Halogen bonding and chalcogen bonding mediated sensing

Chemical Science, Journal Year: 2022, Volume and Issue: 13(24), P. 7098 - 7125

Published: Jan. 1, 2022

Sigma-hole interactions, in particular halogen bonding (XB) and chalcogen (ChB), have become indispensable tools supramolecular chemistry, with wide-ranging applications crystal engineering, catalysis materials chemistry as well anion recognition, transport sensing. The latter has very rapidly developed recent years is becoming a mature research area its own right. This can be attributed to the numerous advantages sigma-hole interactions imbue sensor design, high degrees of selectivity, sensitivity capability for sensing aqueous media. Herein, we provide first detailed overview all developments field XB ChB mediated sensing, detection anions but also neutral (gaseous) Lewis bases. includes wide range optical colorimetric luminescent sensors an array electrochemical sensors, most notably redox-active host systems. In addition, discuss other designs, including capacitive chemiresistors, outlook future fundamental field. Importantly concepts methodologies described herein anions, are generically applicable development receptors general, those cations molecules employing non-covalent interactions. As such believe this review useful guide both general community interests fields host-guest recognition small molecule Moreover, highlight need broader integration analytical synthetic science next generation potent sensors.

Language: Английский

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The Realm of Unconventional Noncovalent Interactions in Proteins: Their Significance in Structure and Function

ACS Omega, Journal Year: 2023, Volume and Issue: 8(25), P. 22268 - 22284

Published: June 13, 2023

Proteins and their assemblies are fundamental for living cells to function. Their complex three-dimensional architecture its stability attributed the combined effect of various noncovalent interactions. It is critical scrutinize these interactions understand role in energy landscape folding, catalysis, molecular recognition. This Review presents a comprehensive summary unconventional interactions, beyond conventional hydrogen bonds hydrophobic which have gained prominence over past decade. The discussed include low-barrier bonds, C5 C-H···π sulfur-mediated n → π* London dispersion halogen chalcogen tetrel bonds. focuses on chemical nature, interaction strength, geometrical parameters obtained from X-ray crystallography, spectroscopy, bioinformatics, computational chemistry. Also highlighted occurrence proteins or complexes recent advances made toward understanding biomolecular structure Probing diversity we determined that variable frequency ability synergize with one another important not only ab initio prediction but also design new functionalities. A better will promote utilization designing engineering ligands potential therapeutic value.

Language: Английский

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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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The Matere Bond

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This article explores matere bonds, supported by theoretical and computational studies. These σ-hole interactions with group 7 elements (Mn, Tc, Re) are key in crystal engineering, catalysis, biological systems.

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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Anion⋯anion self-assembly under the control of σ- and π-hole bonds

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(13), P. 6654 - 6674

Published: Jan. 1, 2024

The electrostatic attraction between charges of opposite signs and the repulsion same sign are ubiquitous influential phenomena in recognition self-assembly processes. However, it has been recently revealed that specific attractive forces ions with relatively common. These can be strong enough to overcome Coulomb sign, leading formation stable anion⋯anion cation⋯cation adducts. Hydroden bonds (HBs) probably best-known interaction effectively direct these counterintuitive assembly In this review we discuss how σ-hole π-hole break paradigm like-charges drive anions into discrete as well one-, two-, or three-dimensional σ-Hole regions excess electron density molecular entities (

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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Intermolecular Covalent Interactions: Nature and Directionality

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(14)

Published: Dec. 7, 2022

Quantum chemical methods were employed to analyze the nature and origin of directionality pnictogen (PnB), chalcogen (ChB), halogen bonds (XB) in archetypal Fm Z⋅⋅⋅F- complexes (Z=Pn, Ch, X), using relativistic density functional theory (DFT) at ZORA-M06/QZ4P. Quantitative Kohn-Sham MO energy decomposition analyses (EDA) show that all these intermolecular interactions have common covalence, is, HOMO-LUMO interactions, provide a crucial contribution bond energy, besides electrostatic attraction. Strikingly, are directional (i.e., F-Z⋅⋅⋅F- is approximately linear) despite, not because of, which, fact, favor bending. This constitutes breakdown σ-hole model. It was shown how model fails by neglecting both, essential physics behind interaction electron-rich interactions. Our findings general extend neutral, weaker ClI⋅⋅⋅NH3 , HClTe⋅⋅⋅NH3 H2 ClSb⋅⋅⋅NH3 complexes.

Language: Английский

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A new look at the chalcogen bond: π-hole-based chalcogen (Se, Te) bonding which does not include a σ-hole interaction

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(10), P. 3065 - 3081

Published: Jan. 1, 2023

Chalcogen bonding which does not include σ-hole interaction.

Language: Английский

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“Anti‐electrostatic” Halogen Bonding between Ions of Like Charge

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(67), P. 16530 - 16542

Published: Aug. 19, 2021

Abstract Halogen bonding occurs between molecules featuring Lewis acidic halogen substituents and bases. It is often rationalized as a predominantly electrostatic interaction thus interactions ions of like charge (e. g., anionic bond donors with halides) seem counter‐intuitive. Herein, we provide an overview on such complexes. First, theoretical studies are described their findings compared. Next, experimental evidences presented in the form crystal structure database analyses, recent examples strong “anti‐electrostatic” crystals, observation also solution. We then compare these complexes to select “counter‐intuitive” adducts formed by other interactions, hydrogen bonding. Finally, comment key differences charge‐transfer polarization.

Language: Английский

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