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1.
Light Sci Appl ; 13(1): 85, 2024 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-38589343

RESUMO

Organic mechanoluminescence materials, featuring dual emission and ultralong phosphorescence characteristics, exhibit significant potential for applications in real-time stress sensing, pressure-sensitive lighting, advanced security marking techniques, and material breakage monitoring. However, due to immature molecular design strategies and unclear luminescence mechanisms, these materials remain rarely reported. In this study, we propose a valuable molecular design strategy to achieve dual-channel mechano-phosphorescence. By introducing the arylphosphine oxide group into a highly twisted molecular framework, enhanced intra- and intermolecular interactions could be achieved within rigid structures, leading to dual-channel mechanoluminescence with greatly promoted ultralong phosphorescence. Further investigations reveal the substantial boosting effect of intra- and intermolecular interactions on mechanoluminescence and ultralong phosphorescence properties by locking the highly twisted molecular skeleton. This work provides a concise and guiding route to develop novel smart responsive luminescence materials for widespread applications in material science.

2.
Nat Commun ; 15(1): 3660, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38688920

RESUMO

Phosphorescence is ubiquitous in heavy atom-containing organic phosphors, which attracts considerable attention in optoelectronics and bioelectronics. However, heavy atom-free organic materials with efficient phosphorescence are rare under ambient conditions. Herein, we report a series of adaptive host-guest materials derived from dibenzo-heterocyclic analogues, showing host-dependent color-tunable phosphorescence with phosphorescence efficiency of up to 98.9%. The adaptive structural deformation of the guests arises from the hyperconjugation, namely the n→π* interaction, enabling them to inhabit the cavity of host crystals in synergy with steric effects. Consequently, a perfect conformation match between host and guest molecules facilitates the suppression of triplet exciton dissipation, thereby boosting the phosphorescence of these adaptive materials. Moreover, we extend this strategy to a ternary host-guest system, yielding both excitation- and time-dependent phosphorescence with a phosphorescence efficiency of 92.0%. This principle provides a concise way for obtaining efficient and color-tunable phosphorescence, making a major step toward potential applications in optoelectronics.

3.
Nat Commun ; 15(1): 2134, 2024 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-38459008

RESUMO

Dynamic luminescence behavior by external stimuli, such as light, thermal field, electricity, mechanical force, etc., endows the materials with great promise in optoelectronic applications. Upon thermal stimulus, the emission is inevitably quenched due to intensive non-radiative transition, especially for phosphorescence at high temperature. Herein, we report an abnormal thermally-stimulated phosphorescence behavior in a series of organic phosphors. As temperature changes from 198 to 343 K, the phosphorescence at around 479 nm gradually enhances for the model phosphor, of which the phosphorescent colors are tuned from yellow to cyan-blue. Furthermore, we demonstrate the potential applications of such dynamic emission for smart dyes and colorful afterglow displays. Our results would initiate the exploration of dynamic high-temperature phosphorescence for applications in smart optoelectronics. This finding not only contributes to an in-depth understanding of the thermally-stimulated phosphorescence, but also paves the way toward the development of smart materials for applications in optoelectronics.

4.
Anal Chem ; 96(12): 4891-4900, 2024 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-38462674

RESUMO

Lateral flow immunoassay (LFIA), a classical point-of-care testing (POCT) technique, plays an important role in disease screening and healthcare monitoring. However, traditional LFIA is either designed for qualitative analysis or requires expensive equipment for quantification, limiting its use in household diagnosis. In this study, we proposed a new generation of LFIA for household health monitoring by using ultralong organic phosphorescence (UOP) nanomaterials as afterglow nanoprobes with a self-developed palm-size sensing device. The UOP nanoprobes exhibit a phosphorescence signal with a second-level lifetime, which completely avoids the interference from excitation light and biological background fluorescence. Therefore, an ultraminiaturized and low-cost UOP nanosensor was successfully designed by eliminating the complex optical path and filtering systems. We chose an inflammatory factor, C-reactive protein (CRP), for household POCT validation. The whole analysis was completed within 9 min. A limit of detection (LOD) of 0.54 ng/mL of CRP antigen was achieved with high stability and good specificity, which is comparable to laboratory instruments and fully satisfying the clinical diagnosis requirement.


