Rotational spectroscopic studies of the tetrel bonded CH3CN-CO2 complex

Gnanasekar, Sharon Priya; Arunan, E.

doi:10.1016/j.jms.2022.111671

Cited by 8 publications

(2 citation statements)

References 44 publications

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“…The σ-hole is a region of positive electrostatic potential along the direction of the extension of a σ bond axis (C-X in the case of carbon bonding). Akin to the hydrogen bond, a carbon bond is depicted as X-C···Y where X is more electronegative than carbon, and Y is, e.g., but not limited to, a molecule containing atoms with lone-pair(s) of electrons. ,,− Similar to hydrogen bonding, electrostatic interactions and orbital interactions are the two major contributors to the stabilization of carbon-bonding interactions . In the case of lone-pair containing molecules acting as Lewis base in hydrogen bonding, the lone-pair occupied orbitals interact with the H-X sigma antibonding orbital, with significant charge transfer taking place from the lone-pair orbital to the H-X antibonding orbital.…”

Section: Introductionmentioning

confidence: 99%

Cooperativity between Intermolecular Hydrogen and Carbon Bonds in ZY···CH₃CN/CH₃NC···HX Trimers (ZY = H₂O, H₂S, HF, HCl, HBr, NH₃, and H₂CO; HX = HF, HCl, and HBr)

Gupta,

Singha,

Mani

2024

J. Phys. Chem. A

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Hydrogen-bonding and carbon-bonding interactions are widespread in nature. We studied the cooperativity between these interactions in 42 trimeric complexes ZY•••CH 3 CN/CH 3 NC•••HX, where ZY molecules are H 2 O, H 2 S, HF, HCl, HBr, NH 3 , and H 2 CO, and HX molecules are HF, HCl, and HBr. Acetonitrile (CH 3 CN) and isoacetonitrile (CH 3 NC) act as hydrogen bond acceptors as well as carbon bond donors in these trimers. Various theoretical methods, such as electronic structure calculations, quantum theory of atoms in molecule (QTAIM), natural bond orbital (NBO), and reduced density gradient analysis, are employed to study these trimers, and the results are compared with the corresponding ZY•••CH 3 CN/CH 3 NC and CH 3 CN/CH 3 NC•••HX dimers.Electronic structure calculations are performed at the second-order Mo̷ ller-Plesset perturbation theory using the 6-311+ +G(2d,2p) basis set. We show that both the interactions act synergistically in these trimers leading to an increase in their bond strength as compared to the strength in the individual dimers. The cooperative energies for these trimers are in the range of 0.69 to 3.22 kJ/mol. It is seen that the carbon bonds benefit more from the cooperativity than the hydrogen bonds. The trends of cooperativity and correlations of interaction energies and cooperative energies with relevant QTAIM and NBO parameters are reported.

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Section: Introductionmentioning

confidence: 99%

Cooperativity between Intermolecular Hydrogen and Carbon Bonds in ZY···CH₃CN/CH₃NC···HX Trimers (ZY = H₂O, H₂S, HF, HCl, HBr, NH₃, and H₂CO; HX = HF, HCl, and HBr)

Gupta,

Singha,

Mani

2024

J. Phys. Chem. A

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“…For instance, the complexes of CO 2 with formic acid 12 and acrylic acid 13 are characterized by a dominant O−H•••O HB and a secondary O�C•••O TB. In contrast, when CO 2 links with molecules like benzaldehyde, 14 acetophenone, 15 formamide, 16 acetonitrile, 17 phenylmethanol, 18 difluoromethane, 19 1,1-difluoroethylene, 20 ethylene oxide/ethylene sulfide 21 and phenyl isothiocyanate, 22 the primary interaction becomes the O�C•••O/N/π/F/S TB, with secondary HBs contributing to the stability of these complexes.…”

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confidence: 99%

How Nonpolar CO₂ Aggregates on Cycloalkenes: A Case Study with Cyclopentene-(CO₂)_1–3 Clusters

