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 NIR‐II Organic Dendrimer with Superb Photothermal Performance Based on Electron‐Donor Iteration for Photothermal Immunotherapy

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Окт. 7, 2024

Abstract Organic photothermal materials have attracted extensive attention due to their designable molecular structure, tunable excited‐state properties, and excellent biocompatibility, however, the development of near‐infrared II (NIR‐II) absorbing organic with high conversion efficiency (PTCE) molar extinction coefficient ( ɛ ) remains challenging. Herein, a novel “electron‐donor iteration” strategy is proposed construct dendrimers (CR‐DPA‐T, CR‐(DPA) 2 ‐T 3 ‐T) donor‐ π ‐acceptor‐ ‐donor (D ‐π‐ A‐ ‐D) features diradical characteristics. Owing enhanced D–A effect intramolecular motions, absorption capacity increase as generation grows. Surprisingly, an performance 1064 × PTCE superb value 2.85 10 4 in NIR‐II region achieved for nanoparticles (CR‐(DPA) NPs) compared most reported counterparts. Besides, NPs exhibit superior antitumor efficacy by synergistic therapy (PTT) immunotherapy, efficiently inhibiting growth both primary distant tumors. To best knowledge, dendrimer first time reported, universal donor engineering offered develop NIR‐II‐absorbing immunotherapy.

Язык: Английский

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NIR‐II Emissive Persistent Neutral π‐Radical with Rapid Doublet Internal Conversion for Efficient Cancer Photothermal Theranostics

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

Abstract Organic radicals are considered prospective materials for near‐infrared (NIR) photothermal applications, however, sustainability remains the major obstacle of recently reported ionic radical agents. This work achieved robust on a series neutral π‐radicals through rational design donor (D)–acceptor (A). With efficient doublet internal conversion, 10H‐spiro(acridine‐9,9′‐fluorene) (SFA)‐BTM presented strong NIR absorption extended to 1000 nm and non‐radiative relaxation. SFA‐BTM nanoparticles (NPs) realized comparable NIR‐I conversion efficiency (PCE) photoacoustic sensitivity. Also, π‐radical NPs displayed NIR‐II emission high‐resolution whole‐body angiography first time by bioimaging. Ultimately, capabilities confirmed in an orthotopic bone tumor model effective ablation cancer cells vitro inhibition deterioration vivo. research offers new horizon conception development sustainable organic imaging theranostics applications.

Язык: Английский

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Atomic Engineering and Aggregation Effect to Regulate Synergistically Type I Reactive Oxygen Species of AIE‐Active Deep Red/Near Infrared Red Photosensitizer

Small, Год журнала: 2025, Номер unknown

Опубликована: Март 3, 2025

Abstract “Molecular science” has long been regarded as the golden rule to guide design of organic materials’ performances in past many years, but some interesting phenomena conventional aggregation‐caused fluorescence quenching and new aggregation‐induced emission reflect that properties would be changed from “molecule” “aggregate”. Therefore, “molecular theory faces certain limitations regulating performance materials at aggregation. In this work, it is discovered photosensitizer's contain reactive oxygen species, which could affected by changing molecular atoms aggregation form. The introduction selenium redshift improve species (ROS) efficiency. addition atomic effect, ROS efficiency photosensitizers after coating a polymeric shell, is, production type II singlet ( 1 O 2 ) suppressed, while I superoxide anion (O −• improved. This work discovers are relevant effect discussing deeply influence mechanism, important research significance for modulating precisely promoting development photodynamic therapy.

Язык: Английский

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Bias‐Switchable Photomultiplication and Photovoltaic Dual‐Mode Near‐Infrared Organic Photodetector

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Photomultiplication-type organic photodetectors (PM-OPDs) provide for signal amplification, ideal detecting faint light, and simplifying detection systems. However, current designs often suffer from slow response speed elevated dark current. Conversely, photovoltaic-type (PV-OPDs) fast high specific detectivity (D*) but have limited photoresponse. This study presents the synthesis incorporation of a non-fullerene acceptor, BFDO-4F, into active layer to introduce trap states capturing photogenerated electrons. The resulting device exhibits dual-mode characteristic is bias-switchable between PV PM-modes. In PV-mode, OPDs achieve D* 1.92 × 10¹2 Jones time 2.83/4.43 µs. PM-mode, exhibit exceptional external quantum efficiency (EQE) up 3484% 1.13 Jones. An on-chip self-powered module with PV-mode pixels driving PM-mode pixel demonstrated, yielding photocurrent approximately five times higher than reference device. approach paves way developing multifunctional OPDs, suitable various applications.

Язык: Английский

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Highly Stable Near-Infrared II Luminescent Diradicaloids for Cancer Phototheranostics

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(47), С. 32582 - 32594

Опубликована: Ноя. 13, 2024

Near-infrared II (NIR-II) phototheranostic agents have become prominent for the early diagnosis and precise treatment of cancer. Organic open-shell diradicaloids with distinct structure narrow band gap are promising candidates phototherapeutic due to their strong spin-coupling effect NIR light-harvesting capacity. However, achieving stable efficient NIR-II luminescent is crucial yet rather challenging considering high chemical reactivity self-absorption. Herein, two highly diradicaloids, 2PhNVDPP PhNVDPP, were successfully fabricated by employing an acceptor planarization/π-conjugation extension donor rotation strategy. After encapsulation into water-dispersible nanoparticles (NPs), NPs exhibit luminescence, PCE 53%, improved photo/heat stability. In vivo experiments demonstrated clear visualization blood vessels tumors, as well successful imaging-guided photothermal ablation tumors. This study not only develops a pioneering diradicaloid agent luminescence but also provides unique perspective effectiveness multimodal anticancer therapy.

