Halogen bond interaction: Role of hybridization and induction

Nunzi, Francesca; Cesario, Diego; Tarantelli, Francesco; Belpassi, Leonardo

doi:10.1016/j.cplett.2021.138522

Cited by 11 publications

(8 citation statements)

References 33 publications

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“…The positive potential is due in large part to the displacement of electron density that occurs when a σ(RX) bonding orbital is formed and occupied, shifting density to the internuclear region from the outside peripheral areas. This motion leaves a deficiency of density in what has come to be known as a σ-hole along the extension of the R–X axis. − The reduction in the density of this σ-hole is exacerbated if R is highly electronegative, which displaces the σ-orbital away from X to some extent. It is for this reason that this entire set of noncovalent bonds fall into a general category of “σ-hole bond”.…”

Section: Introductionmentioning

confidence: 99%

“…The intensive scrutiny of σ-hole bonds has led to a solid understanding of the fundamental phenomena from which they draw their strength. The chain of processes, beginning with the distortion of the σ(R–X) covalent bond arising from the R–X electronegativity difference, and the resulting σ-hole in the density, which in turn leads to the positive potential, have been characterized. ,,,− Also studied extensively has been the relationship between the magnitude of the σ-hole potential and the strength of the ensuing interaction with a nucleophile and how other factors enter into the equation such as charge transfer and dispersion. ,− Research has also built a body of understanding of the effects of the σ-hole bond on the intermolecular distance and perturbations within the individual monomers, both geometric and spectroscopic. − …”

Section: Introductionmentioning

confidence: 99%

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Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Scheiner

2021

J. Phys. Chem. A

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Accompanying the rapidly growing list of σ-hole bonds has come the acknowledgment of parallel sorts of noncovalent bonds which owe their stability in large part to a deficiency of electron density in the area above the molecular plane, known as a π-hole. The origins of these π-holes are probed for a wide series of molecules, comprising halogen, chalcogen, pnicogen, tetrel, aerogen, and spodium bonds. Much like in the case of their σ-hole counterparts, formation of the internal covalent π-bond in the Lewis acid molecule pulls density toward the bond midpoint and away from its extremities. This depletion of density above the central atom is amplified by an electron-withdrawing substituent. At the same time, the amplitude of the π*-orbital is enhanced in the region of the density-depleted π-hole, facilitating a better overlap with the nucleophile’s lone pair orbital and a stabilizing n → π* charge transfer. The presence of lone pairs on the central atom acts to attenuate the π-hole and shift its position somewhat, resulting in an overall weakening of the π-hole bond. There is a tendency for π-hole bonds to include a higher fraction of induction energy than σ-bonds with proportionately smaller electrostatic and dispersion components, but this distinction is less a product of the σ- or π-character and more a function of the overall bond strength.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Scheiner

2021

J. Phys. Chem. A

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“…Akin to related halogen bonds, charge transfer contributions are expected to be part of the interaction energy. [100][101][102][103][104][105] While the exact role of charge transfer in σ -hole interactions is still under debate, [106][107][108] the original AMOEBA force field expression suffers from a lack of explicit charge transfer description, 48 which could explain its collapse in the long-range. An adjustment of the multipoles (including higher order terms) and Van der Waals terms 109 (by softening the VdW radii 110,111 ) could be a route to retrieve the missing charge transfer term.…”

Section: Role Of Ncis In Benzotelluradiazole-classociationmentioning

confidence: 99%

Assessing the persistence of chalcogen bonds in solution with neural network potentials

