Ein bidentates Antimon‐Pniktogenbrücken‐Wirtsystem DOI Creative Commons
J. Louis Beckmann, Jonas Krieft, Yury V. Vishnevskiy

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(46)

Published: Sept. 29, 2023

Abstract Ein zweizähniges Pniktogenbrücken‐Wirtsystem auf der Basis von 1,8‐Diethinylanthracen wurde mittels einer selektiven Zinn‐Antimon‐Austauschreaktion hergestellt und seine Fähigkeit untersucht, als Lewis‐saure Wirtskomponente für die Komplexierung Lewis‐basischen oder anionischen Gästen zu fungieren. In dieser Arbeit mit C≡C−Sb(C 2 F 5 ) ‐Gruppe eine neuartige Akzeptorfunktion etabliert, das Potenzial Antimon(III)‐Funktionen Vertreter kaum erforschten Pniktogenbrücken‐Donatoren untersucht werden kann. Die Akzeptorfähigkeit dieses teilfluorierten Wirtsystems gegenüber Halogenidanionen (Cl − , Br I ), Dimethylchalkogeniden Me Y (Y = O, S, Se, Te) Stickstoffheterozyklen (Pyridin, Pyrimidin) untersucht. Einblicke in Adduktbildungsverhalten sowie Bindungssituation solcher E⋅⋅⋅Sb−C ‐Einheiten wurden Lösung NMR‐Spektroskopie, im festen Zustand durch Röntgenbeugung, Elementaranalysen rechnerische Methoden (DFT, QTAIM, IQA) gewonnen.

Anion⋯anion self-assembly under the control of σ- and π-hole bonds DOI Creative Commons
Andrea Pizzi, Arun Dhaka, Roberta Beccaria

et al.

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

Citations

10
Definition of the Halogen Bond (IUPAC Recommendations 2013): A Revisit DOI
Pradeep R. Varadwaj, Arpita Varadwaj, Helder M. Marques

et al.

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

Citations

10
A Bidentate Antimony Pnictogen Bonding Host System DOI Creative Commons
J. Louis Beckmann, Jonas Krieft, Yury V. Vishnevskiy

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 29, 2023

Abstract A bidentate pnictogen bonding host‐system based on 1,8‐diethynylanthracene was synthesized by a selective tin‐antimony exchange reaction and investigated regarding its ability to act as Lewis acidic host component for the complexation of basic or anionic guests. In this work, novel C≡C−Sb(C 2 F 5 ) unit established study potential antimony(III) sites representatives scarcely explored donors. The capability partly fluorinated system towards halide anions (Cl − , Br I ), dimethyl chalcogenides Me Y (Y=O, S, Se, Te), nitrogen heterocycles (pyridine, pyrimidine). Insights into adduct formation behavior well situation such E⋅⋅⋅Sb−C moieties were obtained in solution means NMR spectroscopy, solid state X‐ray diffraction, elemental analyses, computational methods (DFT, QTAIM, IQA), respectively.

Language: Английский

Citations

21
The Formation of σ-Hole Bonds: A Physical Interpretation DOI Creative Commons
Jane S. Murray

Molecules, Journal Year: 2024, Volume and Issue: 29(3), P. 600 - 600

Published: Jan. 26, 2024

This paper discusses two quite different computational experiments relating to the formation of σ-hole bonds A···B. The first involves looking at complex equilibrium and finding contour X electronic density which allows iso-density envelopes A B be nearly touching. increases, becoming closer nuclei, as strength interaction increases. second experiment allowing approach each other, with aim distance their 0.001 a.u. are merging into one envelope. What is found in may somewhat surprising, that ratio between interacting atoms this point-divided by sum van der Waals radii these atoms-covers a narrow range, typically 1.2 1.3. It intriguing note for dataset presented, approaching molecules attracted other appear do so unknowing ultimate interaction. also supports notion should expect favorable interactions, some instances, have close contacts significantly greater than sums radii.

Language: Английский

Citations

5
Halogen Bonds Formed by Halogen’s p/π-Hole in Molecules Help Shape Crystalline Materials DOI
Pradeep R. Varadwaj, Helder M. Marques, Ireneusz Grabowski

et al.

Crystal Growth & Design, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Language: Английский

Citations

0
Pd and Pt metal atoms as electron donors in σ-hole bonded complexes DOI Creative Commons
Wiktor Zierkiewicz, Beata Kizior, Mariusz Michalczyk

et al.

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(38), P. 26172 - 26184

Published: Jan. 1, 2023

In the investigated complexes, metal atom acts as a Lewis base, with occupied d z 2 orbital serving source of charge transferred to acid.

Language: Английский

Citations

3
A Model Halogen-Bonded Network as a Potential Tube-like Host for Li+: A DFT Study DOI Creative Commons

Rubén D. Parra

Inorganics, Journal Year: 2023, Volume and Issue: 12(1), P. 16 - 16

Published: Dec. 30, 2023

The formation of a halogen-bonded network using four NHX-(CH2)3-NX-(CH2)3-NHX molecules (X = Cl, Br, or I) is investigated DFT. self-assembly the basic motifs results in tube-like structure with C4h symmetry, one located at each end and its center. Each has quasi-planar N-X···N interactions binding energies that increase size X. found to bind Li+ networks, albeit more strongly driven by halogen atom lone pairs produce rich electron density orthogonal bond. presence strength are further examined AIM NBO calculations. Lastly, IRC calculations performed examine transitions between complex minima and, thus, potential for transporting metal ion from tube other. Based on tetrameric structure, model intramolecular built considered as host Li+. In this case, central intermolecular replaced an Si-C≡C-Si network. Interestingly, both structures exhibit similar abilities.

Language: Английский

Citations

2
Ein bidentates Antimon‐Pniktogenbrücken‐Wirtsystem DOI Creative Commons
J. Louis Beckmann, Jonas Krieft, Yury V. Vishnevskiy

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(46)

Published: Sept. 29, 2023

Abstract Ein zweizähniges Pniktogenbrücken‐Wirtsystem auf der Basis von 1,8‐Diethinylanthracen wurde mittels einer selektiven Zinn‐Antimon‐Austauschreaktion hergestellt und seine Fähigkeit untersucht, als Lewis‐saure Wirtskomponente für die Komplexierung Lewis‐basischen oder anionischen Gästen zu fungieren. In dieser Arbeit mit C≡C−Sb(C 2 F 5 ) ‐Gruppe eine neuartige Akzeptorfunktion etabliert, das Potenzial Antimon(III)‐Funktionen Vertreter kaum erforschten Pniktogenbrücken‐Donatoren untersucht werden kann. Die Akzeptorfähigkeit dieses teilfluorierten Wirtsystems gegenüber Halogenidanionen (Cl − , Br I ), Dimethylchalkogeniden Me Y (Y = O, S, Se, Te) Stickstoffheterozyklen (Pyridin, Pyrimidin) untersucht. Einblicke in Adduktbildungsverhalten sowie Bindungssituation solcher E⋅⋅⋅Sb−C ‐Einheiten wurden Lösung NMR‐Spektroskopie, im festen Zustand durch Röntgenbeugung, Elementaranalysen rechnerische Methoden (DFT, QTAIM, IQA) gewonnen.

Citations

0