Assuntos
Nanoestruturas , Imunoensaio/métodos , Limite de Detecção
5.
Angew Chem Int Ed Engl ; 63(14): e202319694, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38314961

RESUMO

Organic phosphors offer a promising alternative in optoelectronics, but their temperature-sensitive feature has restricted their applications in high-temperature scenarios, and the attainment of high-temperature phosphorescence (HTP) is still challenging. Herein, a series of organic cocrystal phosphors are constructed by supramolecular assembly with an ultralong emission lifetime of up to 2.16 s. Intriguingly, remarkable stabilization of triplet excitons can also be realized at elevated temperature, and green phosphorescence is still exhibited in solid state even up to 150 °C. From special molecular packing within the crystal lattice, it has been observed that the orientation of isolated water cluster and well-controlled molecular organization via multiple interactions can favor the structural rigidity of cocrystals more effectively to suppress the nonradiative transition, thus resulting in efficient room-temperature phosphorescence and unprecedented survival of HTP.

6.
Angew Chem Int Ed Engl ; 63(14): e202319650, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38275283

RESUMO

Luminescent ferroelectrics are holding exciting prospect for integrated photoelectronic devices due to potential light-polarization interactions at electron scale. Integrating ferroelectricity and long-lived afterglow emission in a single material would offer new possibilities for fundamental research and applications, however, related reports have been a blank to date. For the first time, we here achieved the combination of notable ferroelectricity and afterglow emission in an organic-inorganic hybrid material. Remarkably, the presented (4-methylpiperidium)CdCl3 also shows noticeable antiferroelectric behavior. The implementation of cationic customization and halogen engineering not only enables a dramatic enhancement of Curie temperature of 114.4 K but also brings a record longest emission lifetime up to 117.11 ms under ambient conditions, realizing a leapfrog improvement of at least two orders of magnitude compared to reported hybrid ferroelectrics so far. This finding would herald the emergence of novel application potential, such as multi-level density data storage or multifunctional sensors, towards the future integrated optoelectronic devices with multitasking capabilities.

7.
Adv Mater ; 36(18): e2310663, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38267010

RESUMO

Organic phosphorescent scintillating materials have shown great potential for applications in radiography and radiation detection due to their efficient utilization of excitons. However, revealing the relationship between molecule stacking and the phosphorescent radioluminescence of scintillators is still challenging. This study reports on two phenothiazine derivatives with polymorphism-dependent phosphorescence radioluminescence. The experiments reveal that molecule stacking significantly affects the non-radiation decay of the triplet excitons of scintillators, which further determines the phosphorescence scintillation performance under X-ray irradiation. These phosphorescent scintillators exhibit high radio stability and have a low detection limit of 278 nGys-1. Additionally, the potential application of these scintillators in X-ray radiography, based on their X-ray excited radioluminescence properties, is demonstrated. These findings provide a guideline for obtaining high-performance phosphorescent scintillating materials by shedding light on the effect of crystal packing on the radioluminescence of organic molecules.

8.
Adv Mater ; 36(18): e2311922, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38270348

RESUMO

Long-lived and highly efficient room temperature phosphorescence (RTP) materials are in high demand for practical applications in lighting and display, security signboards, and anti-counterfeiting. Achieving RTP in aqueous solutions, near-infrared (NIR) phosphorescence emission, and NIR-excited RTP are crucial for applications in bio-imaging, but these goals pose significant challenges. Supramolecular self-assembly provides an effective strategy to address the above problems. This review focuses on the recent advances in the enhancement of RTP via supramolecular self-assembly, covering four key aspects: small molecular self-assembly, cocrystals, the self-assembly of macrocyclic hosts and guests, and multi-stage supramolecular self-assembly. This review not only highlights progress in these areas but also underscores the prominent challenges associated with developing supramolecular RTP materials. The resulting strategies for the development of high-performance supramolecular RTP materials are discussed, aiming to satisfy the practical applications of RTP materials in biomedical science.

9.
Small ; : e2309559, 2024 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-38243884

RESUMO

Hopper-shaped microcrystals, an unusual type of crystal with a large specific surface area, are promising for use in catalysis, drug delivery, and gas sensors. In contrast to well-studied inorganic hopper-shaped crystals, organic phosphorescent concave hopper-shaped microstructures are rarely reported. This study reports the synthesis of two types of organic stepped indented hopper-shaped microstructures with efficient room temperature phosphorescence (RTP) using a liquid phase self-assembly strategy. The formation mechanism is attributed to the interfacial instability induced by the concentration gradient and selective etching. Compared with flat microstructures, the stepped indented hopper-like RTP microstructures exhibit high sensitivity to oxygen. This work also demonstrates that packing the photochromic material into the concave hopper "vessel" effectively controls the switch of phosphorescence from energy transfer, expanding the potential applications of phosphorescent materials.

