Elsevier eBooks, Год журнала: 2024, Номер unknown, С. 157 - 175
Опубликована: Окт. 1, 2024
Язык: Английский
Advanced Materials, Год журнала: 2024, Номер 36(14)
Опубликована: Янв. 5, 2024
Abstract Achieving efficient near‐infrared room‐temperature phosphorescence of purely organic phosphors remains scarce and challenging due to strong nonradiative decay. Additionally, the investigation triplet excimer is rarely reported, despite fact that excimer, a special emitter commonly formed in crystals with π–π interactions, can efficiently change fluorescent properties compounds. Herein, series dithienopyrrole derivatives low energy levels stable states, exhibiting persistent phosphorescence, developed. Via modification halogen atoms, display tunable emissions monomers from 645 702 nm, maximum lifetime 3.68 ms under ambient conditions. Notably, be switched on at temperatures, enabled by noncovalent interactions rigidifying matrix stabilizing excimer. Unprecedentedly, dynamic transition process captured between monomer temperature variations, revealing unstable excimers tendency dissociate result effective quench phosphorescence. Excited state transitions across varying environments are elucidated, interpreting structural dynamics demonstrating strategies for devising novel phosphors.
Язык: Английский
Процитировано
27
Nano Letters, Год журнала: 2025, Номер unknown
Опубликована: Март 21, 2025
Near-infrared (NIR) to blue triplet-triplet annihilation upconversion (TTA-UC) shows unique applications in optogenetics, photocaging, and stereoscopic three-dimensional printing, etc. Here, we disclose a strategy that narrowed the energy gap between triplet states of NIR photosensitizer annihilator, with aim maximally suppressing photoexcitation loss during TET. Hence, produced NIR-to-blue TTA-UC pair exhibited an exceptionally large anti-Stokes shift (0.76 eV) achieved record quantum yield (15.5%, out 50%). We further prepared for first time small, water-dispersed, oxygen-resistant nanoparticles up 1.8%. Such upconverted were successfully utilized as NIR-responsive photocatalysts reversible transformation enzyme cofactor NAD+/NADH photobiocatalytic system air-saturated aqueous solutions.
Язык: Английский
Процитировано
2
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21791 - 21805
Опубликована: Июль 29, 2024
The diagnosis of disease biomarkers is crucial for the identification, monitoring, and prognostic assessment malignant disease. However, biological samples with autofluorescence, complex components, heterogeneity pose major challenges to reliable biosensing. Here, we report self-assembly natural proteins triplet–triplet annihilation upconversion (TTA-UC) pair form upconverted protein clusters (∼8.2 ± 1.1 nm), which were further assembled into photon supramolecular assemblies (PUSA). This PUSA exhibited unique features, including a small size (∼44.1 4.1 oxygen tolerance, superior biocompatibility, easy storage via lyophilization, all are long sought after materials. Further, have revealed that steric hindrance annihilator suppresses stacking in PUSA, vital maintaining water dispersibility enhancing performance PUSA. In conjunction sarcosine oxidase, this near infrared (NIR)-excitable nanoprobe could perform background-free biosensing urinary sarcosine, common biomarker prostatic carcinoma (PCa). More importantly, not only allows qualitative identification from PCa patients by unaided eye under NIR-light-emitting diode (LED) illumination but also quantifies concentration sarcosine. These remarkable findings propelled materials new evolutionary stage expedited progress clinical diagnostics.
Язык: Английский
Процитировано
6
Nanoscale, Год журнала: 2023, Номер 16(1), С. 123 - 137
Опубликована: Ноя. 29, 2023
An energy transfer cascade in a three-component upconversion system improves the emission quantum yield and reduces intrinsic filter effects. Investigations of molecular interactions are combined with lab-scale applications photocatalysis.
