Boosted Circularly Polarized Luminescence of a Chiral Metallacage Through Co‐Assembly in Confined Microfluidic Environments DOI
Jianjian Zhao, Kai Zeng, Wei‐Tao Dou

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 35(3)

Published: Sept. 20, 2024

Abstract Chiral metallacages, with their precisely distributed luminescent and chiral units inherent adaptive chirality, represent an ideal framework for developing circularly polarized luminescence (CPL)‐active materials. Despite potential, enhancing the dissymmetry factor ( g lum ) of metallacage‐based materials remains a significant challenge. In this study, useful approach is proposed by co‐assembling donor metallacage Δ 4 / Λ ‐Zn A achiral acceptor Nile red (NiR), achieving efficient energy chirality transfer resulting in enhanced CPL these co‐assemblies. More importantly, microfluidic laminar flow utilized, known providing stable driving forces confined spaces, to achieve marked improvement values co‐assemblies within polymethyl methacrylate (PMMA) films. Computational fluid dynamics (CFD) simulations small‐angle X‐ray scattering (SAXS) experiments confirm that films containing /NiR, prepared via chips, display well‐defined distributions metallacages NiR due controllable assembly process facilitated flow. This work pioneers new methodology significantly enhance materials, opening avenues field photonics.

Language: Английский

The codriven assembly of molecular metalla-links (613, 623) and metalla-knots (41, 31) via coordination and noncovalent interactions DOI Creative Commons
Shu‐Jin Bao, Yan Zou, Haining Zhang

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(27)

Published: June 28, 2024

Although mechanically interlocked molecules (MIMs) display unique properties and functions associated with their intricate connectivity, limited assembly strategies are available for synthesis. Herein, we presented a synergistic strategy based on coordination noncovalent interactions (π–π stacking CH⋯π interactions) to selectively synthesize molecular closed three-link chains ( 6 1 3 links), highly entangled figure-eight knots 4 knots), trefoil knot knot), Borromean ring 2 link). links can be created by the strategic of nonlinear multicurved ligands incorporating furan or phenyl group long binuclear half-sandwich organometallic Cp*Rh III (Cp* = η 5 -pentamethylcyclopentadienyl) clip. However, utilizing much shorter units union 2,6-naphthyl-containing ligand led because increased π–π between four consecutive stacked layers interactions. Weakening such resulted in knot. The universality this building was verified 1,5-naphthyl-containing ligand. Quantitative conversion simple macrocycle species accomplished adjusting concentrations monitored NMR spectroscopy electrospray ionization mass spectrometry (ESI-MS). Furthermore, increasing stiff π-conjugated area unit afforded ring, topology is topological isomer link. These artificial metalla-links metalla-knots were confirmed single-crystal X-ray diffraction, ESI-MS. results offer potent higher-order MIMs emphasize critical role that play creating sophisticated topologies.

Language: Английский

Citations

14
BINOL‐Based Chiral Macrocycles and Cages DOI

Yabing Yu,

Yaning Hu,

Chengbing Ning

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 6, 2024

Abstract Chirality, a fundamental principle in chemistry, biology, and medicine, is prevalent nature organisms. Chiral molecules, such as DNA, RNA, proteins, are crucial biomolecular synthesis, well the development of functional materials. Among these, 1,1′‐binaphthyl‐2,2′‐diol (BINOL) stands out for its stable chiral configuration, versatile functionality, commercial availability. BINOL widely employed asymmetric catalysis This review mainly focuses on recent research over past five years concerning use derivatives constructing macrocycles cages. Their contributions to luminescence, enantiomeric separation, transmembrane transport, were examined.

Language: Английский

Citations

11
Shape‐Complementary Multicomponent Assembly of Low‐Symmetry Co(III)Salphen‐Based Coordination Cages DOI Creative Commons
Bo Zhang, Haeri Lee, Julian J. Holstein

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 4, 2024

Abstract While metal‐mediated self‐assembly is a popular technique to construct discrete nanosized objects, highly symmetric structures, built from one type of ligand at time, are dominating reported systems. The tailored integration set different ligands requires sophisticated approaches avoid narcissistic separation or formation statistical mixtures. Here, we demonstrate how the combination three structure‐guiding effects (metal‐templated macrocyclization, additional bridging and shape‐complementarity) based on Co(III)salphen metal nodes allows for rational high‐yielding synthesis structurally complex, lantern‐shaped cages with up four differentiable bridges. Three new heteroleptic coordination dinuclear macrocycles were synthesized in one‐pot reaction approach fully characterized, including single crystal X‐ray analyses. One cage groups two same ligands, another around Co 2 ‐bis‐salphen ring. In most complex structure, this ring unsymmetric, rendering all connections between centers distinguishable. assembly Pd(II) has been shown be dynamic, beneficial cage‐to‐cage transformations, cascades adaptive systems, herein introduced kinetically more inert will advantageous applications enzyme‐like catalysis molecular machinery that require enhanced structural chemical stability.

