The ab initio study of halogen and hydrogen σ N -bonded para -substituted pyridine⋯(X 2 /XY/HX) complexes

Sládek, Vladimı́r; Škorňa, Peter; Poliak, Peter; Lukeš, Vladimı́r

doi:10.1016/j.cplett.2014.11.026

Cited by 14 publications

(15 citation statements)

References 28 publications

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“…In the first place, it has been tested and found successful repeatedly in applications of noncovalent interactions . The latter included halogen bonds, and even anionic systems not entirely unlike those considered here. Other types of related systems for which it has found good success include HBs, both neutral, and those involving an anion, especially pertinent here.…”

Section: Discussionmentioning

confidence: 98%

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Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Scheiner

2016

Chemistry A European J

101

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The interactions of halides with a number of bipodal receptors were examined by quantum chemical methods. The receptors were based on a dithieno thiophene framework in which two S atoms can engage in a pair of chalcogen bonds with a halide. These two S atoms were replaced by P and As atoms to compare chalcogen with pnicogen bonding, and by Ge which engages in tetrel bonds with the receptor. Zero, one, and two O atoms were added to the thiophene S atom which is not directly involved in the interaction with the halides. Fluoride bound the most strongly, followed by Cl , Br , and I , respectively. Replacing S by the pnicogen bonds of P strengthened the binding, as did moving down to As in the third row of the periodic table. A further large increment is associated with the switch to the tetrel bonds of Ge. Even though the thiophene S atom is remote from the binding site, each additional O atom added to it raises the binding energy, which can be quite large, as much as 63 kcal mol for the Ge⋅⋅⋅F interaction. The receptors have a pronounced selectivity for F over the other halides, as high as 27 orders of magnitude. The data suggest that incorporation of tetrel atoms may lead to new and more powerful halide receptors.

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Section: Discussionmentioning

confidence: 98%

“…[85] The latter included halogen bonds, [86,87] and even anionic systems [88] not entirely unlike those considered here. In the first place, it has been tested and found successfulr epeatedly in applications of noncovalent interactions.…”

Section: Discussionmentioning

confidence: 99%

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Scheiner

2016

Chemistry A European J

101

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“…They do not represent a fifth covalent bond around the S which would alter its overall geometry. Nor is the formation of a chalcogen (or pnicogen or halogen) bond impeded by the presence of one or more lone pairs on the central atom in the general direction[37][38][39][40][41][42][43][44][45][46][47][48] of the noncovalent bond. The equatorial SF bonds have associated with them a vacant position which may be occupied by a S••O chalcogen bond.…”

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confidence: 99%

Intramolecular S···O Chalcogen Bond as Stabilizing Factor in Geometry of Substituted Phenyl-SF₃Molecules

Nziko

Scheiner

2015

J. Org. Chem.

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Density functional methods are used to examine the geometries and energetics of molecules containing a phenyl ring joined to the trigonal bipyramidal SF3 framework. The phenyl ring has a strong preference for an equatorial position. This preference remains when one or two ether -CH2OCH3 groups are added to the phenyl ring, ortho to SF3, wherein an apical structure lies nearly 30 kcal/mol higher in energy. Whether equatorial or apical, the molecule is stabilized by a S···O chalcogen bond, sometimes augmented by CH···F or CH···O H-bonds. The strength of the intramolecular S···O bond is estimated to lie in the range between 3 and 6 kcal/mol. A secondary effect of the S···O chalcogen bond is elongation of the S-F bonds. Solvation of the molecule strengthens the S···O interaction. Addition of substituents to the phenyl ring has only modest effects upon the S···O bond strength. A strengthening arises when an electron-withdrawing substituent is placed ortho to the ether and meta to SF3, while electron-releasing species produce an opposite effect.

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“… The fourth reaction is a transient cation–molecule complex formation (TC) owing to an ion−dipole interaction [ 106 ]. The constituent units interact electrostatically due to the attractive force between the charge of the H 2 + ions and the permanent dipole moment (2.21 D [ 107 ]) of pyridine. Akin to the charge transfer reaction, the complex formation occurs at a relatively long projectile−target distance.…”

Section: Resultsmentioning

confidence: 99%

Neutral Dissociation of Pyridine Evoked by Irradiation of Ionized Atomic and Molecular Hydrogen Beams

Wąsowicz

2021

IJMS

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The interactions of ions with molecules and the determination of their dissociation patterns are challenging endeavors of fundamental importance for theoretical and experimental science. In particular, the investigations on bond-breaking and new bond-forming processes triggered by the ionic impact may shed light on the stellar wind interaction with interstellar media, ionic beam irradiations of the living cells, ion-track nanotechnology, radiation hardness analysis of materials, and focused ion beam etching, deposition, and lithography. Due to its vital role in the natural environment, the pyridine molecule has become the subject of both basic and applied research in recent years. Therefore, dissociation of the gas phase pyridine (C5H5N) into neutral excited atomic and molecular fragments following protons (H+) and dihydrogen cations (H2+) impact has been investigated experimentally in the 5–1000 eV energy range. The collision-induced emission spectroscopy has been exploited to detect luminescence in the wavelength range from 190 to 520 nm at the different kinetic energies of both cations. High-resolution optical fragmentation spectra reveal emission bands due to the CH(A2Δ → X2Πr; B2Σ+ → X2Πr; C2Σ+ → X2Πr) and CN(B2Σ+ → X2Σ+) transitions as well as atomic H and C lines. Their spectral line shapes and qualitative band intensities are examined in detail. The analysis shows that the H2+ irradiation enhances pyridine ring fragmentation and creates various fragments more pronounced than H+ cations. The plausible collisional processes and fragmentation pathways leading to the identified products are discussed and compared with the latest results obtained in cation-induced fragmentation of pyridine.

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The ab initio study of halogen and hydrogen σ N -bonded para -substituted pyridine⋯(X 2 /XY/HX) complexes

Cited by 14 publications

References 28 publications

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Intramolecular S···O Chalcogen Bond as Stabilizing Factor in Geometry of Substituted Phenyl-SF₃Molecules

Neutral Dissociation of Pyridine Evoked by Irradiation of Ionized Atomic and Molecular Hydrogen Beams

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The ab initio study of halogen and hydrogen σ N -bonded para -substituted pyridine⋯(X 2 /XY/HX) complexes

Cited by 14 publications

References 28 publications

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Intramolecular S···O Chalcogen Bond as Stabilizing Factor in Geometry of Substituted Phenyl-SF3Molecules

Neutral Dissociation of Pyridine Evoked by Irradiation of Ionized Atomic and Molecular Hydrogen Beams

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Intramolecular S···O Chalcogen Bond as Stabilizing Factor in Geometry of Substituted Phenyl-SF₃Molecules