Acceptor engineering of quinone-based cycloparaphenylenes via post-synthesis for achieving white-light emission in single-molecule

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

Published: Jan. 7, 2025

Developing donor-acceptor [n]cycloparaphenylenes (D-A [n]CPPs) with multiple emissions from different emissive states remains challenging yet crucial for achieving white-light emission in single-molecule. Here, we report our explorations into acceptor engineering of quinone-based D-A [10]CPPs (Nq/Aq/Tq[10]CPPs) via a post-lateral annulation using Diels-Alder reactions oxTh[10]CPP. X-ray analysis reveals that Nq[10]CPP displays side by packing naphthoquione stacking while Aq[10]CPP adopts an intercalated conformation through anthraquinone interaction. Fluorescence investigations reveal the display distinctive acceptor-dependent dual-emission both locally excited state and charge transfer after single-wavelength excitation organic solvents, consequently leading to multicolor emissions, particular, CHCl3 Aq[10]CPP. In THF/water mixture, oxTh[10]CPP wide range fluorescence including as increasing fraction water, accompanying formation nanoparticles demonstrated Tyndall effect SEM. Interestingly, can be switched white blue upon redox. Our demonstrate not only endows two distint but also highlights effective post-synthetic strategy functionalizing CPP nanohoops desirable properties. authors yield emission.

Language: Английский

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Circularly Polarized Luminescent π‐Conjugated Chiral Nanorings and Nanobelts

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

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Monitoring Hierarchical Assembly of Ring-in-Ring and Russian Doll Complexes Based on Carbon Nanoring by Förster Resonance Energy Transfer

JACS Au, Journal Year: 2024, Volume and Issue: 4(2), P. 402 - 410

Published: Jan. 22, 2024

We presented the construction of ring-in-ring and Russian doll complexes on basis triptycene-derived carbon nanoring (TP-[12]CPP), which not only acts as a host for pillar[5]arene (P5A) but also serves an energy donor building Förster resonance transfer (FRET) systems. demonstrated that their hierarchical assembly processes could be efficiently monitored in real time using FRET. NMR, UV–vis fluorescence, mass spectroscopy analyses confirmed successful encapsulation guests P5A/P5A-An by TP-[12]CPP, facilitated C–H···π ···π interactions, resulting formation distinct complex with binding constant Ka = 2.23 × 104 M–1. The encapsulated can further reverse its role to acceptors form complexes, evidenced occurrence FRET analyses. apparent was up 3.6 M–1, thereby suggesting enhanced synergistic effect. Importantly, exhibited both intriguing one-step sequential dependent subcomponent during assembly, reminiscent structure light-harvesting system purple bacteria.

Language: Английский

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Modular Synthesis of Improbable Rotaxanes with All‐Benzene Scaffolds

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 26, 2024

"Improbable" rotaxanes consisting of interlocked conjugated components represent non-trivial synthetic targets, not to mention those with all-benzene scaffolds. Herein, a modular strategy has been established using an isolable azo-linked pre-rotaxane as the core module, in which azo group functions tracelessly removable template direct mechanical bond formations. Through versatile connections and other customizable modules, [2]- [3]rotaxanes derived from scaffolds have accomplished, demonstrating utility potential design for supramolecules.

Language: Английский

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Synthesis, Characterization, and Resistive Memory Behaviors of Highly Strained Cyclometalated Platinum(II) Nanohoops

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 13226 - 13235

Published: May 3, 2024

Strained carbon nanohoops exhibit attractive photophysical properties due to their unique π-conjugated structure. However, incorporation of such into the pincer ligand metal complexes has rarely been explored. Herein, a new family highly strained cyclometalated platinum(II) synthesized and characterized. Strain-promoted C–H bond activation observed during coordination process, Hückel–Möbius topology random-columnar packing in solid state are found. Transient absorption spectroscopy revealed size-dependent excited nanohoops. Moreover, have successfully employed as active materials fabrication solution-processable resistive memory devices, including use smallest nanohoop for binary memory, with low switching threshold voltages ca. 1.5 V, high ON/OFF current ratios, good stability. These results demonstrate that strain structure can be an effective strategy fundamentally fine-tune reactivity, optoelectronic, properties.

