[5]Helicene Based π‐Conjugated Macrocycles with Persistent Figure‐Eight and Möbius Shapes: Efficient Synthesis, Chiral Resolution and Bright Circularly Polarized Luminescence DOI Open Access
Qifeng Zhou, Wei Yuan, Yunfei Li

et al.

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

Published: Oct. 21, 2024

Abstract π‐Conjugated chiral shape‐persistent molecular nanocarbons hold great potential as chiroptical materials, though their synthesis remains a considerable challenge. Here, we present simple approach using Suzuki coupling of [5]helicene building block with various aromatic units, enabling the one‐pot series macrocycles persistent figure‐eight and Möbius shapes. Single‐crystal structures 7 compounds were solved, 22 enantiomers separated by preparative HPLC. A notable pyrene‐bridged macrocycle, its rigid, fully π‐conjugated overcrowded structure, exhibited pure excimer emission outstanding circularly polarized luminescence (CPL) properties, including large dissymmetric factor (| g lum |=3.8×10 −2 ) significant CPL brightness ( B =710.5 M −1 cm ). This method provides versatile synthetic platform for producing D 2 ‐symmetric singly or triply twisted C 3 symmetry, offering tunable properties applications.

Language: Английский

Circularly Polarized Luminescent π‐Conjugated Chiral Nanorings and Nanobelts DOI

Yuting Xue,

Yafei Shi,

Pangkuan Chen

et al.

Advanced Optical Materials, Journal Year: 2024, Volume and Issue: 12(18)

Published: May 20, 2024

Abstract Molecular chirality plays a pivotal role across the disciplines of chemical and physical sciences, as well holding significant implications in realms medicine technology. Chiral macrocycles have attracted recent interests synthetic chemistry, material science, supramolecular chemistry. Due to cyclic arrangements stereogenic elements or special orientations confined rigid structures, π‐conjugated chiral are expected be highly luminescent, configurationally stable, thus serve develop high‐performance chiroptical materials. Given rapid progress achieved this new area years, it is highlight concepts breakthroughs. This minireview will offer overview wide range from traditional molecules which include axially, helically, planar skeletons nanobelts with focus on structure‐function relationship between unique properties.

Language: Английский

Citations

10
Modular access to π-conjugated planar chiral diradicaloids using redox-active pillar[5]arenes DOI

Yuting Xue,

Yi Zeng,

Yafei Shi

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

Language: Английский

Citations

0
Recent development of azahelicenes showing circularly polarized luminescence DOI Creative Commons
Chihiro Maeda, Tadashi Ema

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This feature article summarizes the recent developments of azahelicenes showing circularly polarized luminescence.

Language: Английский

Citations

0
Double Spin with a Twist: Synthesis and Characterization of a Neutral Mixed-Valence Organic Stable Diradical DOI
Vyacheslav V. Sentyurin, Oleg A. Levitskiy, Tatiana S. Yankova

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 11, 2024

A convenient design strategy opens access to neutral open-shell mixed-valence species

Language: Английский

Citations

3
Topology-Directed Synthesis of Helical Phosphoniums with High Diradical Character and Polar-Dependent Electron Transfer DOI Creative Commons
Bo Yang,

Suqiong Yan,

Shirong Ban

et al.

Published: June 7, 2024

Molecular topology synthesis of polycyclic aromatic heterocycles (PAHs) with diradical character takes root in the intramolecular coupling breakthrough. Herein, we report selectively Mn(III)/Cu(II)-mediated C−P and C−H bond cleavage to obtain robust donorfused phosphoniums helical or planar geometries distinct cationic charges. The former structures incorporate a common phospha[5]helication acceptor different arylamines donors, latter one contains phospha[6]dication same donors. These unprecedented donor-acceptor (D−A) pairs show unique topology-dependent optoelectronic properties. folded radical centers possess an extreme electron-deficient state throughspace isolation high (y0 = 0.989). Moreover, ingenious charge transfer (CT) locally excited (LE) transition components facilitate diverse hybridized local (HLCT) solvents, endowing highest emission bandgap variation 0.78 eV (~217 nm). could also be adjusted from blue near-infrared regions via tailoring polardependent HLCT, which output additional circularly polarized luminescence compatible chiral menthol matrix elevated quantum efficiency retained deep-red glow. It is worth mentioning that atomically precise Mn(III) halide has been unprecedentedly captured determined for activation

Language: Английский

Citations

2
Topology-Directed Synthesis of Helical Phosphoniums with High Diradical Character and Polar-Dependent Electron Transfer DOI

