B‐N Covalent Bond Embedded Double Hetero‐[n]helicenes for Pure Red Narrowband Circularly Polarized Electroluminescence with High Efficiency and Stability

Advanced Materials, Год журнала: 2023, Номер 36(5)

Опубликована: Сен. 12, 2023

Chiral B/N embedded multi-resonance (MR) emitters open a new paradigm of circularly polarized (CP) organic light-emitting diodes (OLEDs) owing to their unique narrowband spectra. However, pure-red CP-MR and devices remain exclusive in literature. Herein, by introducing B-N covalent bond lower the electron-withdrawing ability para-positioned B-π-B motif, first pair double hetero-[n]helicenes (n = 6 7) emitter peaking 617 nm with small full-width at half-maximum 38 high photoluminescence quantum yield ≈100% toluene is developed. The intense mirror-image CP light produced enantiomers characterized dissymmetry factors (g

Язык: Английский

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Dynamic Near‐Infrared Circularly Polarized Luminescence Encoded by Transient Supramolecular Chiral Assemblies

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)

Опубликована: Май 13, 2024

Abstract Circularly polarized luminescence (CPL) is promising for applications in many fields. However, most systems involving CPL are within the visible range; near‐infrared (NIR) CPL‐active materials, especially those that exhibit high g lum values and can be controlled spatially temporally, rare. Herein, dynamic NIR‐CPL with a value of 2.5×10 −2 was achieved through supramolecular coassembly energy‐transfer strategies. The chiral assemblies formed by between adenosine triphosphate (ATP) pyrene derivative exhibited red signal ( 10 −3 ). further introduction sulfo‐cyanine5 resulted process, which not only led to NIR but also increased . Temporal control these realized introducing alkaline phosphatase fabricate biomimetic enzyme‐catalyzed network, allowing turned on. Based on enzyme‐regulated temporally controllable assemblies, multilevel information encryption system developed. This study provides pioneering example construction materials ability perform temporal via assembly strategy, expected aid design complex more closely resemble natural biological systems.

Язык: Английский

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Advances in circularly polarized luminescence materials based on chiral macrocycles

Chemical Communications, Год журнала: 2023, Номер 59(88), С. 13089 - 13106

Опубликована: Янв. 1, 2023

This review comprehensively summarizes circularly polarized luminescence materials from chiral macrocycles, especially macrocyclic hosts and their derivatives.

Язык: Английский

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Highly Luminescent Chiral Double π-Helical Nanoribbons

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5295 - 5304

Опубликована: Фев. 16, 2024

Unveiling the mechanism behind chirality propagation and dissymmetry amplification at molecular level is of significance for development chiral systems with comprehensively outstanding chiroptical performances. Herein, we have presented a straightforward Cu-mediated Ullmann homocoupling approach to synthesize perylene diimide-entwined double π-helical nanoribbons encompassing dimer, trimer, tetramer while producing homochiral or heterochiral linking centers. A significant was achieved, absorption factors (|gabs|) increasing from 0.009 0.017 further 0.019, luminescence (|glum|) rising 0.007 0.013 eventually 0.015 oligomers. The disparity magnetic transition dipole moment (m) densities in tetramers by time-dependent density functional theory calculations confirmed that oligomerization can maximize total m, which favorable achieving ever-increasing g factors. Notably, these π-helices exhibited exceptional photoluminescence quantum yields (ΦPL) ranging 83 95%. circularly polarized brightness (BCPL) reached remarkable 575 M–1 cm–1 tetramer, among highest values reported small molecules. This kind linearly extended offers platform comprehensive understanding amplification.

Язык: Английский

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A Stable Chichibabin Diradicaloid with Near‐Infrared Emission

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(29)

Опубликована: Май 2, 2024

Abstract Conjugated molecules with multiple radical centers such as the iconic Chichibabin diradicaloid hold promise building blocks in materials for quantum sensing and information processing. However, it is a considerable challenge to design simple analogues of hydrocarbon that are chemically inert, exhibit high diradical character emit light at distinct wavelength may offer an optical readout spin state functional ensembles. Here we describe serendipitous discovery stable TTM‐TTM diradicaloid, which exhibits character, striking sky‐blue color near‐infrared (NIR) emission (in solution). This combination properties unique among related diradicaloids due presence hydrogen chlorine atoms “just right positions”, allowing perfectly planar, yet predominantly benzenoid bridge connect two sterically stabilized centers. In‐depth studies magnetic suggest this structural motif could become mainstay block organic materials.