10.
Adv Mater ; 36(15): e2308290, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-37884272

RESUMO

Metal-organic hybrid (MOH) materials with room-temperature phosphorescence (RTP) have drawn attention in recent years due to their superior RTP properties of high phosphorescence efficiency and ultralong emission lifetime. Great achievement has been realized in developing MOH materials with high-performance RTP, but a systematic study on MOH materials with RTP feature is lacking. This review highlights recent advances in metal-organic hybrid RTP materials. The molecular packing, the photophysical properties, and their applications of metal-organic hybrid RTP materials are discussed in detail. Metal-organic hybrid RTP materials can be divided into six parts: coordination polymers, metal-organic frameworks (MOFs), metal-halide hybrids, organic ionic crystals, organic ionic polymers, and organic-inorganic hybrid perovskites. These RTP materials have been successfully applied in time-resolved data encryption, fingerprint recognition, information logic gates, X-ray imaging, and photomemory. This review not only provides the basic principles of designing RTP metal-organic hybrids, but also propounds the future research prospects of RTP metal-organic hybrids. This review offers many effective strategies for developing metal-organic hybrids with excellent RTP properties, thus satisfying practical applications.

11.
Angew Chem Int Ed Engl ; 63(11): e202318836, 2024 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-38141053

RESUMO

Organic materials with room-temperature phosphorescence (RTP) are in high demand for optoelectronics and bioelectronics. Developing RTP materials highly relies on expert experience and costly excited-state calculations. It is a challenge to find a tool for effectively screening RTP materials. Herein we first establish ground-state orbital descriptors (πFMOs ) derived from the π-electron component of the frontier molecular orbitals to characterize the RTP lifetime (τp ), achieving a balance in screening efficiency and accuracy. Using the πFMOs , a data-driven machine learning model gains a high accuracy in classifying long τp , filtering out 836 candidates with long-lived RTP from a virtual library of 19,295 molecules. With the aid of the excited-state calculations, 287 compounds are predicted with high RTP efficiency. Impressively, experiments further confirm the reliability of this workflow, opening a novel avenue for designing high-performance RTP materials for potential applications.

12.
Angew Chem Int Ed Engl ; 62(52): e202312151, 2023 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-37909102

RESUMO

The ability to harness charges and spins for control of organic excitonic states is critical in developing high-performance organic luminophores and optoelectronic devices. Here we report a facile strategy to efficiently manipulate the electronic energy states of various organic phosphors by coupling them with inorganic lanthanide nanocrystals. We show that the metallic atoms exposed on the nanocrystal surface can introduce strong coupling effects to 9-(4-ethoxy-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole (OCzT) and some organic chromophores with carbazole functional groups when the organics are approaching the nanocrystals. This unconventional organic-inorganic hybridization enables a nearly 100 % conversion of the singlet excitation to fast charge transfer luminescence that does not exist in pristine organics, which broadens the utility of organic phosphors in hybrid systems.

13.
Adv Mater ; 35(49): e2306501, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37793797

RESUMO

Ultralong organic phosphorescence (UOP) materials have attracted considerable attention in recent years. Herein, a new type of flexible films is fabricated by doping amphipathic pyrene tetrasulfonic acid sodium salts into amorphous poly(vinyl alcohol) matrix, which enables the realization of color-tunable UOP spanning from orange-red to green after excitation light is switched off. Interestingly, precise control of the proportion of isolated-molecular and aggregated-state phosphorescence is demonstrated for colorful afterglow using photo-activation. An increase in the dynamic phosphorescence lifetime of isolated molecules is observed from 894.75 to 1735.71 ms following an 8 min irradiation under ambient conditions. The photo-activation, however, showed little influence on aggreated-state phosphorescence. This flexible and processable film exhibits versatile applications in multicolor afterglow displays, ultraviolet detection, multilevel information encryption, etc. This study not only provides a strategy for the rational regulation of UOP colors but also expands the application potential of color-tunable UOP materials.

14.
Adv Mater ; 35(36): e2210489, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37390483

RESUMO

Achieving multicolor organic afterglow materials with narrowband emission and high color purity is important in various optoelectronic fields but remains a great challenge. Here, an efficient strategy is presented to obtain narrowband organic afterglow materials via Förster resonance energy transfer from long-lived phosphorescence donors to narrowband fluorescence acceptors in a polyvinyl alcohol matrix. The resulting materials exhibit narrowband emission with a full width at half maximum (FWHM) as small as 23 nm and the longest lifetime of 721.22 ms. Meanwhile, by pairing the appropriate donors and acceptors, multicolor and high color purity afterglow ranging from green to red with the maximum photoluminescence quantum yield of 67.1% are achieved. Moreover, given their long luminescence lifetime, high color purity, and flexibility, the potential applications are demonstrated in high-resolution afterglow displays and dynamic and quick information identification in low-light conditions. This work provides a facile approach for developing multicolor and narrowband afterglow materials as well as expands the features of organic afterglow.

