Boron-containing helicenes as new generation of chiral materials: opportunities and challenges of leaving the flatland

Chemical Science, Год журнала: 2024, Номер 15(20), С. 7408 - 7440

Опубликована: Янв. 1, 2024

Recent advances in synthesis have opened the way to a variety of boron helicenes. We highlight main achievements these chiral compounds and discuss their photophysical properties potential as functional materials.

Язык: Английский

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BODIPY-based photocages: rational design and their biomedical application

Chemical Communications, Год журнала: 2024, Номер 60(45), С. 5770 - 5789

Опубликована: Янв. 1, 2024

This highlight reviews various strategies for constructing BODIPY-based photocages, their photodecaging mechanisms, and applications in the biomedical field.

Язык: Английский

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Supramolecular Polymerization as a Tool to Reveal the Magnetic Transition Dipole Moment of Heptazines

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 15843 - 15849

Опубликована: Май 30, 2024

Heptazine derivatives have attracted significant interest due to their small S1-T1 gap, which contributes unique electronic and optical properties. However, the nature of lowest excited state remains ambiguous. In present study, we characterize transition heptazine by its magnetic dipole moment. To measure moment, flat must be chiroptically active, is difficult achieve for single molecules. Therefore, used supramolecular polymerization as an approach make homochiral stacks derivatives. Upon formation polymers, preferred helical stacking introduces circular polarization absorption fluorescence. The moments S1 ← S0 → are determined 0.35 0.36 Bohr magneton, respectively. These high values support intramolecular charge transfer from nitrogen carbon in further confirm degeneracy T1.

Язык: Английский

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Helicene‐type β‐isoindigo‐based boron‐dipyrromethene analogs with strong near‐infrared chiroptical activity

Aggregate, Год журнала: 2024, Номер 5(3)

Опубликована: Янв. 5, 2024

Abstract Near‐infrared (NIR) chiroptical response has been less explored because it is challenging to achieve both chirality and NIR absorption/emission. Herein, we describe the design of heterohelicene‐type β‐isoindigo‐based boron‐dipyrromethene (BODIPY) analogs (β‐IBs), which shift absorption peak 800 nm produce significant Cotton effects (127.8 M −1 cm ) absorbance dissymmetry factors (| g abs | = 3.5 × 10 −3 ). The luminescence factor ( lum circularly polarized (CPL) brightness B CPL up 1.24 1.78 were realized beyond nm. These β‐IBs are first examples helicene‐type compounds with highest in region Theoretical calculations demonstrate that strong activities triggered by their large transition magnetic dipole moments. This study not only provides a new approach synthesis larger variety unprecedented BODIPY but also demonstrates excellent properties.

Язык: Английский

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Construction of Circular Polarized Luminescence Molecules for Intense Near Infrared OLEDs

Advanced Optical Materials, Год журнала: 2024, Номер 12(16)

Опубликована: Март 14, 2024

Abstract The exploration of organic near‐infrared (NIR) luminescence, along with circularly polarized luminescence (CPL), is vital importance due to its significance in medical and optoelectronic applications. Integrating a chiral unit into D–A molecular structure this research realized emission peaks at 744 nm, exhibiting dissymmetric factor −1.67 × 10 −3 . introduced TPA derivative not only imparts aggregation‐induced properties CPL capabilities but also induces redshift the spectrum. Consequently, fabricated NIR light‐emitting devices (OLEDs), achieve maximum electroluminescent 748 nm nondoped external quantum efficiency 13.7% doped devices. This pioneering provides inspiration for design molecules possessing future, particularly promoting application intense NIR‐OLEDs.