Lei,

Tian,

Wang

et al. 2024

J. Phys. Chem. Lett.

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This study explores the molecular clusters of cyclopentene (CPE) with one to three CO 2 molecules (CPE-(CO 2 ) 1−3 ) through their jet-cooled rotational spectra using Fourier transform microwave spectroscopy with supplementary quantum chemical calculations. The assembly of CPE-(CO 2 ) 1−3 clusters is predominantly driven by tetrel bonding networks, notably C•••π(C� C) and C•••O interactions, with additional stabilization from weak C� H(CH 2 )•••C�O hydrogen bonds. Critically, the dispersive forces play a pivotal role in stabilizing CO 2 aggregation on CPE, eclipsing the effects of electrostatic and orbital interactions. This highlights the complex balance of forces that govern the formation and stabilization of these molecular clusters. Our findings offer precise insights into noncovalent interactions that could enhance atmospheric chemistry models and sustain climate science through informed environmental chemistry strategies.

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CO₂Aggregation on Monoethanolamine: Observations from Rotational Spectroscopy

et al. 2023

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The initial stages of the gas-phase nucleation between CO 2 and monoethanolamine were investigated via broadband rotational spectroscopy with the aid of extensive theoretical structure sampling. Sub-nanometer-scale aggregation patterns of monoethanolamine-(CO 2 ) n , n = 1-4, were identified. An interesting competition between the monoethanolamine intramolecular hydrogen bond and the intermolecular interactions between monoethanolamine and CO 2 upon cluster growth was discovered, revealing an intriguing CO 2 binding priority to the hydroxyl group over the amine group. These findings are in sharp contrast to the general results for aqueous solutions. In the quinary complex, a cap-like CO 2 tetramer was observed cooperatively surrounding the monoethanolamine. As the cluster approaches the critical size of new particle formation, the contribution of CO 2 self-assembly to the overall stability increases.

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Rotational spectroscopic studies of the tetrel bonded CH3CN-CO2 complex

Cited by 8 publications

References 44 publications

Cooperativity between Intermolecular Hydrogen and Carbon Bonds in ZY···CH₃CN/CH₃NC···HX Trimers (ZY = H₂O, H₂S, HF, HCl, HBr, NH₃, and H₂CO; HX = HF, HCl, and HBr)

Cooperativity between Intermolecular Hydrogen and Carbon Bonds in ZY···CH₃CN/CH₃NC···HX Trimers (ZY = H₂O, H₂S, HF, HCl, HBr, NH₃, and H₂CO; HX = HF, HCl, and HBr)

How Nonpolar CO₂ Aggregates on Cycloalkenes: A Case Study with Cyclopentene-(CO₂)_1–3 Clusters

CO₂Aggregation on Monoethanolamine: Observations from Rotational Spectroscopy

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Rotational spectroscopic studies of the tetrel bonded CH3CN-CO2 complex

Cited by 8 publications

References 44 publications

Cooperativity between Intermolecular Hydrogen and Carbon Bonds in ZY···CH3CN/CH3NC···HX Trimers (ZY = H2O, H2S, HF, HCl, HBr, NH3, and H2CO; HX = HF, HCl, and HBr)

Cooperativity between Intermolecular Hydrogen and Carbon Bonds in ZY···CH3CN/CH3NC···HX Trimers (ZY = H2O, H2S, HF, HCl, HBr, NH3, and H2CO; HX = HF, HCl, and HBr)

How Nonpolar CO2 Aggregates on Cycloalkenes: A Case Study with Cyclopentene-(CO2)1–3 Clusters

CO2Aggregation on Monoethanolamine: Observations from Rotational Spectroscopy

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Cooperativity between Intermolecular Hydrogen and Carbon Bonds in ZY···CH₃CN/CH₃NC···HX Trimers (ZY = H₂O, H₂S, HF, HCl, HBr, NH₃, and H₂CO; HX = HF, HCl, and HBr)

Cooperativity between Intermolecular Hydrogen and Carbon Bonds in ZY···CH₃CN/CH₃NC···HX Trimers (ZY = H₂O, H₂S, HF, HCl, HBr, NH₃, and H₂CO; HX = HF, HCl, and HBr)

How Nonpolar CO₂ Aggregates on Cycloalkenes: A Case Study with Cyclopentene-(CO₂)_1–3 Clusters

CO₂Aggregation on Monoethanolamine: Observations from Rotational Spectroscopy