Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds DOI Creative Commons
Shilin Yu, Khai‐Nghi Truong,

Marcel Siepmann

et al.

Crystal Growth & Design, Journal Year: 2023, Volume and Issue: 23(2), P. 662 - 669

Published: Jan. 23, 2023

A series of LH[Z–I–Z] halogen(I) complexes, where Z = saccharinato or phthalimido anions and LH pyridinium, pyrazinium, tetrabutyl (TBA)- tetramethylammonium (TMA) cations, were prepared, structurally characterized, discussed as complexes consisting a [N–I–N]− anion with three-center–four-electron (3c-4e) halogen bond, hydrogen-bonding (pyridinium pyrazinium) inert (TBA TMA) cation. The symmetric anion, reminiscent the triiodide [I–I–I]− is found to be equivalent its cationic analogue [N–I–N]+ N–I bond lengths 2.26 Å. In contrast homoleptic asymmetry (2.21 2.28 Å) was observed for those which manifested hydrogen only one moiety, thus being analogous asymmetric heteroleptic complexes. results show that 3c-4e [N–I–N] either positively negatively charged, can asymmetrized by an external ([N–I–N]−) using two different ligands (heteroleptic [N–I–N]+).

Language: Английский

Diaryliodoniums as Hybrid Hydrogen- and Halogen-Bond-Donating Organocatalysts for the Groebke–Blackburn–Bienaymé Reaction DOI Creative Commons
Mikhail V. Il’in, Alexandra A. Sysoeva, Alexander S. Novikov

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(7), P. 4569 - 4579

Published: Feb. 17, 2022

Dibenziodolium and diphenyliodonium triflates display high catalytic activity for the multicomponent reaction that leads to a series of imidazopyridines. Density functional theory (DFT) calculations indicate both salts can play role hybrid hydrogen- halogen-bond-donating organocatalysts, which electrophilically activate carbonyl imine groups during process. The ortho-H atoms in vicinal position I atom dual role: forming additional noncovalent bonds with ligated substrate increasing maximum electrostatic potential on σ-hole at iodine owing effects polarization. triflate exhibits higher activity, results obtained from 1H nuclear magnetic resonance (NMR) titrations, conjunction those DFT calculations, this could be explained terms energy required rotation phenyl ring cation ligation substrate.

Language: Английский

Citations

55
Sulfonium and Selenonium Salts as Noncovalent Organocatalysts for the Multicomponent Groebke–Blackburn–Bienaymé Reaction DOI
Mikhail V. Il’in, Alexander S. Novikov, Dmitrii S. Bolotin

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(15), P. 10199 - 10207

Published: July 20, 2022

Sulfonium and selenonium salts, represented by S-aryl dibenzothiophenium Se-aryl dibenzoselenophenium triflates, were found to exhibit remarkable catalytic activity in the model Groebke–Blackburn–Bienaymé reaction. Kinetic analysis density functional theory (DFT) calculations indicated that their effect is induced ligation of reaction substrates σ-holes on S or Se atom cations. The experimental data although 10-fold excess chloride totally inhibits sulfonium salt remains catalytically active, which can be explained experimentally lower binding constant derivative comparison with analogue. Both types salts than dibenziodolium species.

Language: Английский

Citations

40
Halogen Bonds of Halogen(I) Ions─Where Are We and Where to Go? DOI Creative Commons
Lianne H. E. Wieske, Máté Erdélyi

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 3 - 18

Published: Dec. 20, 2023

Halenium ions, X+, are particularly strong halogen-bond donors that interact with two Lewis bases simultaneously to form linear [D···X···D]+-type halonium complexes. Their three-center, four-electron halogen bond is both fundamentally interesting and technologically valuable as it tames the reactivity of halogen(I) opening up new horizons in a variety fields including synthetic organic supramolecular chemistry. Understanding this bonding situation enables development improved transfer reactions advanced functional materials. Following decade investigations basic principles, range applications now rapidly widening. In Perspective, we assess status field identify its key advances main bottlenecks. Clearing common misunderstandings may hinder future progress, aim inspire direct research efforts.