Language: Английский

Citations

7
Highly Anisotropic Pd2Lab2Lcc2 and Pd2Lab2Lcd2 Type Cages by Heteromeric Completive Self‐Sorting DOI

Minaz Parbin,

Vellaiyadevan Sivalingam, Dillip Kumar Chand

et al.

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

Published: Aug. 20, 2024

Pd(II)-based low-symmetry coordination cages possessing anisotropic cavities are of great interest. The common strategies employed to achieve such utilize either more than one type symmetrical ligands (e.g., L

Language: Английский

Citations

7
The cutting edge of lantern-shaped cage methodologies DOI

Zack T. Avery,

Jess L. Algar, Dan Preston

et al.

Trends in Chemistry, Journal Year: 2024, Volume and Issue: 6(7), P. 352 - 364

Published: April 9, 2024

Language: Английский

Citations

5
Guest Segregation in Heteromeric Multicage Systems DOI
Élie Benchimol,

Andrea Rivoli,

Michele Kabiri

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Dynamically interconvertible metallo-supramolecular multicomponent assemblies, coexisting orthogonally in solution, serve as simplified mimics for complex networks found biological systems. Building on recent advances controlling the nonstatistical self-assembly of heteroleptic coordination cages and heteromeric completive self-sorting, i.e., coformation multiple low-symmetry we herein describe first instance emerging functionality from a multicage system. In particular, one cage coexists equilibrium with or two different homoleptic cages, each capable preferentially encapsulating out three guests within their cavities. Guest segregation occurs under thermodynamic control can be reached following several distinct paths. Each pathway involves sequential transformations, eventually leading to same outcome. We that most mixture components (three ligands, guests, plus palladium cations) always yields an ordered, pathway-independent final state host–guest species, thus representing case simplexity self-sorted This study forms basis expanding scope dynamic transformation processes implemented Together incorporation stimuli-responsive elements other functionality, populations bioinspired applications controllable compound separation schemes, compartmentalized cascade reactions, multistep (even bifurcated) molecular information processing will become accessible.

Language: Английский

Citations

0
Synthesis of Precisely Functionalized Nano-confinement: a Bottom-up Approach to the Evolution of Selective Molecular Receptors DOI Creative Commons
Yonggang Tan,

Lumei Zhang,

Qixia Bai

et al.

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

Published: Jan. 1, 2025

Precise endo -functionalization tailors the host cavity to fit shape and charge distribution of target guest molecules, offering a novel bottom-up strategy for constructing customized molecular receptors.

Language: Английский

Citations

0
Synergistic regulation of metal–organic cage architectures via temperature- and solvent-driven atropisomerism DOI Creative Commons
Jiaqi Liang,

Li‐Jun Peng,

Kelin Zhu

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2025, Volume and Issue: 122(19)

Published: May 8, 2025

Regulating multistimulus responses in artificial systems remains a challenge smart material development. We present versatile chemical switching system that precisely controls the self-assembly of metal–organic cages via temperature and solvent changes. The key component, cyclo[2](1,3-(4,6-dimethyl)benzene) (4-pyridine)[6](1,3-(4,6-dimethyl)benzene) ( CP2 ), was generated as three atropisomers 1 , 2 3 ) with C s 2v symmetries. Thermally, metastable isomers convert into stable isomer which reacts Pd 2+ to form specific molecular cages. Depending on solvent, either rectangular M L 5′ 5 1,4-dioxane or hexagonal 6 1,1′,2,2′-tetrachloroethane. dictates cage type enables reversible transformation between . Additionally, ′, formed from can switch other types (i.e., depending conditions. This multipathway offers precise strategy for controlling materials.

Language: Английский

Citations

0
BINOL‐Based Chiral Macrocycles and Cages DOI

Yabing Yu,

Yaning Hu,

Chengbing Ning

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(29)

Published: May 6, 2024

Abstract Chirality, a fundamental principle in chemistry, biology, and medicine, is prevalent nature organisms. Chiral molecules, such as DNA, RNA, proteins, are crucial biomolecular synthesis, well the development of functional materials. Among these, 1,1′‐binaphthyl‐2,2′‐diol (BINOL) stands out for its stable chiral configuration, versatile functionality, commercial availability. BINOL widely employed asymmetric catalysis This review mainly focuses on recent research over past five years concerning use derivatives constructing macrocycles cages. Their contributions to luminescence, enantiomeric separation, transmembrane transport, were examined.

Language: Английский

Citations

3
London Dispersion driven Compaction of Coordination Cages in the Gas-phase – A combined Ion Mobility and Theoretical Study DOI Creative Commons

Christoph Drechsler,

Ananya Baksi,

André Platzek

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(46), P. 19264 - 19272

Published: Jan. 1, 2024

Large self-assembled systems (such as metallosupramolecular rings and cages) can be difficult to structurally characterize, in particular when they show a highly dynamic behavior.

Language: Английский

Citations

1