Halogen bonds, chalcogen bonds, pnictogen bonds, tetrel bonds and other σ-hole interactions: a snapshot of current progress

Acta Crystallographica Section C Structural Chemistry, Journal Year: 2023, Volume and Issue: 79(6), P. 204 - 216

Published: May 15, 2023

We report here on the status of research halogen bonds and other σ-hole interactions involving p -block elements in Lewis acidic roles, such as chalcogen bonds, pnictogen tetrel bonds. A brief overview available literature this area is provided via a survey many review articles that address field. Our focus has been to collect together most published since 2013 provide an easy entry into extensive area. snapshot current by introduction virtual special issue compiled journal, comprising 11 entitled ` Halogen, chalcogen, bonds: structural chemistry beyond .'

Language: Английский

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Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non‐Covalent Organocatalysis: An Update

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 11, 2024

The use of noncovalent interactions based on electrophilic halogen, chalcogen, pnictogen, or tetrel centers in organocatalysis has gained noticeable attention. Herein, we provide an overview the most important developments last years with a clear focus experimental studies and catalysts which act via such non-transient interactions.

Language: Английский

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Aerogen Bond, Halogen Bond, Chalcogen Bond, Pnictogen Bond, Tetrel Bond, Triel Bond ... Why So Many Names?

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(10), P. 4003 - 4012

Published: May 6, 2024

The nomenclature exemplified in this paper's title has more terms than necessary. It conceals the often-similar physical natures of noncovalent interactions that it names, and pointlessly imitates term used for most important interaction, hydrogen bond. In doing so, becomes inconsistent with naming style covalent several interactions. other shortcomings attracted criticism from quarters. is suggested here simplest alternative consists three terms: σ-hole π-hole p-hole interaction. first two are well-known often regarded as implying an electrostatic Given Hellmann–Feynman theorem, expectation completely satisfied. Additional could be σ- or almost but not quite hypervalent dative ("perihypervalent bond" "pericovalent suggested). With some exceptions, argued "interaction" should preferred to "bond". Effecting a change would difficult. best started by open objective exchange views on current state

Language: Английский

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Definition of the Halogen Bond (IUPAC Recommendations 2013): A Revisit

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(13), P. 5494 - 5525

Published: June 24, 2024

This Article revisits the "Definition of Halogen Bond (IUPAC Recommendations 2013)" [Desiraju, G. R. Pure Appl. Chem. 2013, 85 (8), 1711–1713], recommendations that fail to include fundamental, underlying concept (electrophilic) σ- and p-/π-hole theory orbital-based charge transfer interactions accompany halogen bond formation. An electrophilic σ-hole, or p-/π-hole, is an electron-density-deficient region positive polarity (and potential) on electrostatic surface side along, orthogonal to, a covalently bonded in molecular entity leads development noncovalent interaction─a bond─when close proximity electron-density-rich nucleophilic same another identical different entity, with which it interacts. re-examines characteristic features lists wide variety donors acceptors participate bonding. We add caveats are essential for identifying bonding chemical systems, necessary appropriate use terminologies involved. Illustrative examples systems feature inter- intramolecular bonds other crystalline phase given, together case study some dimer using first-principles calculations. also point out π-hole/belt (or p-hole/belt) may develop derivative halogenated molecules be prone forming when nucleophiles similar entity.

Language: Английский

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From covalent to noncovalent: The role of metals in activating ligand sites toward noncovalent interactions (NCIs)

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 529, P. 216440 - 216440

Published: Jan. 15, 2025

Language: Английский

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

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(30), P. 7597 - 7602

Published: July 19, 2024

This study explores the molecular clusters of cyclopentene (CPE) with one to three CO2 molecules (CPE-(CO2)1–3) through their jet-cooled rotational spectra using Fourier transform microwave spectroscopy supplementary quantum chemical calculations. The assembly CPE-(CO2)1–3 is predominantly driven by tetrel bonding networks, notably C···π(C═C) and C···O interactions, additional stabilization from weak C─H(CH2)···C═O hydrogen bonds. Critically, dispersive forces play a pivotal role in stabilizing aggregation on CPE, eclipsing effects electrostatic orbital interactions. highlights complex balance that govern formation these clusters. Our findings offer precise insights into noncovalent interactions could enhance atmospheric chemistry models sustain climate science informed environmental strategies.

Language: Английский

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Halogen Bond via an Electrophilic π-Hole on Halogen in Molecules: Does It Exist?

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(9), P. 4587 - 4587

Published: April 23, 2024

This study reveals a new non-covalent interaction called π-hole halogen bond, which is directional and potentially non-linear compared to its sister analog (σ-hole bond). A shown here be observed on the surface of in halogenated molecules, can tempered display aptness form bond with series electron density-rich sites (Lewis bases) hosted individually by 32 other partner molecules. The [MP2/aug-cc-pVTZ] level characteristics bonds 33 binary complexes obtained from charge density approaches (quantum theory intramolecular atoms, molecular electrostatic potential, independent gradient model (IGM-δginter)), intermolecular geometries energies, second-order hyperconjugative transfer analyses are discussed, similar interactions. That molecules substantiated experimentally reported crystals documented Cambridge Crystal Structure Database. importance design growth chemical systems synthetic chemistry, crystallography, crystal engineering yet fully explicated.

Language: Английский

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Exploring the effect of substituents on the supramolecular assemblies built by non-covalent interactions in three closely related 1,3,4-oxadiazole-2(3H)-thione derivatives: An evaluation of antimicrobial and anti-proliferative activities

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1302, P. 137501 - 137501

Published: Jan. 5, 2024

Language: Английский

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Computational study on the characteristics of the complexes resulting from the interaction of carbonyl selenide and hypohalous acids

Molecular Physics, Journal Year: 2024, Volume and Issue: 122(17)

Published: Feb. 3, 2024

This study computationally investigates the properties and competition of complexes formed by interaction between hypohalous acids (HOX, where X = F, Cl, Br, I) carbonyl selenide (COSe) at MP2/aug-cc-pVTZ computational level. Three distinct groups were obtained. The first group, consisting with a cyclic structure (HB-TB), exhibited highest stability. remaining two less stable linear structures different characteristics (ChB XB). In electronegativity halogen atom significantly influenced stability complexes. Conversely, in II III was primarily determined acid base strengths interacting monomers. To comprehensively evaluate obtained results, various analyses employed, including Molecular electrostatic potential (MEP), geometry Optimization, Spectroscopic, Interaction energy (SE), Natural bond orbital (NBO) analysis, Atoms molecules (AIM) Non-covalent (NCI) index, Energy decomposition analysis (EDA), Electron density difference(EDD) analysis.

Language: Английский

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From ‘halogen’ to ‘tetrel’ bond: Matrix isolation IR spectroscopic and quantum mechanical studies on the effect of central atom substitution in donor tetrahalogens on binary complex formation with formic acid

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(32), P. 21538 - 21547

Published: Jan. 1, 2024

Binary complex formation between silicon tetrachloride (SiCl

Language: Английский

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