Bowl‐Shaped Kekulene Analogues: Cycloarenes with two Five‐Membered Rings DOI Creative Commons

Hideyuki Murakami,

H Iwabuchi,

Miki Asari

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(45)

Published: May 31, 2024

Kekulene, a cycloarene composed of 12 fused benzene rings in circular arrangement, exhibits highly planar and robust structure. Kekulene has been the subject investigation into its aromaticity electronic structure, particularly relation to cyclic benzenoid. We have successfully synthesized novel bowl-shaped kekulene analogues with five-membered incorporated The results DFT calculations VT-NMR spectra indicate that inversion their concave-convex structures occurs at room temperature. NICS AICD plots predict Clar's type resonance structure is found manner analogous pristine kekulene, albeit interruption π-conjugation on sp

Language: Английский

Facile Synthesis of Donor–Acceptor Heterocycloarenes Based on Pyrazine Derivatives Possessing Intriguing Iodide Ion Capture Properties DOI

Jiangyu Zhu,

Teng Wang,

Dongyue An

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21922 - 21931

Published: July 25, 2024

Donor–acceptor (D–A) conjugated systems have been extensively investigated and play important roles in organic electronics. Incorporating D–A structures into (hetero)cycloarenes endows them tunable electronic properties, while the well-defined cavity remains. However, synthetic complexity of introducing electron-acceptor moieties limits their development applications. In this paper, first family electronically heterocycloarenes (DAHCn, n = 1–5) based on pyrazine derivatives was facilely synthesized through cyclocondensation reaction from a tetraketone-functionalized heterocycloarene precursor prepared using ketal-protection strategy. The effect expanded conjugation inserted electron-withdrawing group studied systematically by X-ray crystallographic analysis, various spectroscopic measurements, theoretical calculations. Interestingly, presence an polarizes inner C(sp2)–H significantly increases binding affinities to iodide anion. Meanwhile, anion affinity can be further modulated type attached substituents distance polarization. More importantly, dicyanopyrazine derivative DAHC3 shows highest strength ion as 2:1 sandwich complex (log β2 12.3 ΔG −69.1 kJ mol–1), which is strongest receptor hydrogen bonding interactions reported date. Our finding provides new strategy design synthesize strong receptors.

Language: Английский

Citations

8
Four‐Membered Ring‐Embedded Cycloarene Enabling Anti‐Aromaticity and Ultra‐Narrowband Emission DOI
Rong Zhang, Zuping Xiong,

Dongyue An

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 11, 2024

Abstract The synthesis of fully fused π‐conjugated cycloarenes embedded with nonbenzenoid aromatics is challenging. In this work, the first example four‐membered ring‐embedded cycloarene ( MF2 ) was designed and synthesized in single‐crystal form by macrocyclization ring fusion strategies. For comparison, single bond‐linked chiral macrocycle MS2 without two rings its linear‐shaped polycyclic benzenoid monomer L1 were also synthesized. pronounced anti‐aromaticity significantly adjusts electronic structures photophysical properties cycloarene, resulting an enhancement photoluminescence quantum yield (PLQY) from 10.66 % 10.74 for , respectively, to 54.05 which highest PLQY among reported cycloarenes. Notably, owing anti‐aromatic that reduce structural displacements, exhibits ultra‐narrowband emission a single‐digit full‐width at half‐maximum (FWHM) only 7 nm (0.038 eV), sets new record all organic narrowband luminescent molecules, represents conventional aromatic hydrocarbons (PAHs) devoid heteroatoms.

Language: Английский

Citations

6
Design Strategies, Properties, and Applications toward Cycloarenes and Heterocycloarenes DOI Creative Commons

Jiangyu Zhu,

Rong Zhang,

Dongyue An

et al.

Accounts of Materials Research, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

Language: Английский

Citations

0
Oxa-phenalene [b]-fused BODIPY Dyes: Synthesis, Structures, and Photophysical Properties DOI
Hao Guan, Ruihan Yang,

Limin He

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134728 - 134728

Published: May 1, 2025

Language: Английский

Citations

0
Heteroatom-contained carbon-rich macrocycles and carbon nanobelts: Synthesis, molecular architectures, characteristics and applications DOI
Xin Sun,

Jinku Bai,

Xinyue Wang

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 518, P. 216063 - 216063

Published: July 17, 2024

Language: Английский

Citations

2
Four‐Membered Ring‐Embedded Cycloarene Enabling Anti‐Aromaticity and Ultra‐Narrowband Emission DOI
Rong Zhang, Zuping Xiong,

Dongyue An

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(43)

Published: July 11, 2024

Abstract The synthesis of fully fused π‐conjugated cycloarenes embedded with nonbenzenoid aromatics is challenging. In this work, the first example four‐membered ring‐embedded cycloarene ( MF2 ) was designed and synthesized in single‐crystal form by macrocyclization ring fusion strategies. For comparison, single bond‐linked chiral macrocycle MS2 without two rings its linear‐shaped polycyclic benzenoid monomer L1 were also synthesized. pronounced anti‐aromaticity significantly adjusts electronic structures photophysical properties cycloarene, resulting an enhancement photoluminescence quantum yield (PLQY) from 10.66 % 10.74 for , respectively, to 54.05 which highest PLQY among reported cycloarenes. Notably, owing anti‐aromatic that reduce structural displacements, exhibits ultra‐narrowband emission a single‐digit full‐width at half‐maximum (FWHM) only 7 nm (0.038 eV), sets new record all organic narrowband luminescent molecules, represents conventional aromatic hydrocarbons (PAHs) devoid heteroatoms.

Language: Английский

Citations

1
Proton Conductivity Switch for Hydrogen-Bonding Octaaminotetraphenylene Salts Through Crystal–Amorphous Transformation During H2O Sorption DOI
Mu Li, Takashi Takeda, Shun Dekura

et al.

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(35), P. 14834 - 14841

Published: Aug. 23, 2024

The phosphate salt of octaaminotetraphenylene (OATP), [(H4OATP4+)(H2PO4–)4], was prepared. Single crystals were isolated with a crystal formula (H4OATP4+)(H2PO4–)4(H3PO4)0.25·2.5H2O, whereas the powder sample at 300 K formed an amorphous (H4OATP4+)(H2PO4–)4.0·nH2O n = 1–2. In anhydrous solids (n 0), formation hydrogen-bonding network H2PO4– anions and dielectric relaxation associated motional freedom observed. Adsorption–desorption isotherms H2O 298 showed transformation between (H4OATP4+)(H2PO4–)4 hydrous crystalline (H4OATP4+)(H2PO4–)4·6H2O, proton conductivity increased by 2 orders magnitude after adsorption. reached 7.58 × 10–5 S cm–1. cation–anion in amorphous–crystalline exhibited switching phenomena ON/OFF ratio about 100 upon adsorption–desorption.

Language: Английский

Citations

1
Bowl‐Shaped Kekulene Analogues: Cycloarenes with two Five‐Membered Rings DOI Creative Commons

Hideyuki Murakami,

H Iwabuchi,

Miki Asari

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(45)

Published: May 31, 2024

Kekulene, a cycloarene composed of 12 fused benzene rings in circular arrangement, exhibits highly planar and robust structure. Kekulene has been the subject investigation into its aromaticity electronic structure, particularly relation to cyclic benzenoid. We have successfully synthesized novel bowl-shaped kekulene analogues with five-membered incorporated The results DFT calculations VT-NMR spectra indicate that inversion their concave-convex structures occurs at room temperature. NICS AICD plots predict Clar's type resonance structure is found manner analogous pristine kekulene, albeit interruption π-conjugation on sp

Language: Английский

Citations

0