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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Crystallization-Induced Chirality Transfer in Conformationally Flexible Azahelicene Au(I) Complexes with Circularly Polarized Luminescence Activation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12463 - 12472

Опубликована: Апрель 16, 2024

Flexible and twisted annulated π-systems exhibit numerous unique desirable features, owing to their ability display chirality. However, preventing racemization due the dynamic nature of chirality remains a challenge. One promising approach stabilize homochirality in such systems is transfer from chiral auxiliary moiety displaying Herein, we introduce new for stabilization conformationally flexible azahelicene species via crystallization-induced intermolecular Au(I) complexes featuring (dibenzo[

Язык: Английский

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Hierarchical chiral MOFs with the induced chirality of AIE ligands exhibiting non-reciprocal CPL

Chemical Communications, Год журнала: 2024, Номер 60(48), С. 6182 - 6185

Опубликована: Янв. 1, 2024

Two pairs of chiral MOFs, DCF-15/LCF-15 and DCF-16/LCF-16, were constructed through assembly achiral aggregation-induced emission (AIE)-type multidentate linkers (TPPE TPA) camphoric acid ( d / l -cam), exhibiting non-reciprocal CPL.

Язык: Английский

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Magnetic Circularly Polarized Luminescence of Organic Compounds

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(37)

Опубликована: Авг. 10, 2023

Abstract Achiral purely organic molecules can show selectivity towards circularly polarized light in emission the presence of a magnetic field. This phenomenon is called luminescence (MCPL). Recently few examples MCPL from have appeared literature. Through this technique, interesting photophysical information be inferred and, moreover, technological applications devised based on principle. short review has purpose to give general introduction recent field research and some critical insights reported examples.

Язык: Английский

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Significance of Vibronic Coupling that Shapes Circularly Polarized Luminescence of Double Helicenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(16)

Опубликована: Фев. 7, 2024

Abstract The circularly polarized luminescence (CPL) spectra of S ‐ and X ‐shaped double helicenes exhibit distinct vibrational structures overall shape variations. In this study, we conducted an in‐depth investigation into the vibronic effects influencing CPL two helicenes, namely DPC DNH . Employing state‐of‐the‐art computations utilizing FC‐HT 1 |VH model at CAM−B3LYP/def2‐TZVP level, unveiled paramount impact Franck–Condon (FC), Herzberg‐Teller (HT), Duschinsky on their chiroptical responses. Our research underscores pivotal role structural deformations associated with ‐to‐S 0 electronic transition in molding wavelength‐dependent dissymmetry ( g ) factor values, as well significance HT shaping enhancing This extensive not only advances our comprehension characteristics configurationally but also offers valuable insights for design chiral molecules featuring controllable or finely‐tunable

Язык: Английский

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Enantiomerically Pure Helical Bilayer Nanographenes: A Straightforward Chemical Approach

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 6, 2024

The semiconductor properties of nanosized graphene fragments, known as molecular nanographenes, position them exceptional candidates for next-generation optoelectronics. In addition to their remarkable optical and electronic features, chiral nanographenes exhibit high dissymmetry factors in circular dichroism circularly polarized luminescence measurements. However, the synthesis enantiomerically pure remains a significant challenge. Typically, these materials are synthesized racemic form, followed by separation enantiomers using high-performance liquid chromatography (HPLC). While effective, this method often requires expensive instrumentation, extensive optimization conditions, typically yields analytical quantities desired samples. An alternative approach is enantioselective nanographenes; however, date, only two examples have been documented literature. work, we present straightforward chemical resolution helical bilayer nanographenes. This enables effective scalable preparation while avoiding need HPLC. incorporation BINOL core into polyarene precursor facilitates diastereomers through esterification with camphorsulfonyl chloride. Following standard chromatographic column, hydrolysis group nanographene precursors. subsequent graphitization, achieved Scholl reaction, occurs an enantiospecific manner concomitant formation furan ring heterohelicene moiety. absolute configurations final enantiomers, P-oxa[9]HBNG M-oxa[9]HBNG, determined X-ray diffraction. Additionally, electrochemical, photophysical, chiroptical thoroughly evaluated.

Язык: Английский

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A Perspective on the Simulation of Electronic Circular Dichroism and Circularly Polarized Luminescence Spectra in Chiral Solid Materials

The Journal of Physical Chemistry A, Год журнала: 2024, Номер 128(7), С. 1197 - 1206

Опубликована: Янв. 31, 2024

Chiral materials have shown tremendous potential for many technological applications, such as optoelectronics, sensing, magnetism, information technology, and imaging. Characterization of these is mostly based on chiroptical spectroscopies, electronic circular dichroism (ECD) circularly polarized luminescence (CPL). These experimental measurements would greatly benefit from theoretical simulations interpretation the spectra well predictions new materials. While ECD CPL are established molecular systems, they not In this Perspective, we describe quantities necessary to simulate in oriented systems. Then, discuss approximate strategies currently used perform calculations, what computational machinery already available develop more general approaches, some open challenges simulation solid When methods that reliable computationally efficient those molecules developed, will provide invaluable insight guidance rational design optically active

Язык: Английский

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Bridging of Cove Regions: A Strategy for Realizing Persistently Chiral Double Heterohelicenes with Attractive Luminescent Properties

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Фев. 9, 2024

The racemization of chiral organic compounds is a common chemical phenomenon. However, it often poses configurational-stability issues to the application this class compounds. Achieving without risk fascinating, but challenging due lack strategies. Here, we reveal cove-regions bridging strategy for achieving persistently multi-helicenes (incapable racemization), based on synthesized proof-of-concept double hetero[4]helicenes featuring macrocycle structures with small 3D cavity. Additionally, demonstrate that also effective in tuning electronic multi-helicenes, resulting conversion from luminescence silence into thermally activated delayed fluorescence (TADF) present system. Furthermore, red circularly polarized TADF [4]helicene systems achieved first time using strategy. disclosed provides an opportunity modulate and luminescent properties concern racemization, thus significantly enhancing structural property diversity various applications.

Язык: Английский

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Synthesis, photophysical and chiroptical properties of 9–cyano[7]helicene for OLED applications. A combined experimental and theoretical investigation

Journal of Materials Science Materials in Electronics, Год журнала: 2024, Номер 35(7)

Опубликована: Март 1, 2024

Язык: Английский

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Triple para-Functionalized Cations and Neutral Radicals of Enantiopure Diaza[4]helicenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 8308 - 8319

Опубликована: Март 14, 2024

Modulation of absorbance and emission is key for the design chiral chromophores. Accessing a series compounds absorbing emitting (circularly polarized) light over wide spectral window often toward near-infrared practical value in (chir)optical applications. Herein, by late-stage functionalization on derivatives bridging triaryl methyl helicene domains, we have achieved regioselective triple introduction para electron-donating or electron-withdrawing substituents. Extended tuning electronic (e.g., E1/2red −1.50 V → −0.68 V) optical covering from 550 to 850 nm) properties cations neutral radicals; latter being easily prepared mono electron reductions under electrochemical chemical conditions. While luminescence quantum yields can be increased up 70% cationic series, strong Cotton effects are obtained certain radicals at low energies (λabs ∼ 700–900 with gabs values above 10–3. The open-shell nature was further characterized paramagnetic resonance revealing an important spin density delocalization that contributes their persistence.

Язык: Английский

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