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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Host‐Guest Chemistry in Binary and Ternary Complexes Utilizing π‐Conjugated Carbon Nanorings

ChemPlusChem, Journal Year: 2023, Volume and Issue: 89(7)

Published: Dec. 21, 2023

The carbon nanorings, possessing a radial π system, have garnered significant attention primarily due to their size-dependent photophysical properties and the presence of unique curved π-conjugated cavity. This is evidenced by rapid proliferation publications. Furthermore, integration building blocks into CPP skeletons can confer [n]CPPs with novel exceptional electronic characteristics, as well chiral host-guest interactions, thereby augmenting diversity [n]CPPs. Notably, surface structures concave cavity nanorings enable them host aromatic or non-aromatic guests complementarily surface, resulting in interesting binary ternary complexes. review provides comprehensive treatment literature reports on complexes, focusing both interactions properties. It important note that scope this limited chemistry complexes based nanorings.

Language: Английский

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Highly Luminescent Chiral Carbon Nanohoops via Symmetry Breaking with a Triptycene Unit: Bright Circularly Polarized Luminescence and Size‐Dependent Properties

Small, Journal Year: 2023, Volume and Issue: 20(14)

Published: Nov. 21, 2023

Abstract Chiral carbon nanohoops with both high fluorescence quantum yield and large luminescence dissymmetry factor are essential to the development of circularly polarized (CPL) materials. Herein, rational design synthesis a series highly fluorescent chiral TP‐[8–13]CPPs via symmetry breaking triptycene motif is reported. Theoretical calculations revealed that causes unique size‐dependent localization in highest occupied molecular orbitals (HOMOs) lowest unoccupied obtitals (LUMOs) as increasing sizes, which sharply different from those [n]cycloparaphenylenes. Photophysical investigations demonstrated TP‐[n]CPPs display emissions yields up 92.9% for TP‐[13]CPP, value among reported conjugated nanohoops. The presumably attributed acyclic, radial conjugations radiative transition rates, further supported by theoretical investigations. Chiroptical studies exhibit bright CPL brightness 100.5 M −1 cm TP‐[11]CPP due yield. Importantly, intrigued properties regards (chir)optical properties, follow nice linear relationship versus 1/n. Such not observed other including CPPs.

Language: Английский

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Fluorescence-enhanced supra-amphiphilies based on pillar[5]arene: construction, controllable self-assembly and application in cell-imaging

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(59), P. 7646 - 7649

Published: Jan. 1, 2024

Fluorescence-enhanced supra-amphiphiles based on (WP5)

Language: Английский

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Perphenazine Modified Pillar[5]arene Based Nano-Assemblies for Synergistic Photothermal and Photodynamic Cancer Therapy

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(64), P. 8387 - 8390

Published: Jan. 1, 2024

Nano-assemblies based on perphenazine modified pillar[5]arene were constructed successfully for synergistic photothermal and photodynamic (I&II) cancer therapy.

Language: Английский

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Recent advance development in pillar[5]arene-based nanomaterials for cancer therapy

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

Published: Jan. 1, 2025

In this review, we summarize five different types of pillar[5]arene-based nanomaterials and their applications in chemotherapy, photodynamic therapy, photothermal multimodal synergistic therapy for tumors.

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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Pyridine‐Based Rigidochromic Fluorescent Security Ink

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Comprehensive Summary Traditional fluorescent probes typically display blueshifted emission in rigidifying media; however, a newly developed class of rigidochromic fluorophores derived from phenanthridine demonstrates remarkable redshifted under similar conditions. Pyridine, with N‐heterostructure to those group, is considered promising candidate for achieving comparable rigidity‐induced redshift behavior. In this work, we synthesized eight organic featuring diverse functional units and substitutes by systematically combining pyridine carbazole, triazatruxene (TAT), tetraphenylethylene (TPE), respectively. These molecules exhibit significant redshifts (up 225 nm, record high value ever reported) or notable intensity changes as the rigidity polymer matrix increases, along unique acid responsiveness. The differences polar‐π interactions between polymers diversify behavior, advancing development secure printing intelligent optical materials. By embedding these into films helical phase structures, tunable chirality was achieved. Notably, leveraging acid‐responsive properties fluorophores, time‐dependent light‐controlled dynamic encryption system constructed, successfully enabling multi‐level information encryption. This research greatly expands scope their applications anti‐counterfeiting storage.

Language: Английский

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