Facile Synthesis of Donor–Acceptor Heterocycloarenes Based on Pyrazine Derivatives Possessing Intriguing Iodide Ion Capture Properties

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21922 - 21931

Published: July 25, 2024

Donor–acceptor (D–A) conjugated systems have been extensively investigated and play important roles in organic electronics. Incorporating D–A structures into (hetero)cycloarenes endows them tunable electronic properties, while the well-defined cavity remains. However, synthetic complexity of introducing electron-acceptor moieties limits their development applications. In this paper, first family electronically heterocycloarenes (DAHCn, n = 1–5) based on pyrazine derivatives was facilely synthesized through cyclocondensation reaction from a tetraketone-functionalized heterocycloarene precursor prepared using ketal-protection strategy. The effect expanded conjugation inserted electron-withdrawing group studied systematically by X-ray crystallographic analysis, various spectroscopic measurements, theoretical calculations. Interestingly, presence an polarizes inner C(sp2)–H significantly increases binding affinities to iodide anion. Meanwhile, anion affinity can be further modulated type attached substituents distance polarization. More importantly, dicyanopyrazine derivative DAHC3 shows highest strength ion as 2:1 sandwich complex (log β2 12.3 ΔG −69.1 kJ mol–1), which is strongest receptor hydrogen bonding interactions reported date. Our finding provides new strategy design synthesize strong receptors.

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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FRET-Mediated Photoswitchable Catalytic Metallacage with Tunable Activity for Organic Dye Degradation

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

Published: April 2, 2025

Photoswitchable catalysts provide a versatile strategy for controlling catalytic activities through light stimuli, presenting significant potential the precise regulation of synthetic transformations. Herein, we successfully synthesized novel photoswitchable metallacage MC from meso-tetra-(2-pyridyl)-porphines (TPP) and Pt(II)-bisthienylethene (DTE-1) via coordination-driven self-assembly. The ligand within exhibits reversible conversion between its ring-opened ring-closed isomers upon alternating UV visible radiation, facilitating Förster resonance energy transfer (FRET) in systems. Notably, two forms exhibit switchable performance highly poorly catalytical activity degradation Rhodamine B. This work not only develops metallacage-based FRET system but also provides new avenue constructing artificial photoregulated enzymes.

Language: Английский

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Oxindole-Terminated Quinoidal Compounds with Ultrahigh Electron Affinity: Synthesis and Applications

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Six quinoidal compounds terminated by oxindole have been synthesized via selective nucleophilic addition, dehydroxylation, and oxidation. Through the modification of core terminal benzene rings with fluoride atoms or cyano groups, LUMO energy levels can be tuned within range -4.05 to -4.54 eV. The molecules exhibited electron transport behavior used as dopants dope an oligo(ethylene glycol)-substituted polythiophene.

Language: Английский

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1,4-Azaborine Participation Enables Inaccessible Cycloarene with Unique Photophysical Properties

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

Published: Feb. 26, 2025

Cycloarenes and heterocycloarenes, characterized by fused macrocyclic π-conjugated structures, hold significant promise in synthetic chemistry materials science. However, their further development remains constrained formidable challenges, particularly for those with contracted cavities. Inspired advances the synthesis of organoboron-based multiresonance thermally activated delayed fluorescence (TADF) emitters, we herein report convenient access detailed characterization a 1,4-azaborine-embedded cycloarene that features smallest cavity among known (hetero)cycloarenes. The induces bowl-shaped molecular geometry, as confirmed crystallographic analysis, while also triggering through-space conjugation delocalized π-electrons at site. Comparative studies between this compound its helical analogue reveal substantial topological impact on photophysical properties, including bathochromic-shifted broadened emission band, prolonged radiative decay process, more efficient triplet-to-singlet spin-flip. Capitalizing TADF remarkably high quantum yield, successfully fabricated first (hetero)cycloarene-based organic light-emitting diodes, achieving over 30% external efficiency minimal roll-off. These findings offer new insights into design topologically distinct compounds unique properties.

Language: Английский

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Design Strategies, Properties, and Applications toward Cycloarenes and Heterocycloarenes

Accounts of Materials Research, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

Language: Английский

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Cyano-functionalized bis-carbazole derivatives for high contrast electrochromism

Dyes and Pigments, Journal Year: 2024, Volume and Issue: 226, P. 112117 - 112117

Published: March 29, 2024

Language: Английский

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The anti-correlation effect of alkyl chain size on the photovoltaic performance of centrally extended non-fullerene acceptors

Materials Horizons, Journal Year: 2024, Volume and Issue: 11(18), P. 4413 - 4423

Published: Jan. 1, 2024

Contrary to previous results, a unique anti-correlation effect of the alkyl chain size on photovoltaic performance acceptors was observed. For centrally-extended acceptor, replacing linear chains (

Language: Английский

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A review on diverse streams of interface engineering for organic thin-film transistors

Journal of Materials Chemistry C, Journal Year: 2023, Volume and Issue: 12(1), P. 29 - 49

Published: Nov. 20, 2023

This review article provides a critical overview of the diverse technological streams interface engineering formed in field OTFTs.

Language: Английский

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Effect of substituents on self-assembling behaviors and charge transport properties of nonplanar heterocycloarenes

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(10), P. 2903 - 2911

Published: Sept. 11, 2023

Language: Английский

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