Sulfone-Functionalized Chichibabin’s Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 6763 - 6772

Опубликована: Фев. 28, 2024

While monoradical emitters have emerged as a new route toward efficient organic light-emitting diodes, the luminescence property of diradicaloids is still scarcely explored. Herein, by devising novel radical–radical coupling-based synthetic approach, we report class sulfone-functionalized Chichibabin's hydrocarbon derivatives, SD-1–3, featuring varied substituent patterns and moderate to high diradical characters 0.44–0.70, highly stable with rarely seen NIR emission beyond 900 nm. Via comprehensive experimental theoretical investigations, reveal that optoelectronic magnetic properties these materials are significantly tuned variations substitutions (H/CF3/OMe) on molecular skeletons. More importantly, quantum chemical computations indicate embedding sulfone groups has contributed breaking their quasi-C2 symmetry diradicaloid molecules results in an excited-state charge transfer character. Therefore, remarkably deep emissive wavelength up 998 nm, together large Stokes shift (∼386 nm), achieved for CF3-based SD-2 molecule tetrahydrofuran. To best our knowledge, such luminescent represented longest wavelengths among currently reported fluorescent radicals. Overall, work not only establishes approach hydrocarbons but also paves way designing open-shell both fundamental understanding feasible control properties.

Язык: Английский

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A Stable Open-Shell Conjugated Diradical Polymer with Ultra-High Photothermal Conversion Efficiency for NIR-II Photo-Immunotherapy of Metastatic Tumor

Nano-Micro Letters, Год журнала: 2023, Номер 16(1)

Опубликована: Ноя. 20, 2023

Massive efforts have been concentrated on the advance of eminent near-infrared (NIR) photothermal materials (PTMs) in NIR-II window (1000-1700 nm), especially organic PTMs because their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-II-responsive was explored, and conversion efficiencies (PCEs) still remain relatively low. Herein, donor-acceptor conjugated diradical polymers open-shell characteristics are explored for synergistically immunotherapy metastatic tumors window. By employing side-chain regulation, polymer TTB-2 obvious absorption developed, its nanoparticles realize record-breaking PCE 87.7% upon light illustration. In vitro vivo experiments demonstrate that show good tumor photoablation navigation photoacoustic imaging window, without any side-effect. Moreover, by combining PD-1 antibody, pulmonary metastasis breast cancer is high-effectively prevented efficient photo-immunity effect. Thus, this study explores superior theranostics offering new horizon developing radical-characteristic materials.

Язык: Английский

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bay/ortho-Octa-substituted Perylene: A Versatile Building Block toward Novel Polycyclic (Hetero)Aromatic Hydrocarbons

Accounts of Chemical Research, Год журнала: 2024, Номер 57(5), С. 763 - 775

Опубликована: Фев. 22, 2024

ConspectusPolycyclic (hetero)aromatic hydrocarbons (PAHs) have emerged as a focal point in current interdisciplinary research, spanning the realms of chemistry, physics, and materials science. Possessing distinctive optical, electronic, magnetic properties, these π-functional exhibit significant potential across diverse applications, including molecular electronic devices, organic spintronics, biomedical functions, among others. Despite extensive documentation various PAHs over decades, efficient precise synthesis π-extended remains formidable challenge, hindering their broader application. This challenge is primarily attributed to intricate often elusive nature synthesis, compounded by issues related low solubility unfavored stability.The development π-building blocks that can be facilely modularly transformed into π-frameworks constitutes potent strategy for creation novel PAH materials. For instance, based on classic perylene diimide (PDI) unit, researchers such Würthner, Wang, Nuckolls successfully synthesized plethora structurally PAHs, well numerous other However, until now availability versatile building still severely limited, especially those simultaneously having facile preparation process, adequate solubilizing groups, favored material stability, critically, rich possibilities structural extension spaces.In this Account, we present an overview our invention highly bay-/ortho-octa-substituted block, designated Per-4Br, construction series scaffolds with tailor-made structures optoelectronic properties. First, starting brief discussion challenges associated bottom-up rationalize key features Per-4Br enable access new molecules its ease large-scale preparation, stability solubility, multiple flexible reaction sites, comparison PDI motif. Then, showcase rational design sophisticated body neutral or charged, closed- open-shell, curved, planar via controlled annulative π-extensions different directions peripheral, diagonal, dimensions skeleton. In part, fundamental structure–property relationships between conformations, structures, self-assembly behaviors unique physiochemical properties unusual open-shell ground states, global aromaticity, state-associated/stimuli-responsive activity, charge transport characteristics will emphatically elaborated. Finally, offer perspective continued advancement which, posit, may stimulate heightened research interest motifs typified consequently catalyzing further progress realm

Язык: Английский

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From π-conjugated macrocycles to heterocycloarenes based on benzo[2,1-b:3,4-b′]dithiophene (BDTh): size- and geometry-dependent host–guest properties

Chemical Science, Год журнала: 2024, Номер 15(12), С. 4590 - 4601

Опубликована: Янв. 1, 2024

Single bond linked macrocycles (MS-4T/MS-6T) and corresponding heterocycloarenes (MF-4T/MF-6T) were designed synthesized, which show size- geometry-dependent host–guest properties.