Язык: Английский
Процитировано
13
ACS Applied Optical Materials, Год журнала: 2024, Номер 2(9), С. 1803 - 1824
Опубликована: Март 22, 2024
Triplet–triplet annihilation upconversion (TTA-UC), which converts low-energy photons into high-energy photons, is based on linear photon absorption and shows high efficiency of luminescence with large anti-Stokes shifts; thus, it has vast applications in solar cells, photocatalysis, artificial photosynthesis, etc. Due to cascade photophysical processes intersystem crossing (ISC) triplet–triplet energy transfer (TTET) involved TTA-UC, the properties triplet photosensitizers (PSs) are critical for designing TTA-UC materials. For instance, strong light long excited-state lifetimes will make PSs abundant at state, makes consequent intermolecular TTET process more efficient, be improved as well. In this review, we include recent developments focus photochemistry these PSs, including molecular design rationales, ISC mechanisms electron-spin selectivity ISC. The methods increasing shifts heavy-atom-free discussed briefly. This information helpful future PSs.
Язык: Английский
Процитировано
5
The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(17), С. 4647 - 4654
Опубликована: Апрель 22, 2024
Ultraviolet (UV) light plays a crucial role in various applications, but currently, the efficiency of generating artificial UV is low. The visible-to-ultraviolet (Vis-to-UV) system based on triplet–triplet annihilation upconversion (TTA-UC) mechanism can be viable solution. Metal-free multiple resonance thermally activated delayed fluorescence (MR-TADF) materials are ideal photosensitizers (PSs) apart from drawback high photoluminescence quantum yields (PLQYs). Herein, we systematically investigated impact heavy-atom effect (HAE) MR-TADF sensitizers. BNCzBr was then synthesized by incorporating bromine atom into skeleton precursor BNCz. Impressively, internal HAE (iHAE) leads to significantly decreased PLQY and remarkably increased intersystem crossing yield (ΦISC). Consequently, higher 12.5% realized. While external (eHAE) harms UC performance. This work guides further development sensitizers for high-performance Vis-to-UV TTA-UC systems.
Язык: Английский
Процитировано
5
Trends in Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Март 1, 2025
Язык: Английский
Процитировано
0
Chemical Communications, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
A benzene-based annihilator and a high triplet energy sensitizer were combined in an upconversion scheme, emitting photons with unprecedented energy.
Язык: Английский
Процитировано
0
Advanced Optical Materials, Год журнала: 2025, Номер unknown
Опубликована: Апрель 21, 2025
Abstract Triplet‐triplet annihilation photon upconversion (TTA‐UC) converts low‐energy photons to higher‐energy ones under low‐intensity incoherent excitation, thus enabling applications in fields ranging from medicine solar energy conversion. Silylethynyl mono‐ and di‐substitution of acenes offers an attractive route creating new annihilators that operate with minimal loss. Here, it is demonstrated this approach can be extended pyrene, yielding display efficient red‐to‐blue upconversion. While pyrene the namesake P‐type delayed fluorescence, original name for triplet‐triplet annihilation, known a poor annihilator due its propensity forming excimers. By tetra‐substituting silylethynyl groups, excimer formation substantially hindered while simultaneously minimizing gap between singlet triplet pair states participate TTA‐UC, outstanding quantum yields upward 19% (29% when corrected inner filter effects). Further, found reducing bulkiness silyl substituents key achieving high TTA‐UC yields, which highlights importance side group selection optimizing
Язык: Английский
Процитировано
0
Molecules, Год журнала: 2024, Номер 29(10), С. 2203 - 2203
Опубликована: Май 8, 2024
The triplet annihilator is a critical component for triplet–triplet annihilation upconversion (TTA-UC); both the photophysical properties of and intermolecular orientation have pivotal effects on overall efficiency TTA-UC. Herein, we synthesized two supramolecular annihilators A-1 A-2 by grafting 9,10-diphenylanthracene (DPA) fragments, which been widely used as TTA-UC, macrocyclic host—pillar[5]arenes. In A-1, DPA units was random, while, in A-2, were pushed to parallel arrangement intramolecular hydrogen-bonding interactions. compounds showed very similar host–guest binding affinities toward electron-deficient guests, but totally different TTA-UC emissions. UC quantum yield could be optimized 13.7% when an alkyl ammonia chain-attaching sensitizer S-2 used, only 5.1% achieved. Destroying interactions adding MeOH significantly decreased emissions, demonstrating that orientations contributed greatly These results should beneficial designs provide new promising strategy enhancing
Язык: Английский
Процитировано
2