[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

Chiral Covalent Organic Cages: Structural Isomerism and Enantioselective Catalysis DOI
Kaixuan Wang, Xianhui Tang, Bai Amutha Anjali

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 6638 - 6651

Published: Feb. 28, 2024

Covalent organic cages are a prominent class of discrete porous architectures; however, their structural isomerism remains relatively unexplored. Here, we demonstrate the chiral covalent that renders distinct enantioselective catalytic properties. Imine condensations tetra-topic 5,10-di(3,5-diformylphenyl)-5,10-dihydrophenazine and ditopic 1,2-cyclohexanediamine produce two [4 + 8] cage isomers with totally different topologies geometries depend on orientations four tetraaldehyde units respect to each other. One isomer (

Language: Английский

Citations

22
A pseudo-cubic metal–organic cage with conformationally switchable faces for dynamically adaptive guest encapsulation DOI Creative Commons
Houyang Xu, Tanya K. Ronson, Andrew W. Heard

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Abstract The creation of hosts capable accommodating different guest molecules may enable these to play useful roles in chemical purifications, among other applications. Metal–organic cages are excellent for various guests, but they generally incorporate rigid structural units that hinder dynamic adaptation specific guests. Here we report a conformationally adaptable pseudo-cubic cage can dynamically increase its cavity volume fit guests with differing sizes. This pseudo-cube incorporates tetramine subcomponent 2,6-naphthalene arms cooperatively adopt non-planar conformation, enabling the faces switch between endo and exo states. A wide range were observed bind within this cage, spanning sizes from 46% 154% empty cage. Experimental computational evidence characterizes flipping , expanding upon binding larger

Language: Английский

Citations

3
The Topological Transformation of Trefoil Knots to Solomon Links via Diels–Alder Click Reaction DOI
Haitong Tang, Haining Zhang, Xiang Gao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16020 - 16027

Published: May 30, 2024

The quest for more efficient, user-friendly, and less wasteful topological transformations remains a significant challenge in the realm of postassembly modifications. In this article, high yields two molecular trefoil knots (Rh-1, Ir-1) were obtained using ligand 3,6-bis(3-(pyridin-4-yl)phenyl)-1,2,4,5-tetrazine (L1) with reactive tetrazine units binuclear half-sandwich organometallic [Cp*2M2(μ-TPPHZ)(OTf)2](OTf)2 (Rh-B, M = RhIII; Ir-B, IrIII). 2,5-Norbornadiene was used as an inducer Diels–Alder click reaction to modulate rapidly efficiently transformation Trefoil Solomon links. However, key achieving structural change is subtle increase site steric pyridazine fragments (L2), which allows structures spread bend three-dimensional space, confirmed by single-crystal X-ray diffraction, ESI-TOF/MS, elementary analysis detailed solution-state NMR techniques.

Language: Английский

Citations

13
Supramolecular coordination platinum metallacycle–based multilevel wound dressing for bacteria sensing and wound healing DOI Creative Commons

Wen-Zhen Li,

Xiaoqiang Wang,

L. Liu

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(14)

Published: March 25, 2024

The exploitation of novel wound healing methods with real-time infection sensing and high spatiotemporal precision is highly important for human health. Pt-based metal-organic cycles/cages (MOCs) have been employed as multifunctional antibacterial agents due to their superior Pt-related therapeutic efficiency, various functional subunits specific geometries. However, how rationally apply these nanoscale MOCs on the macroscale controllable output still challenging. Here, a centimeter-scale Pt MOC film was constructed via multistage assembly subsequently coated N,N′-dimethylated dipyridinium thiazolo[5,4-d]thiazole (MPT)-stained silk fabric form smart dressing bacterial healing. MPT could be used monitor in through bacteria-mediated reduction its radical color change. also exhibited an excellent photothermal effect under 660 nm light irradiation, which not only applied therapy but induce disassembly suprastructure. ordered suprastructure biosafety, while it showed improved efficiency after thermally induced disassembly. In vitro vivo studies revealed that combination MPT-stained can provide information timely treatment noninvasive techniques. This study paves way materials.

Language: Английский

Citations

6
The multifaceted roles of MnL2n cages in catalysis DOI
Zoe Ashbridge, Joost N. H. Reek

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(10), P. 1197 - 1207

Published: July 24, 2024

Language: Английский

Citations

6
Helical Cage Rotors Switched on by Brake Molecule with Variable Fluorescence and Circularly Polarized Luminescence DOI
Weili Shang, Yuan Wang, Xuefeng Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(50), P. 27639 - 27649

Published: Dec. 6, 2023

While chiral molecular rotors have unique frames and cavities to possibly generate switchable chiroptical functions, it still remains a formidable challenge precisely restrict their rotations activate certain functions such as fluorescence well circularly polarized luminescence (CPL), which are strongly related the local rotations. Herein, we design pair of enantiopure helical cage rotors, emit light neither at state nor in crystal or aggregation states, although they contain luminophore groups. However, upon mounting with fluoroaromatic borane (TFPB) brake, phenyl rotation can be effectively hindered CPL activities switched on. Crystal structure analysis reveals that is restricted through synergistic B-O-H-N bonding fluoroaromatic-aromatic (ArF-Ar) dipole interaction. Moreover, cages on stepwise color-variable by inner brake outer supramolecular assemblies, respectively. This work not only provides idea but also unveils how could generated rotor systems.

Language: Английский

Citations

12
Computer-aided design of triazolo-cages as anion receptors DOI Creative Commons
Minwei Che, Sibali Debnath, Amar H. Flood

et al.

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Molecular cages with three-dimensional cavities have garnered significant interest due to their enhanced encapsulation abilities.

Language: Английский

Citations

0
Conformationally Adaptive Metal–Organic Cages for Dynamic Guest Encapsulation DOI
Yujuan Zhou, Kecheng Jie

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111007 - 111007

Published: Feb. 1, 2025

Language: Английский

Citations

0
Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cages DOI Creative Commons

Qiong‐Yan Hong,

Bin Huang,

Meng‐Xiang Wu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 13, 2025

Interpenetration is a phenomenon frequently encountered in self-assembled Pd2L4-type coordination cages, while the mechanism of interpenetration process remains unclear. Here we show synthesis and solvent-mediated interconversion highly soluble phenoxazine-based monomeric cage 1 corresponding interlocked dimer 2. We succeed isolation single-crystal structure analysis both 2 with same guest anion by changing solvents utilized self-assembly. The monomeric-to-dimeric conversion occurs heating weakly coordinating solvents, dimeric-to-monomeric takes place through disassembly reassembly strongly at low concentration or addition/removal competing ligand. may be driven distinct thermodynamic stabilities different solvents. Additionally, Cl– anions template because strong chloride binding affinity which could serve as an anion-binding catalyst for C–Cl bond cleavage. While cages tend to form dimers, characterization its very challenging. Herein, authors report dimer.

Language: Английский

Citations

0
A Redox‐Active Phenothiazine‐based Pd2L4‐Type Coordination Cage and Its Isolable Crystalline Polyradical Cations DOI
Bin Huang,

Manfei Zhou,

Qiong‐Yan Hong

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 14, 2024

Polyradical cages are of great interest because they show very fascinating physical and chemical properties, but many challenges remain, especially for their synthesis characterization. Herein, we present the a polyradical cation cage 1

Language: Английский

Citations

2