Grass

Blue-Shifted Hydrogen Bonding in the Gas Phase CH/D3CN···HCCl3 Complexes

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Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR′CO···DCCl₃ and RR′S···DCCl₃ Complexes

Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR′CO···DCCl₃ and RR′S···DCCl₃ Complexes

Blue-Shifted Hydrogen Bonding in the Gas Phase CH/D₃CN···HCCl₃ Complexes