Language: Английский

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A Conjugated Phenylene Nanocage with a Guest‐Adaptive Deformable Cavity

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: Feb. 29, 2024

Abstract The highly strained, phenylene‐derived organic cages are typically regarded as very rigid entities, yet their deformation potential and supramolecular properties remain underexplored. Herein, we report a pliable conjugated phenylene nanocage by synergistically merging flexible building blocks. anisotropic cage molecule contains branched chains capped calix[6]arene moiety, the delicate conformational changes of which endow with remarkably deformable cavity. When complexing fullerene guests, showcases excellent guest‐adaptivity, its cavity volume capable swelling much 85 %.

Language: Английский

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Key-to-lock halogen bond-based tetragonal pyramidal association of iodonium cations with the lacune rims of beta-octamolybdate

Chemical Science, Journal Year: 2024, Volume and Issue: 15(31), P. 12459 - 12472

Published: Jan. 1, 2024

The structure-directing "key-to-lock" interaction of double σ-(I

Language: Английский

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Naphthalene Diimide-Embedded Donor–Acceptor Carbon Nanohoops: Photophysical, Photoconductive, and Charge Transport Properties

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Designing the architecture of donor–acceptor (D–A) pairs is an effective strategy to tailor electronic structure conjugated macrocycles for optoelectronic devices. Herein, we present synthesis three D–A nanohoops NDI-[n]CPP (n = 7, 8, 9) containing a naphthalene diimide (NDI) unit as acceptor and [n]cycloparaphenylenes ([n]CPPs) moieties donors. The characteristics NDI-[7–9]CPPs were substantiated through absorption fluorescence spectroscopic studies, electrochemical investigations, computational analysis. device investigations demonstrated that can serve photoconductive layer demonstrate significant generation photocurrent with fast response upon exposure light. magnitude shows high dependence on size their rings, increasing tendency ring decreases. in free acceptor-based CPP has rarely been reported previous literature. Significantly, C60 complexes exhibited marked enhancement under identical conditions; particular, C60⊂NDI-[7]CPP ca. 3.5 times greater than NDI-[7]CPP alone. Furthermore, potential applications electron- hole-transport devices have also explored, revealing clear evidence bipolar behavior active charge transport layer.

Language: Английский

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A DFT insight into the potential of cycloparaphenylenes as efficient sensors for detecting Paracetamol

Scientific Reports, Journal Year: 2025, Volume and Issue: 15(1)

Published: March 9, 2025

Paracetamol (PCT) frequently contaminates natural water sources, posing potential risks to both human health and ecosystems. This study presents a computational investigation into the sensing capabilities of methylene-bridged [n]cycloparaphenylene ([n]MCPP, where n= 6, 8, 10) nanorings for detection paracetamol using density functional theory (DFT) calculations. It was found that stability PCT@[n]MCPP complexes increases with size [n]MCPP nanorings. The energy gap is significantly influenced by presence PCT drug, most substantial change (-44.79%) observed PCT@6MCPP complex. Additionally, non-covalent interaction (NCI) analysis reveals van der Waals forces predominantly govern interactions between calculated short recovery times favorable sensor response factors at 298 K suggest can be used as promising materials paracetamol. These findings underscore valuable candidates identifying eliminating drug from environment.

Language: Английский

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Optical Axial Chirality Enhancement and Transfer within Aromatic Micelles upon (Co-)encapsulation

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 586 - 592

Published: Feb. 3, 2025

Axial chirality is the key physiochemical element, yet its chiroptical utilities have been largely limited to covalent synthesis and infinitely assembled systems so far. Here we report a new application of axially chiral binaphthyls for efficient, optical enhancement transfer upon noncovalent encapsulation by achiral aromatic micelles in water. The CD activities dialkoxy are significantly enhanced (up 7-fold) an anthracene-based micelle. Large emission (∼4-fold) efficient guest-to-guest, achieved through coencapsulation with cycloparaphenylenes, guest-within-guest fashion, observed unusual properties derived from tight inclusion guests into macrocyclic guests, efficiently generated only cavity. Moderate CPL can be coencapsulated macrocycles within ternary composites. Furthermore, more than ∼4-fold guest-to-guest demonstrated functionalized cycloparaphenylene present strategy.

Language: Английский

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