Juraskova,

Celerse,

Laplaza

et al. 2022

Preprint

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Non-covalent bonding patterns are commonly harvested as a design principle in the field of catalysis, supramolecular chemistry and functional materials to name a few. Yet, their computational description generally neglects finite temperature and environment effects, which promote competing interactions and alter their static gas-phase properties. Recently, neural network potentials (NNPs) trained on Density Functional Theory (DFT) data have become increasingly popular to simulate molecular phenomena in condensed phase with an accuracy comparable to ab initio methods. To date, most applications have centered on solid-state materials or fairly simple molecules made of a limited number of elements. Herein, we focus on the persistence and strength of chalcogen bonds involving a benzotelluradiazole in condensed phase. While the tellurium-containing heteroaromatic molecules are known to exhibit pronounced interactions with anions and lone pairs of different atoms, the relevance of competing intermolecular interactions, notably with the solvent, are complicated to monitor experimentally but also challenging to model at an accurate electronic structure level. Here, we train a direct and baselined NNPs to reproduce hybrid DFT energies and forces in order to identify what are the most prevalent non-covalent interactions occurring in a solute-Cl --THF mixture. The simulations in explicit solvent highlight the clear competition with chalcogen bonds formed with the solvent and the short-range directionality of the interaction with direct consequences for the molecular properties in the solution. The comparison with other potentials (e.g., AMOEBA, direct NNP and continuum solvent model) also demonstrates that baselined NNPs offer a reliable picture of the non-covalent interaction interplay occurring in solution.

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“…However, this concept could not describe XBs in full. Numerous theoretical studies have shown that charge transfer, electrostatics, dispersion, and polarization interactions contribute to the XB. ,,− ,− …”

Section: Introductionmentioning

confidence: 99%

Solid-State ¹⁹F NMR Chemical Shift in Square-Planar Nickel–Fluoride Complexes Linked by Halogen Bonds

et al. 2023

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The halogen bond (XB) is a highly directional class of noncovalent interactions widely explored by experimental and computational studies. However, the NMR signature of the XB has attracted limited attention. The prediction and analysis of the solidstate NMR (SSNMR) chemical shift tensor provide useful strategies to better understand XB interactions. In this work, we employ a computational protocol for modeling and analyzing the 19 F SSNMR chemical shifts previously measured in a family of square-planar trans Ni II -L 2 -iodoaryl-fluoride (L = PEt 3 ) complexes capable of forming self-complementary networks held by a NiF••• I(C) halogen bond [Thangavadivale, V.; et al. Chem. Sci. 2018, 9, 3767−3781]. To understand how the 19 F NMR resonances of the nickel-bonded fluoride are affected by the XB, we investigate the origin of the shielding in trans-[NiF(2,3,5,6-C 6 F 4 I)(PEt 3 ) 2 ], trans-[NiF(2,3,4,5-C 6 F 4 I)(PEt 3 ) 2 ], and trans-[NiF(C 6 F 5 )(PEt 3) 2 ] in the solid state, where a XB is present in the two former systems but not in the last. We perform the 19 F NMR chemical shift calculations both in periodic and molecular models. The results show that the crystal packing has little influence on the NMR signatures of the XB, and the NMR can be modeled successfully with a pair of molecules interacting via the XB. Thus, the observed difference in chemical shift between solid-state and solution NMR can be essentially attributed to the XB interaction. The very high shielding of the fluoride and its driving contributor, the most shielded component of the chemical shift tensor, are well reproduced at the 2c-ZORA level. Analysis of the factors controlling the shielding shows how the highest occupied Ni/F orbitals shield the fluoride in the directions perpendicular to the Ni−F bond and specifically perpendicular to the coordination plane. This shielding arises from the magnetic coupling of the Ni(3d)/F(2p lone pair) orbitals with the vacant σ Ni−F * orbital, thereby rationalizing the very highly upfield (shielded) resonance of the component (δ 33 ) along this direction. We show that these features are characteristic of square-planar nickel−fluoride complexes. The deshielding of the fluoride in the halogen-bonded systems is attributed to an increase in the energy gap between the occupied and vacant orbitals that are mostly responsible for the paramagnetic terms, notably along the most shielded direction.

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Halogen bond interaction: Role of hybridization and induction

Cited by 11 publications

References 33 publications

Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Assessing the persistence of chalcogen bonds in solution with neural network potentials

Solid-State ¹⁹F NMR Chemical Shift in Square-Planar Nickel–Fluoride Complexes Linked by Halogen Bonds

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Halogen bond interaction: Role of hybridization and induction

Cited by 11 publications

References 33 publications

Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Assessing the persistence of chalcogen bonds in solution with neural network potentials

Solid-State 19F NMR Chemical Shift in Square-Planar Nickel–Fluoride Complexes Linked by Halogen Bonds

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Product

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Solid-State ¹⁹F NMR Chemical Shift in Square-Planar Nickel–Fluoride Complexes Linked by Halogen Bonds