Bo Yang,

Suqiong Yan,

Shirong Ban

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 14, 2024

Molecular topology synthesis of polycyclic aromatic hydrocarbons (PAHs) with diradical character takes root in intramolecular coupling breakthrough. Herein, we report selective Mn(III)/Cu(II)-mediated C–P and C–H bond cleavage to obtain robust donor-fused phosphoniums helical or planar geometries distinct cationic charges. The former structures incorporate a common phospha[5]helication acceptor different arylamine donors, the latter structure contains phospha[6]dication same donors. These unprecedented ionic salts hold distinguishing donor–acceptor (D–A) constructions, showing unique topology-dependent optoelectronic properties. folded radical ammoniums possess an extreme electron-deficient state through-space isolation high (y0 = 0.989). Moreover, tunable charge transfer (CT) locally excited (LE) transition components facilitate diverse hybridized local (HLCT) solvents, endowing highest emission band gap variation 0.78 eV (∼217 nm). fluorescence radiation could also be adjusted from blue near-infrared regions via tailoring polar-dependent states, which output additional circularly polarized luminescence compatible chiral menthol matrix elevated quantum efficiency undisturbed deep-red glow. It is worth mentioning that atomically precise Mn(III) halide has been unprecedentedly captured determined for activation.

Language: Английский

Citations

1
Hybridized Local and Charge Transfer Modulated Triplet Decay Brightens Ultra-Long Circularly Polarized Afterglow and Chiral Diradical Activity DOI Creative Commons
Bo Yang,

Suqiong Yan,

Hui Ma

et al.

Published: June 7, 2024

The design and construction of chiral phosphors with significant long-lived triplet exciton decay have received great attention because their prospective applications in ultra-long circularly polarized room-temperature phosphorescence (CPRTP) for optics. However, the practical utilization pure organics as incubators is often hindered by spin-forbidden transition. Therefore, it a substantial challenge developments organic-derived CP-RTP emitters both long lifetimes asymmetry factors. Herein, via precisely manipulating hybridized local charge transfer (HLCT) multiple n−π* effects, we report first P,N-embedded tactic to construct BINAP-derived emitters, which show tunable luminescence (CPL) high photoluminescence quantum efficiency (up 95%), |glum| values (1.2 6.2 × 10−3), RTP remarkable lifetime 448 ms polymethyl methacrylate. Experiments chemistry simulations unveil that abovementioned derived from HLCT balanced electric-magnetic dipole moment environment. Moreover, synergetic enhancement chemical configurational stability enables stable diradicals diradical character (y0 = 0.953) Near-Infrared Ray (NIR) optical activity. This work provides important clues materials phosphine chemistry.

Language: Английский

Citations

0
[5]Helicene Based π‐Conjugated Macrocycles with Persistent Figure‐Eight and Möbius Shapes: Efficient Synthesis, Chiral Resolution and Bright Circularly Polarized Luminescence DOI Open Access
Qifeng Zhou, Yuan Wei, Yunfei Li

et al.

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

Published: Oct. 21, 2024

π-Conjugated chiral shape-persistent molecular nanocarbons hold great potential as chiroptical materials, though their synthesis remains a considerable challenge. Here, we present simple approach using Suzuki coupling of [5]helicene building block with various aromatic units, enabling the one-pot series macrocycles persistent figure-eight and Möbius shapes. Single-crystal structures 7 compounds were solved, 22 enantiomers separated by preparative HPLC. A notable pyrene-bridged macrocycle, its rigid, fully π-conjugated overcrowded structure, exhibited pure excimer emission outstanding circularly polarized luminescence (CPL) properties, including large dissymmetric factor (|g

Language: Английский

Citations

0
[5]Helicene Based π‐Conjugated Macrocycles with Persistent Figure‐Eight and Möbius Shapes: Efficient Synthesis, Chiral Resolution and Bright Circularly Polarized Luminescence DOI Open Access
Qifeng Zhou, Wei Yuan, Yunfei Li

et al.

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

Published: Oct. 21, 2024

Abstract π‐Conjugated chiral shape‐persistent molecular nanocarbons hold great potential as chiroptical materials, though their synthesis remains a considerable challenge. Here, we present simple approach using Suzuki coupling of [5]helicene building block with various aromatic units, enabling the one‐pot series macrocycles persistent figure‐eight and Möbius shapes. Single‐crystal structures 7 compounds were solved, 22 enantiomers separated by preparative HPLC. A notable pyrene‐bridged macrocycle, its rigid, fully π‐conjugated overcrowded structure, exhibited pure excimer emission outstanding circularly polarized luminescence (CPL) properties, including large dissymmetric factor (| g lum |=3.8×10 −2 ) significant CPL brightness ( B =710.5 M −1 cm ). This method provides versatile synthetic platform for producing D 2 ‐symmetric singly or triply twisted C 3 symmetry, offering tunable properties applications.

Language: Английский

Citations

0