Язык: Английский

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Photoelectromagnetic Responsive Adaptive Porous Frameworks through Dynamic Covalent Chemistry of Tetraarylethylene‐backboned Aryldicyanomethyl Radicals

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(22)

Опубликована: Март 29, 2023

Abstract Dynamic materials undergoing adaptive solid‐state transitions are attractive for soft mechanics and information technology. Here, we report a novel porous framework system based on macrocyclic trimers assembled from open‐shell tetraarylethylene building blocks with aryldicyanomethyl radicals as coupling linkers. Under mechanical, thermal, or chemical stimuli, the showed adaptability by activating conformational dynamics radical‐based transformations, thus displaying macroscopic responsiveness in terms of light absorption, luminescence, magnetism. We studied dynamic processes variable‐temperature nuclear magnetic resonance (VT‐NMR), electron spin (VT‐ESR), superconducting quantum interference device (SQUID) measurement further established proof‐of‐concept application multi‐modal encryption. The strategy may open avenues rational design photoelectromagnetic merging covalent chemistry functional aggregation principles.

Язык: Английский

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From closed-shell edge-extended kekulenes to open-shell carbonylated cycloarene diradicaloid

Chemical Science, Год журнала: 2023, Номер 14(22), С. 6087 - 6094

Опубликована: Янв. 1, 2023

The precise synthesis of cycloarenes remains a challenging topic in both organic chemistry and materials science due to their unique fully fused macrocyclic π-conjugated structure. Herein, series alkoxyl- aryl-cosubstituted (kekulene edge-extended kekulene derivatives, K1-K3) were conveniently synthesized an unexpected transformation the anthryl-containing cycloarene K3 into carbonylated derivative K3-R was disclosed by controlling temperature gas atmosphere Bi(OTf)

Язык: Английский

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Fully-fused boron-doped olympicenes: modular synthesis, tunable optoelectronic properties, and one-electron reduction

Chemical Science, Год журнала: 2023, Номер 14(15), С. 4158 - 4165

Опубликована: Янв. 1, 2023

We report here a novel family of boraolympicenes, structurally featuring boron-doping at the concave 11a-position their π-skeletons and synthetically prepared via facile one-pot triply borylation-based double-fold borocyclization reaction. Despite having no bulky protecting groups, these boraolympicenes exhibit excellent chemical stability against air moisture, ascribed to significant π-electron delocalization over vacant p z orbitals boron atoms as evidenced by both single-crystallographic theoretical analyses. More importantly, modular synthesis allows fine-tuning physicochemical properties, endowing them with intriguing electronic features, such intense visible-to-NIR absorption low-lying LUMO energy levels (∼-3.8 eV) well tunable molecular stacking characteristics in crystalline state. As model compound, radical-anion salt 6-phenyl-11a-boraolympicene was further generated through reduction characterized UV-vis-NIR absorption, ESR, IR spectroscopy. This radical anion is sensitive moisture but shows persistent under inert conditions benefiting from its stable borataalkene-containing resonant form.

Язык: Английский

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Mn(iii)-mediated C–P bond activation of diphosphines: toward a highly emissive phosphahelicene cation scaffold and modulated circularly polarized luminescence

Chemical Science, Год журнала: 2023, Номер 14(38), С. 10446 - 10457

Опубликована: Янв. 1, 2023

Transition metal mediated C-X (X = H, halogen) bond activation provides an impressive protocol for building polyaromatic hydrocarbons (PAHs) in C-C coupling and annulation; however, mimicking both the reaction model Lewis acid mediator simultaneously a hetero-PAH system selective C-P cleavage faces unsolved challenges. At present, developing of phosphonic backbone using noble-metal complexes is predominant passway construction phosphine catalysts P-center redox-dependent photoelectric semiconductors, but non-noble triggered methods are still elusive. Herein, we report Mn(iii)-mediated intramolecular cyclization diphosphines by redox-directed radical phosphonium process, generating phosphahelicene cations or phosphoniums with nice regioselectivity substrate universality under mild conditions. Experiments theoretical calculations revealed existence unusual mechanism electron-deficient character novel phosphahelicenes. These rigid quaternary bonding skeletons facilitated versatile fluorescence good tunability excellent efficiency. Moreover, enantiomerically enriched crystals phosphahelicenes emitted intense circularly polarized luminescence (CPL). Notably, modulated CPL racemic was induced chiral transmission cholesteric mesophase, showing ultrahigh asymmetry factors (+0.51, -0.48). Our findings provide new approach design emissive towards emitters synthesized precursors.

Язык: Английский

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Hetero-polycyclic aromatic systems: A data-driven investigation of structure–property relationships

Beilstein Journal of Organic Chemistry, Год журнала: 2024, Номер 20, С. 1817 - 1830

Опубликована: Июль 31, 2024

Polycyclic aromatic systems (PASs) are pervasive compounds that have a substantial impact in chemistry and materials science. Although their specific structure–property relationships hold the key to design of new functional molecules, detailed understanding these remains elusive. To elucidate relationships, we performed data-driven investigation newly generated COMPAS-2 dataset, which contains ~500k molecules consisting 11 types antiaromatic rings ranging size from one ten rings. Our analysis explores effects electron count, geometry, atomic composition, heterocyclic composition on range electronic molecular properties PASs.

Язык: Английский

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Diverse Postfunctionalization of Open-Shell Diradicaloids and Impact of Conjugated Functional Substituents on Optoelectronic Properties

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 23, 2025

Organic radicals are usually incapable of postfunctionalization for structure expansion and optoelectronic property optimizations. Herein, based on a sulfone-embedded skeleton derived from Chichibabin's hydrocarbon, we showcase the regioselective bromination further postmodifications open-shell diradicaloids via diverse palladium-catalyzed nucleophilic substitution, Sonogashira coupling, Stille coupling reactions. Such facile structural expansions yielded series conjugated singlet diradicaloids, showing finely tuned physicochemical characteristics, versatile crystalline-state molecular configurations packing modes, impressive charge-carrier mobility 1.5 cm2/V·s.

Язык: Английский

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