Язык: Английский

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Open‐shell Poly(3,4‐dioxythiophene) Radical for Highly Efficient Photothermal Conversion

Advanced Science, Год журнала: 2024, Номер unknown

Опубликована: Сен. 5, 2024

Abstract Open‐shell organic radical semiconductor materials have received increasing attention in recent years due to their distinctive properties compared the traditional with closed‐shell singlet ground state. However, poor chemical and photothermal stability ambient conditions remains a significant challenge, primarily owing high reactivity oxygen. Herein, novel open‐shell poly(3,4‐dioxythiophene) PTTO 2 is designed readily synthesized for first time using low‐cost raw material via straightforward BBr 3 ‐demethylation of copolymer PTTOMe precursor. The character carefully studied confirmed signal‐silent 1 H nuclear magnetic resonance spectrum, highly enhanced electron spin signal , as well ultra‐wide ultraviolet‐visible‐near nfraredUV–vis–NIR absorption other technologies. Interestingly, powder exhibits an extraordinary range spanning from 300 2500 nm can reach 274 °C under irradiation 1.2 W cm −2 substantially higher than 108 achieved by . stands one best conversion among pure provides new scaffold design stable non‐doped polymers.

Язык: Английский

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A Processible and Ultrahigh‐temperature Organic Photothermal Material through Spontaneous and Quantitative [2+2] Cycloaddition–Cycloreversion

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(30)

Опубликована: Май 15, 2024

Energy conversion, particularly light to heat has garnered significant attention owing its prospect in renewable energy exploitation and utilization. Most previous efforts have focused on developing organic photothermal materials for low-temperature applications, whereas the importance of simplifying preparation methods enhancing their maximum temperature been less taken. Herein, we prepare an near-infrared (NIR) material namely ATT by a spontaneous [2+2] cycloaddition-cycloreversion reaction. In addition solution-based method, could also be readily preapred ball milling high yield 90 % just 15 min. powder exhibits broad absorption extending beyond 2000 nm, excellent processability, thermal stability. Remarkably, can reach unprecedently as 450 °C while maintaining photostability upon photoirradiation. Leveraging extraordinary processable properties, was used high-temperature such photo-ignition, photo-controlled metal processing shape memory, all which offer spatiotemporal control capabilities. This work provides new approach with temperatures, pave way applications extreme environments.

Язык: Английский

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A Processible and Ultrahigh‐temperature Organic Photothermal Material through Spontaneous and Quantitative [2+2] Cycloaddition–Cycloreversion

Angewandte Chemie, Год журнала: 2024, Номер 136(30)

Опубликована: Май 15, 2024

Abstract Energy conversion, particularly light to heat has garnered significant attention owing its prospect in renewable energy exploitation and utilization. Most previous efforts have focused on developing organic photothermal materials for low‐temperature applications, whereas the importance of simplifying preparation methods enhancing their maximum temperature been less taken. Herein, we prepare an near‐infrared (NIR) material namely ATT by a spontaneous [2+2] cycloaddition‐cycloreversion reaction. In addition solution‐based method, could also be readily preapred ball milling high yield 90 % just 15 min. powder exhibits broad absorption extending beyond 2000 nm, excellent processability, thermal stability. Remarkably, can reach unprecedently as 450 °C while maintaining photostability upon photoirradiation. Leveraging extraordinary processable properties, was used high‐temperature such photo‐ignition, photo‐controlled metal processing shape memory, all which offer spatiotemporal control capabilities. This work provides new approach with temperatures, pave way applications extreme environments.

Язык: Английский

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Diradicaloid-Loaded Polypeptide Nanoparticles for Two-Photon NIR Phototheranostics

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(44), С. 59907 - 59920

Опубликована: Окт. 23, 2024

Stable organic radicals, with unique electronic transitions from the ground state (D0) to doublet excited (D1), show promise as high-fluorescence quantum yield dyes. While small-molecule photosensitizers (PSs) have advanced for tumor photodynamic therapy (PDT), opportunities exist enhance their performance and functionality. Herein, we synthesized Thiele's fluorocarbon derivative diradicaloid TFC-I nearly 100% PLQY integrated it into amphiphilic polypeptide nanoparticles, P-TI, using a precursor-doping approach. P-TI demonstrated notable features including high photostability, aggregation-induced emission, bright near-infrared fluorescence, substantial (37% PLQY), robust two-photon absorption (∼400 GM cross section), superior ROS generation compared commercial PSs. In vitro in vivo experiments confirmed that performed well mitochondria-targeted PDT, fluorescence imaging, biosafety. This work highlights use of stable radicals efficient PDT deep tissue imaging.

Язык: Английский

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