A general supramolecular strategy for fabricating full-color-tunable thermally activated delayed fluorescence materials

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 16, 2024

Abstract Developing a facile and feasible strategy to fabricate thermally activated delayed fluorescence materials exhibiting full-color tunability remains an appealing yet challenging task. In this work, general supramolecular for fabricating is proposed. Consequently, series of host–guest cocrystals are prepared by electron-donating calix[3]acridan various electron-withdrawing guests. Owing the through-space charge transfer mediated multiple noncovalent interactions, these all display efficient fluorescence. Especially, delicately modulating ability guest molecules, emission colors can be continuously tuned from blue (440 nm) red (610 nm). Meanwhile, high photoluminescence quantum yields up 87% achieved. This research not only provides alternative fabrication materials, but also establishes reliable protocol toward design advanced luminescent materials.

Language: Английский

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Mechanisms of Photoredox Catalysis Featuring Nickel–Bipyridine Complexes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 9055 - 9076

Published: May 29, 2024

Metallaphotoredox catalysis can unlock useful pathways for transforming organic reactants into desirable products, largely due to the conversion of photon energy chemical potential drive redox and bond transformation processes. Despite importance these processes cross-coupling reactions other transformations, their mechanistic details are only superficially understood. In this review, we have provided a detailed summary various photoredox mechanisms that been proposed date Ni-bipyridine (bpy) complexes, focusing separately on photosensitized direct excitation reaction By highlighting multiple key findings, depict how mechanisms, which ultimately define substrate scope, themselves defined by ground- excited-state geometric electronic structures Ni-based intermediates. We further identify knowledge gaps motivate future studies development synergistic research approaches spanning physical, organic, inorganic chemistry communities.

Language: Английский

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A Paradigm Shift in Catalysis: Electro- and Photomediated Nickel-Catalyzed Cross-Coupling Reactions

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(20), P. 2851 - 2865

Published: Sept. 29, 2023

ConspectusTransition-metal catalyzed cross-coupling reactions are fundamental in organic chemistry, facilitating strategic bond formations for accessing natural products, materials, agrochemicals, and pharmaceuticals. Redox chemistry enables access to elusive mechanisms through single-electron processes as an alternative classical two-electron strategies predominated by palladium catalysis. The seminal reports of Baran, MacMillan, Doyle, Molander, Weix, Lin, Fu, Reisman, others merging redox perturbation (photochemical, electrochemical, purely chemical) with catalysis pivotal the current resurgence mechanistic understanding first-row transition metal-based hallmark this platform is systematic modulation transition-metal oxidation states a photoredox catalyst or at heterogeneous electrode surface. Electrocatalysis photocatalysis enhance metal catalysis' capacity formation electron- energy-transfer that promote otherwise challenging elementary steps mechanisms. Cross-coupling conditions promoted electrocatalysis mild, proceeds exceptionally high chemoselectivity wide functional group tolerance. interfacing abundant has brought about paradigm shift technology practitioners quickly applying these tools synthesizing fine chemicals pharmaceutically relevant motifs. In particular, merger Ni electro- photochemistry ushered new era carbon-carbon carbon-heteroatom cross-couplings expanded generality compared their thermally driven counterparts. Over past decade, we have developed enabling photo- electrochemical methods throughout our combined research experience industry (BMS, AstraZeneca) academia (Professor Scripps Research) cross-disciplinary collaborative environments. Account, will outline recent progress from present laboratories electrochemically mediated Ni-catalyzed cross-couplings. By highlighting methodologies, also compare features both photochemical forging C(sp2)-C(sp3), C(sp3)-C(sp3), C-O, C-N, C-S bonds. Through side-by-side comparisons, hope demystify subtle differences between two complementary enact control over Finally, building off collective ourselves rest community, propose tactical user guide aid practitioner rapidly such synthetic designs.

Language: Английский

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Rational Design of 3D Space Connected Donor–Acceptor System in Covalent Organic Frameworks for Enhanced Photocatalytic Performance

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(52)

Published: Aug. 27, 2024

Abstract Herein, a rational strategy is presented to reduce the energy barrier of singlet ground state excited transitions, whilst simultaneously reducing losses in populating triplet states. The approach relies on constructing 3D space connected donor–acceptor systems COFs. D–A system 8‐connected COFs (denoted as COF‐1 and COF‐2) allows efficient transfer electrons, overcoming traditional electron transport limitations 2D significantly boosting solar utilization efficiency under visible light irradiation. COF‐2, possessing an extended π‐conjugated structure relative COF‐1, demonstrated high selectivity for photocatalytic generation H 2 O (6.93 mmol g −1 h ) natural seawater without need sacrificial reagents, exceeding performance most previously reported COF‐based photocatalysts. this work offers new optimizing photocatalysts production other applications.

Language: Английский

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Red Light–Blue Light Chromoselective C(sp²)–X Bond Activation by Organic Helicenium-Based Photocatalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7922 - 7930

Published: March 18, 2024

Chromoselective bond activation has been achieved in organic helicenium (nPr-DMQA+)-based photoredox catalysis. Consequently, control over chromoselective C(sp2)–X multihalogenated aromatics demonstrated. nPr-DMQA+ can only initiate the halogen atom transfer (XAT) pathway under red light irradiation to activate low-energy-accessible C(sp2)–I bonds. In contrast, blue initiates consecutive photoinduced electron (conPET) more challenging C(sp2)–Br Comparative reaction outcomes have demonstrated α-arylation of cyclic ketones with and lights. Furthermore, red-light-mediated selective bonds activated iodobromoarenes keep bromo functional handle untouched. Finally, strength catalysis highlighted two-fold functionalization using both photo-to-transition metal photo-to-photocatalyzed transformations.

Language: Английский

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Photosensitized Gold-Catalyzed Cross-Couplings of Aryl Bromides

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

Published: Feb. 7, 2025

Recently, ligand-promoted Au(I)/Au(III)-catalyzed cross-coupling reactions with aryl iodides have garnered considerable attention. Here, we report the first visible-light-driven gold-catalyzed cross-couplings of challenging bromides. In presence a (P, N)-gold(I) catalyst and an acridinium photocatalyst under blue LED irradiation, C-O coupling bromides carboxylic acids was achieved, soon it found that this photoinduced appliable for other C-C, C-N, C-S bond formation. Experimental computational studies suggest involves two discrete energy transfer (EnT) events: first, from photosensitizer produces excited-state gold(I) complex allows bottleneck oxidative addition to form Au(III) second, reductive elimination aryl-Au(III) regenerate Au(I). Collectively, new synergistic catalytic method developed here highlights tremendous potential photochemical gold catalysis via organogold complexes, as well its facilitate drug discovery due biocompatibility mildness reaction conditions.

Language: Английский

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Thermally Activated Delayed Fluorescence Polymers and Their Application in Organic Light-Emitting Diodes

Progress in Polymer Science, Journal Year: 2024, Volume and Issue: unknown, P. 101892 - 101892

Published: Oct. 1, 2024

Language: Английский

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Old dye safranine as an organic photocatalyst for the synthesis of substituted quinazolinones

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(6), P. 2367 - 2370

Published: Jan. 1, 2024

Safranine-catalyzed oxidative cyclization reaction of substituted 2-aminobenzamides and aldehydes to afford quinazolinone products.

Language: Английский

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Thermally activated delayed fluorescence enhanced by macrocyclization

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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

Language: Английский

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