Язык: Английский

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Real-Time Observation of Ultrafast Concerted Dynamics between Energy and Chirality Transfer by Femtosecond Time-Resolved Circular Polarization Luminescence Spectroscopy

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

Elucidating the underlying mechanism of effective chirality and energy transfer processes observed in biological assemblies has cross-disciplinary significance, it is special interest fields chemistry biology due to pivotal role life. Challenges field include how achieve real-time monitoring dynamics simultaneously, as well distinguish whether these take place ground or excited state. Herein, we first attempt at observation concerted ultrafast between Förster resonance (FRET) generation circularly polarized luminescence (CPL) state near-infrared CPL supramolecular nanofibers (SNFs) by using femtosecond time-resolved (fs-TRCPL) spectroscopy. Our findings reveal a cooperative interplay FRET emission, unfolding over time scales from several hundreds picoseconds. Notably, identify that leading 0.045 glum value SNFs difference rates left- right-handed emission channels, which reason beyond well-known relationship electronic magnetic dipoles. results not only shed light on understanding states but also pave road for development novel materials future.

Язык: Английский

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Intense Circularly Polarized Luminescence Induced by Chiral Supramolecular Assembly: The Importance of Intermolecular Electronic Coupling

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июль 17, 2024

Abstract Herein we report on circularly polarized luminescence (CPL) emission originating from supramolecular chirality of organic microcrystals with a | g lum value up to 0.11. The were prepared highly emissive difluoroboron β‐diketonate (BF 2 dbk) dyes R ‐ 1 or S chiral binaphthol (BINOL) skeletons. and exhibit undetectable CPL signals in solution but manifest intense their microcrystals. superstructures induced by BINOL skeletons confirmed single‐crystal XRD analysis. Spectral analysis theoretical calculations indicate that intermolecular electronic coupling, mediated the asymmetric stacking superstructures, effectively alters excited‐state structures facilitates electron transitions perpendicular BF bdk planes. coupling increases cos θ μ , m 0.05 (monomer) 0.86 (tetramer) triggers optical activity bdk. results demonstrate chromophores within assemblies can be regulated both orientation extent couplings.

Язык: Английский

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Metal Halide Perovskite Nanocrystals for Near-Infrared Circularly Polarized Luminescence with High Photoluminescence Quantum Yield via Chiral Ligand Exchange

The Journal of Physical Chemistry Letters, Год журнала: 2023, Номер 14(24), С. 5489 - 5496

Опубликована: Июнь 8, 2023

Using ligand exchange on FAPbI3 perovskite nanocrystals (PNCs) surface with chiral tridentate l-cysteine (l-cys) ligand, we successfully prepared PNCs that show circularly polarized luminescence (CPL) (dissymmetry factor; glum = 2.1 × 10-3) in the near-infrared (NIR) region from 700 to 850 nm and a photoluminescence quantum yield (PLQY) of 81%. The characteristics are ascribed induction by l/d-cys, high PLQY is attributed passivation defects l-cys. Also, effective l-cys results excellent stability toward atmospheric water oxygen. conductivity treated NC films improved, which partial substitution for insulating long oleyl ligand. CPL film retains -2.7 10-4. This study demonstrates facile yet approach generating NIR photonics applications.

Язык: Английский

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A Deep‐Red Emissive Sulfur‐Doped Double [7]Helicene Photosensitizer: Synthesis, Structure and Chiral Optical Properties

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Авг. 8, 2024

Doping of polycyclic conjugated hydrocarbons (PCHs) with sulfur atoms is becoming more and important as a means creating unique functional materials. Recently, thiophene-containing multiple helicenes have garnered enormous attention due to their intriguing electronic (chir)optical properties compared carbohelicenes. However, the efficient synthesis thiopyran-containing underlying doping mechanisms are rather unexplored. Herein, structural analysis double [7]helicene 3 reported. X-ray crystallographic reveals its dication C

Язык: Английский

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A Catalytic Enantioselective Suzuki Coupling for the Modular Construction of Axially Chiral BODIPYs with Bright Solid-State Emission

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 17, 2024

The development of chiral BODIPYs attracts remarkable interest due to their unique properties, structural diversity, and good photochemical stability, whereas achieving the construction maintains scarce. Herein, we present an enantioselective synthesis axially through Suzuki-Miyaura coupling. newly synthesized coassembly showed desirable photophysical including high fluorescence quantum yields intense CPL, both in solution solid state.

Язык: Английский

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