Язык: Английский

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A Chirally Locked Bis-perylene Diimide Macrocycle: Consequences for Chiral Self-Assembly and Circularly Polarized Luminescence

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5470 - 5479

Опубликована: Фев. 14, 2024

Macrocycles containing chiral organic dyes are highly valuable for the development of supramolecular circularly polarized luminescent (CPL) materials, where a preorganized framework is conducive to directing π–π self-assembly and delivering strong persistent CPL signal. Here, perylene diimides (PDIs) an excellent choice dye component because, alongside their tunable photophysical properties, functionalization PDI's core yields twisted, π-system, capable CPL. However, configurationally stable PDI-based macrocycles rare, those that also beyond dimers unprecedented, both which advantageous robust self-assembled chiroptical materials. In this work, we report first bay-connected bis-PDI macrocycle (ΔG⧧ > 155 kJ mol–1). We use chirally locked uncover new knowledge PDI perform quantitative imaging resulting single-crystal As such, discover chirality 1,7-disubstituted provides rational route designing H-, J- concomitant H- J-type important arrangements optimizing (chir)optical charge/energy transport properties. Indeed, reveal amplified in single crystals our by quantifying degree emitted light circular polarization from such materials time using CPL-Laser Scanning Confocal Microscopy.

Язык: Английский

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Circularly Polarized Luminescent π‐Conjugated Chiral Nanorings and Nanobelts

Advanced Optical Materials, Год журнала: 2024, Номер 12(18)

Опубликована: Май 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.

Язык: Английский

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Hyperconjugation Engineering of π-Extended Azaphosphinines for Designing Tunable Thermally Activated Delayed Fluorescence Emitters

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

Опубликована: Янв. 20, 2025

Implanting heteroatoms into organic π-conjugated molecules (OCMS) offered a great opportunity to fine-tune the chemical structures and optoelectronic properties. This work describes new family of 1,4-azaphosphinines with extended σ–π hyperconjugations. The photophysical studies revealed that azaphosphinines exhibited narrow-band thermally activated delayed fluorescence (TADF) ( full width at half-maximum: 26–40 nm). According orbital localization analysis natural bond analysis, effective σ*−π* hyperconjugation is believed induce multiple-resonance (MR) TADF, which distinct from p−π conjugation-induced MR-TADF in BN systems. Although having large ΔES1–T1s (>3.0 ev), study suggested σ*−π endowed system structural vibration favorable for spin-vibronic-assisted RISC. Having tunable p-centers (lp, O, S, Se, Me+), showed fine-tuned TADF. Generally, strong hyperconjugations small ΔES1–T1s, efficient RISCs, high PLQYs. Leveraging on hyperconjugations, TADF emission spanned UV-blue green. Particularly, photoluminescence quantum yields (74% toluene 92% 10% doped PMMA). As proof concept, two PO center were applied as light-emitting materials lighting-emitting diodes. devices UV- deep-blue EQE 10.3%. current us strategy, namely, hyperconjugation-induced MR-TADF, designing OCMs

Язык: Английский

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Polycationic Open‐Shell Cyclophanes: Synthesis of Electron‐Rich Chiral Macrocycles, and Redox‐Dependent Electronic States

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(27)

Опубликована: Фев. 27, 2024

π-Conjugated chiral nanorings with intriguing electronic structures and chiroptical properties have attracted considerable interests in synthetic chemistry materials science. We present the design principles to access new macrocycles (1 2) that are essentially built on key components of main-group electron-donating carbazolyl moieties or π-expanded aza[7]helicenes. Both show unique molecular conformations a (quasi) figure-of-eight topology as result conjugation patterns 2,2',7,7'-spirobifluorenyl 1 triarylamine-coupled aza[7]helicene-based building blocks 2. This nature redox-active, carbazole-rich backbones enabled these be readily oxidized chemically electrochemically, leading sequential production series positively charged polycationic open-shell cyclophanes. Their redox-dependent states resulting multispin polyradicals been characterized by VT-ESR, UV/Vis-NIR absorption spectroelectrochemical measurements. The singlet (ΔE

Язык: Английский

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Synthesis and Chiroptical Properties of Radially Extended Carbazole with Chiral [2.2]Paracyclophane Core

Advanced Functional Materials, Год журнала: 2024, Номер 34(47)

Опубликована: Фев. 16, 2024

Abstract [2.2]Paracyclophanes ([2.2]PCs) with substituents at specific positions possesses planar chirality and stands as a promising building unit for the development of chiroptical materials associated polarized light. However, one easily accessible starting materials, bromo‐substituted [2.2]PC, shows low reactivity, effective methods π‐extension chiral [2.2]PC are limited. Herein, an method has established four substitutions from 4,7,12,15‐tetrabromo[2.2]PC. This led to tetrakis(trimethylsilylphenyl)‐[2.2]PC that serves versatile resource radial‐type π‐conjugated compounds core. In this study, synthesizing further succeeded introduction carbazole ( Cbz 4 ‐[2.2]PC t BuCbz ) investigated their properties induction ability in achiral polymers. A thin film [Poly[9,9‐dioctylfluorenyl‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)]] (F8BT) 3wt% prepared by spin‐coating exhibits circularly luminescence (CPL) high dissymmetry factor (| g lum | = 0.01), which is much higher than CH 2 Cl solution. By contrast, doped F8BT exhibited only weak CPL properties. addition, these show facile redox owing presence units. Furthermore, undergoes electropolymerization produce insoluble on electrode.

Язык: Английский

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