Language: Английский

Citations

23
Ag-LSPR and molecular additive: A collaborative approach to improve the photovoltaic performance of perovskite solar cells DOI
Le Zhang, Haipeng Jiang, Tao Huang

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 481, P. 148572 - 148572

Published: Jan. 4, 2024

Language: Английский

Citations

13
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
Yet another perspective on hole interactions DOI
Naziha Tarannam, Rahul Shukla, Sebastian Kozuch

et al.

Physical Chemistry Chemical Physics, Journal Year: 2021, Volume and Issue: 23(36), P. 19948 - 19963

Published: Jan. 1, 2021

Hole interactions are known by different names depending on their key atom ( e.g. halogen, chalcogen, triel or hydrogen bonds), and the geometry of interaction (σ, π, δ). Maybe we can make some order analysing molecular orbitals?

Language: Английский

Citations

44
Carbonyl Hypoiodites as Extremely Strong Halogen Bond Donors DOI Creative Commons
Shilin Yu, Jas S. Ward, Khai‐Nghi Truong

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(38), P. 20739 - 20743

Published: July 16, 2021

Abstract Neutral halogen‐bonded O−I−N complexes were prepared from in situ formed carbonyl hypoiodites and aromatic organic bases. The have a strongly polarized iodine atom with larger σ‐holes than any known uncharged halogen bond donor. Modulating the Lewis basicity of selected pyridine derivatives carboxylates leads to where classical O−I⋅⋅⋅N transforms more into COO − ⋅⋅⋅I−N + ion‐pair (salt) an asymmetric moiety. X‐ray analyses, NMR studies, calculations reveal bonding geometries hypoiodite‐based complexes, confirming that solid‐state is much closer N‐atom its original position at carboxylate O‐atom.

Language: Английский

Citations

43
Halogen Bond Unlocks Ultra‐High Birefringence DOI
Jin Chen, Mingsheng Xu,

Huai‐Yu Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 10, 2024

Anisotropy is crucial for birefringence (Δn) in optical materials, but optimizing it remains a formidable challenge (Δn >0.3). Supramolecular frameworks incorporating π-conjugated components are promising achieving enhanced because of their structural diversity and inherent anisotropy. Herein, we first synthesized (C

Language: Английский

Citations

8
Hypervalent Iodine (III)‐Based Complexation for Chiroptical Supramolecular Glass, Deep Eutectic Solvent and Luminescent Switch DOI

Shuguo An,

Aiyou Hao, Pengyao Xing

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: July 16, 2024

Hypervalent iodine(III) have widely been utilized for organic synthetic reagents. They are also recognized as positive charge-assisted, exceptionally robust biaxial halogen bond donors, while their potential in supramolecular materials is barely explored. This work reports a cyclic diaryliodonium ion bonding donor that displays remarkable binding affinity toward phenanthroline or acridine acceptors with chiral pendants. Biaxial enables chiroptical evolution solution, allowing rational control over chirality. Leveraging strong affinity, the complexes manifested amorphous properties and deep eutectic behavior solid state. Capitalizing on these attributes, this achieves successful preparation of glasses solvents. Additionally, appended light irradiation-triggered luminescence through hydrogen atom transfer process, showing applications anti-counterfeit display.

Language: Английский

Citations

6
Exploring the Structural Attributes of Yoda1 for the Development of New-Generation Piezo1 Agonist Yaddle1 as a Vaccine Adjuvant Targeting Optimal T Cell Activation DOI

Sunny Goon,

Chinky Shiu Chen Liu, Uddipta Ghosh Dastidar

et al.

Journal of Medicinal Chemistry, Journal Year: 2024, Volume and Issue: 67(10), P. 8225 - 8246

Published: May 8, 2024

Piezo1, a mechano-activated ion channel, has wide-ranging physiological and therapeutic implications, with the ongoing development of specific agonists unveiling cellular responses to mechanical stimuli. In our study, we systematically analyzed chemical subunits in Piezo1 protein agonist Yoda1 comprehend structure-activity relationship push forward next-generation development. Preliminary screening assays for agonism were performed using Piezo1-mCherry-transfected HEK293A cell line, keeping as positive control. We introduce novel Yaddle1 (

Language: Английский

Citations

6