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

A zinc porphyrin-based halogen-bonded organic framework with the heavy atom effect as a highly efficient photocatalyst for oxidative coupling of amines DOI
Penghao Sun, Hongqiang Dong,

Siheng Lv

et al.

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 12(2), P. 1128 - 1134

Published: Dec. 1, 2023

A novel zinc porphyrin-based [N⋯I + ⋯N] halogen-bonded organic framework has high photocatalytic 1 O 2 yields, which results from the heavy atom effect of I , and acts as a highly efficient photocatalyst for synthesis.

Language: Английский

Citations

12
N−X⋅⋅⋅O−N Halogen Bonds in Complexes of N‐Haloimides and Pyridine‐N‐oxides: A Large Data Set Study DOI Creative Commons
Rakesh Puttreddy, J. Mikko Rautiainen, Shilin Yu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: June 14, 2023

N-X⋅⋅⋅- O-N+ halogen-bonded systems formed by 27 pyridine N-oxides (PyNOs) as halogen-bond (XB) acceptors and two N-halosuccinimides, N-halophthalimides, N-halosaccharins XB donors are studied in silico, solution, the solid state. This large set of data (132 DFT optimized structures, 75 crystal 168 1 H NMR titrations) provides a unique view to structural bonding properties. In computational part, simple electrostatic model (SiElMo) for predicting energies using only properties halogen oxygen is developed. The SiElMo perfect accord with calculated from complexes high-level approaches. Data silico bond single-crystal X-ray structures correlate; however, solution do not. polydentate characteristic PyNOs' atom revealed solid-state attributed lack correlation between DFT/solid-state data. strength slightly affected PyNO [(atomic charge (Q), ionization energy (Is,min ) local negative minima (Vs,min )], σ-hole (Vs,max donor key determinant leading sequence N-halosaccharin>N-halosuccinimide>N-halophthalimide on strength.

Language: Английский

Citations

11
Pyridine Iodine(I) Cations: Kinetic Trapping as a Sulfonate Complexes DOI Creative Commons
Rakesh Puttreddy, Parveen Kumar, Kari Rissanen

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(16)

Published: Jan. 9, 2024

Seven pyridine iodine(I) sulfonate complexes were prepared and isolated at low temperatures characterized by X-ray diffraction analysis. The inherently instable cations are stabilized an oxygen of anions via the I⋅⋅⋅O halogen bond. In these complexes, iodine atom cation acts as electron acceptor donor. These stable enough in crystalline state, yet decompose rapidly under ambient conditions, also being unstable solution. (pyridine)N-I bond lengths [2.140(3)-2.197(2) Å] bonds [2.345(6)-2.227(3) analogous to (imide)N-I⋅⋅⋅O-N-pyridine uncharged halogen-bonded formed from N-haloimides N-oxides, thus confirming existence elusive cation.

Language: Английский

Citations

4
Chiral carbonyl hypoiodites DOI Creative Commons
Milla Mattila, Kari Rissanen, Jas S. Ward

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(31), P. 4648 - 4651

Published: Jan. 1, 2023

Three chiral carbonyl hypoiodites, R-C(O)OI, have been prepared from N-protected (S)-valine to give the ligand-stabilised (S)-valinoyl hypoiodite complexes with 4-dimethylaminopyridine, 4-pyrrolidinopyridine, and 4-morpholinopyridine as stabilising ligands. The identity of was established by NMR (1H, 13C, 1H-15N HMBC) single crystal X-ray diffraction analysis.

Language: Английский

Citations

10
Ligand exchange among iodine(i) complexes DOI Creative Commons
Shilin Yu, Jas S. Ward

Dalton Transactions, Journal Year: 2022, Volume and Issue: 51(12), P. 4668 - 4674

Published: Jan. 1, 2022

The ligand exchange behavior among iodine( i ) complexes was comprehensively investigated via the stoichiometric combination of two homoleptic complexes.

Language: Английский

Citations

16
Xenon Derivatives as Aerogen Bond-Donating Catalysts for Organic Transformations: A Theoretical Study on the Metaphorical “Spherical Cow in a Vacuum” Provides Insights into Noncovalent Organocatalysis DOI
Alexander S. Novikov, Dmitrii S. Bolotin

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(4), P. 1936 - 1944

Published: June 9, 2022

Computations indicate that cationic and noncharged xenon derivatives should exhibit higher catalytic activity than their iodine-based noncovalent organocatalytic congeners. Perfluorophenyl xenonium(II) is expected to demonstrate the best balance between chemical stability for use in organocatalysis. Comparing its with of isoelectronic perfluoroiodobenzene indicates high organocatalysts predominantly attributed electrostatic interactions reaction substrates, which cause polarization ligated species during progress. In contrast, electron transfer covalent contributions bonding catalyst substrate have negligible effects. The dominant effect results a strong negative correlation calculated Gibbs free energies activation modeled reactions highest potentials σ-holes on central atoms catalysts. No such observed

Language: Английский

Citations

15
Fluoro and Trifluoromethyl Benzoyl Hypoiodite Complexes with Substituted Pyridines DOI Creative Commons

Václav Kolařík,

Kari Rissanen, Jas S. Ward

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(13)

Published: April 5, 2024

Based on the prior observation of trifluoroacetate hypoiodite, CF

Language: Английский

Citations

3
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

3
Halogen Bond Unlocks Ultra‐High Birefringence DOI
Jin Chen,

Miao‐Bin Xu,

Huai‐Yu Wu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: July 10, 2024

Abstract Anisotropy is crucial for birefringence (Δ n ) in optical materials, but optimizing it remains a formidable challenge >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 6 H NO 2 + Cl − ( NAC then constructed halogen‐bonded supramolecular framework I 4 INA by halogen aliovalent substitution with . The organic moieties protonated deprotonated nicotinic acid NA ), respectively. antiparallel arrangement birefringent‐active units leads to significant differences the bonding characteristics between interlayer intralayer domains. Moreover, [O⋅⋅⋅I ⋅⋅⋅N] bond 1D [I ] chain exhibits stronger interactions stricter directionality, resulting more pronounced in‐plane anisotropy intrachain interchain directions. Consequently, exceptional birefringent performance, value 0.778 at 550 nm, twice that (0.363 nm). This significantly exceeds those commercial crystals, such as CaCO 3 (0.172 546 nm), highest reported among ultraviolet crystals. work presents novel design strategy employs bonds connection sites modes units, opening new avenues developing high‐performance

Language: Английский

Citations

3
Dihypoiodites stabilised by 4-ethylpyridine through O–I–N halogen bonds DOI Creative Commons

Eric Kramer,

Shilin Yu, Jas S. Ward

et al.

Dalton Transactions, Journal Year: 2021, Volume and Issue: 50(42), P. 14990 - 14993

Published: Jan. 1, 2021

Four bis(O-I-N) compounds have been synthesised from various dihypoiodites and 4-ethylpyridine. The were characterised in both the solution solid states by NMR spectroscopy (1H, 15N), X-ray diffraction, computational calculations.

Language: Английский

Citations

19