Cooperativity and halonium transfer in the ternary NCI···CH 3 I··· - CN halogen-bonded complex: An ab initio gas phase study DOI Creative Commons

Rubén D. Parra

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 7, 2024

Abstract Context The strength and nature of the two halogen bonds in NCI···CH3I···−CN halogen-bonded ternary complex are studied gas phase via ab initio calculations. Different indicators bond were employed to examine interactions including geometries, complexation energies, NBO Wiberg indices, AIM parameters. results show that is strong partly covalent when CH3I donates bond, but weak noncovalent accepts bond. Significant cooperativity emerges relative corresponding heterodimer complexes, NCI···CH3I CH3I···−CN, respectively. For example, CCSD(T) energy (-18.27 kcal/mol) about twice sum energies component dimers (-9.54 kcal/mol). halonium transfer reaction converts into an equivalent one was also investigated. electronic barrier for calculated be 6.70 kcal/mol at level. Although MP2 level underestimates MP3 overestimates barrier, their MP2.5 average (6.44 close more robust Insights on ion obtained by examining force profiles along intrinsic coordinate, IRC. evolution other properties such as lengths, Mulliken charges provides specific insight extent structural rearrangements redistribution throughout entire IRC space.Methods method used geometry optimizations. Energy calculations performed using method. aug-cc-pVTZ basis set all atoms than iodine which aug-cc-pVTZ-PP instead.

Language: Английский

Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non‐Covalent Organocatalysis: An Update DOI Creative Commons
Dragana Jovanovic,

Meghana Poliyodath Mohanan,

Stefan M. Huber

et al.

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

Citations

28
Photoluminescent organic crystals and co-crystals DOI
Aijaz A. Dar,

Asif A. Malik

Journal of Materials Chemistry C, Journal Year: 2024, Volume and Issue: 12(27), P. 9888 - 9913

Published: Jan. 1, 2024

This perspective highlights the significance of crystal engineering intervention in design and development applied optical materials.

Language: Английский

Citations

11
Halogen‐Bonded Organic Frameworks (XOFs) Based on N⋯Br+⋯N Bonds: Robust Organic Networks Constructed by Fragile Bonds DOI
Shigui Chen,

Xuguan Bai,

Zhen‐Nan Tian

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)

Published: June 7, 2024

Organic frameworks face a trade-off between the framework stability and bond dynamics, which necessitates development of innovative linkages that can generate stable without hindering efficient synthesis. Although iodine(I)-based halogen-bonded organic (XOFs) have been developed, constructing XOFs based on bromine(I) is desirable yet challenging due to high sensitivity species. In this work, we present inaugural construction bromine(I)-bridged two-dimensional (2D) frameworks, XOF(Br)-TPy-BF

Language: Английский

Citations

8
Halonium and Chalconium Salt-Catalyzed Schiff Condensation: Kinetics and DFT Insights into Organocatalyst Activity Parameters DOI
Alexandra A. Sysoeva, Yana V. Safinskaya, Mikhail V. Il’in

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Chalconium and halonium salts catalyze Schiff condensation. Kinetic data DFT calculations show that the catalytic activity correlates with maximum electrostatic potential on σ-holes, whereas other factors are less significant.

Language: Английский

Citations

1
Halogen Bond via an Electrophilic π-Hole on Halogen in Molecules: Does It Exist? DOI Open Access
Pradeep R. Varadwaj

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

Citations

6
Iodonium and Telluronium Triflates Serving as Noncovalent Organocatalysts Provide Catalytic Effect in the Schiff Condensation Due to Different Reasons DOI
Ivan O. Putnin, Alexandra A. Sysoeva, Mikhail V. Il’in

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: June 15, 2024

Abstract Sulfonium, selenonium, telluronium triflates, as well chloronium, bromonium, and iodonium triflates have been examined in the model Schiff condensation chalcogen‐ halogen bond donating organocatalysts, respectively. The kinetic data indicated that catalytic effect of salt is provided via decrease enthalpy activation reaction, whereas – unexpectedly caused by value entropy activation. In addition, it was experimentally shown activity sulfonium selenonium salts significantly lower than chloronium bromonium salts, but latter pair species less stable under reaction conditions former pair.

Language: Английский

Citations

5
Hypervalent Iodine(III) Mediated Halogen Bonded Supramolecular Chiral System with Cholesteryl Naphthalimides DOI
Jie Zhang,

Aiyou Hao,

Pengyao Xing

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(32)

Published: April 8, 2024

Abstract Halogen bonding acknowledged as a noteworthy weak interaction, has gained growing recognition in the field of supramolecular chemistry. In this study, we selected structurally rigid diaryliodonium ions (I(III)) with two biaxial σ‐holes halogen‐bond donors, to bind three chiral acceptor molecules bearing cholesteryl and naphthalimides distinct geometries. The abundant carbonyl oxygen atoms side‐arm substituents function multiple acceptors for halogen bonding. self‐aggregation demonstrates adaptiveness solvent media, evidenced by inversion Cotton effect morphological evolution from spherical rod‐like nanoarchitectures different systems. geometries conferred various binding modes I(III). introduction I(III) donor regulates aggregation achieving amplification chiroptical signals inheriting responsiveness self‐aggregated assembly. This study successfully utilized rational structural design multimodal control strategies achieve regulation chirality.

Language: Английский

Citations

4
Radial Behavior of Electrostatic Potentials of Atoms and Ions Revisited: Isotropy and Anisotropy DOI
Ponnadurai Ramasami, Jane S. Murray

ChemPhysChem, Journal Year: 2024, Volume and Issue: 25(17)

Published: May 22, 2024

In this paper we revisit earlier work relating to monoatomic atoms and ions published by pioneers in the area of electrostatic potentials. We include plots radial distributions potentials for spherically symmetric cations, singly, doubly triply negative anions. For with anisotropy their densities potentials, such as halonium it is shown how molecular surface approach plotting complements that achieved directional distributions.

Language: Английский

Citations

4
Construction of radical halogen-bonded organic frameworks with enhanced magnetism and conductivity DOI
Hongqiang Dong, Shang‐Bo Yu,

Shu-Meng Wang

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110730 - 110730

Published: Dec. 1, 2024

Language: Английский

Citations

3
Halogen and hydrogen bonded 2-X-pyridin-3-ol (X = Cl, Br, I) organic crystals with large shear piezoelectricity DOI Creative Commons

Geetanjali Kumari,

Charlie O’Mahony,

Ragima V. P. Veluthaparambath

et al.

Matter, Journal Year: 2025, Volume and Issue: unknown, P. 102098 - 102098

Published: April 1, 2025

Language: Английский

Citations

0