Synthesis of Nonplanar Push–Pull Chromophores with Various Heterocyclic Moieties via [2 + 2] Cycloaddition-Retroelectrocyclization Reaction

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

A series of 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) derivatives with various heterocyclic moieties, including pyridine, carbazole, indole, and benzothiadiazole, was newly synthesized through a [2 + 2] cycloaddition-retroelectrocyclization reaction. Symmetric electron-rich 1,3-butadiynes end-capped substituents were reacted tetracyanoethylene (TCNE), yielding the target TCBD products in 60–80% yields under ambient or mild heating conditions. The thermal stability optical electrochemical properties both 1,3-butadiyne precursors corresponding investigated by using thermogravimetric analysis (TGA), UV–vis spectroscopy, cyclic voltammetry (CV). featured narrow bandgaps due to intramolecular charge transfer interactions push–pull chromophores. In addition, optimized structures frontier molecular orbitals their energy levels determined density functional theory (DFT) calculations.

Language: Английский

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Carbamate‐Functionalized NLOphores via a Formal [2+2] Cycloaddition‐Retroelectrocyclization Strategy

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

This study introduces a new donor group capable of activating click-type [2+2] cycloaddition-retroelectrocyclizations, generally known for their limited scope. Target chromophores were synthesized using isocyanate-free urethane synthesis. The developed synthetic method allows the tuning optical properties by modifying groups, acceptor units, and side chains. charge transfer (CT) bands exhibit λmax values ranging from 363 to 692 nm. CT observed have been supported solvatochromism protonation experiments. compounds positive solvatochromism. Due potential as NLOphore candidates, stability investigated both experimentally through TGA theoretically calculating parameters such frontier orbital energy differences, electronegativity, global hardness/softness. TD-DFT calculations used elucidate nature electronic transitions, revealing that correspond arising HOMO-to-LUMO excitations. NLO DFT methods EFISHG technique. Both results are shown be in agreement with HOMO-LUMO differences. experimental μβ selected molecules range 470×10-48 5400×10-48 esu.

Language: Английский

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Introducing Pyridone[α]-Fused BOPHYs as Red-Shifted Bright Fluorophore Potentially Useful as Non-fullerene Acceptors in Donor–Acceptor Dyads

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

Published: Jan. 24, 2025

A series of 2-pyridone[α]-fused BOPHYs 6–8 were prepared via a two-step procedure involving the preparation enamine, followed by an intramolecular heterocyclization reaction. In addition to being fully conjugated with BOPHY core pyridone fragment, 7 and 8 have pyridine group connected one- or two –CH2– groups. New characterized spectroscopy as well X-ray diffraction. Conjugation fragment into results in significant red shift absorption fluorescence while maintaining extremely high quantum yields. Axial coordination photophysical properties supramolecular dyads formed between pyridine-appended pyridone-fused TPPF20Zn (TPPF20Zn = zinc 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin) investigated using UV–vis gave binding constant range 1.46 × 105 4.6 M–1. The electronic structures excited-state new their donor–acceptor assemblies studied density functional theory (DFT) time-dependent DFT (TDDFT). HOMO – 1 complexes TPPF20Zn-7/8 are centered, LUMO is localized on entity, allowing potential → charge transfer from donor acceptor.

Language: Английский

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Design, synthesis, and redox properties of donor-π-donor ferrocenyl functionalized phenothiazine derivatives

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The redox-active species of ferrocene-functionalized phenothiazine derivatives exhibit NIR absorption (700–1000 nm), and extending conjugation at the N -position reduces energy gap.

Language: Английский

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NIR absorbing ferrocenyl phenothiazine based push–pull chromophores

Journal of Organometallic Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 123622 - 123622

Published: March 1, 2025

Language: Английский

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