15.
Angew Chem Int Ed Engl ; 62(24): e202301564, 2023 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-37026975

RESUMO

Dynamic room temperature phosphorescence (RTP) materials have potential applications in optoelectronics, which inevitably suffer from poor processability, flexibility or stretchability. Herein, we report a concise strategy to develop supercooled liquids (SCLs) with dynamic RTP behavior using terminal hydroxyl engineering. The terminal hydroxyls effectively hinder the nucleation process of molecules for the formation of stable SCLs after thermal annealing. Impressively, the SCLs show reversible RTP emission via alternant stimulation by UV light and heat. Photoactivated SCLs have phosphorescent efficiency of 8.50 % and a lifetime of 31.54 ms under ambient conditions. Regarding the dynamic RTP behavior and stretchability of SCLs, we demonstrate the applications in erasable data encryption and patterns on flexible substrates. This finding provides a design principle for obtaining SCLs with RTP and expands the potential applications of RTP materials in flexible optoelectronics.

16.
Light Sci Appl ; 12(1): 90, 2023 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-37037811

RESUMO

Purely organic phosphorescent materials with dynamically tunable optical properties and persistent luminescent characteristics enable more novel applications in intelligent optoelectronics. Herein, we reported a concise and universal strategy to achieve photoactivated ultralong phosphorescence at room temperature through stereo-hindrance engineering. Such dynamically photoactivated phosphorescence behavior was ascribed to the suppression of non-radiative transitions and improvement of spin-orbit coupling (SOC) as the variation of the distorted molecular conformation by the synergistic effect of electrostatic repulsion and steric hindrance. This "trainable" phosphorescent behavior was first proposed to mimic biological synaptic plasticity, especially for unique experience-dependent plasticity, by the manipulation of pulse intensity and numbers. This study not only outlines a principle to design newly dynamic phosphorescent materials, but also broadens their utility in intelligent sensors and robotics.

17.
Research (Wash D C) ; 6: 0090, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37000186

RESUMO

Organic scintillators, materials with the ability to exhibit luminescence when exposed to X-rays, have aroused increasing interest in recent years. However, the enhancement of radioluminescence and improving X-ray absorption of organic scintillators lie in the inherent dilemma, due to the waste of triplet excitons and weak X-ray absorption during scintillation. Here, we employ halogenated thermally activated delayed fluorescence materials to improve the triplet exciton utilization and X-ray absorption simultaneously, generating efficient scintillation with a low detection limit, which is one order of magnitude lower than the dosage for X-ray medical diagnostics. Through experimental study and theoretical calculation, we reveal the positive role of X-ray absorption, quantum yields of prompt fluorescence, and intersystem crossing in promoting the radioluminescence intensity. This finding offers an opportunity to design diverse types of organic scintillators and expands the applications of thermally activated delayed fluorescence.

18.
Small ; 19(31): e2207104, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-36810867

RESUMO

Carbon dots (CDs) have gradually become a new generation of nano-luminescent materials, which have received extensive attention due to excellent optical properties, wide source of raw materials, low toxicity, and good biocompatibility. In recent years, there are many reports on the luminescent phenomenon of CDs, and great progress has been achieved. However,there are rarely systematic summaries on CDs with persistent luminescence. Here, a summary of the recent progress on persistent luminescent CDs, including luminous mechanism, synthetic strategies, property regulation, and potential applications, is given. First, a brief introduction is given to the development of CDs luminescent materials. Then, the luminous mechanism of afterglow CDs from room temperature phosphorescence (RTP), delayed fluorescence (DF), and long persistent luminescence (LPL) is discussed. Next, the constructed methods of luminescent CDs materials are summarized from two aspects, including matrix-free self-protected and matrix-protected CDs. Moreover, the regulation of afterglow properties from color, lifetime, and efficiency is presented. Afterwards, the potential applications of CDs, such as anti-counterfeiting, information encryption, sensing, bio-imaging, multicolor display, LED devices, etc., are reviewed. Finally, an outlook on the development of CDs materials and applications is proposed.

19.
Angew Chem Int Ed Engl ; 62(6): e202214483, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36346193

RESUMO

Excitation-dependent emission (Ex-de) materials have been of considerable academic interest and have potential applications in real life. Such multicolour luminescence is a characteristic exception to the ubiquitously accepted Kasha's rule. This phenomenon has been increasingly presented in some studies on different luminescence systems; however, a systematic overview of the mechanisms underlying this phenomenon is currently absent. Herein, we resolve this issue by classifying multicolour luminescence from single chromophores and dual/ternary chromophores, as well as multiple emitting species. The underlying processes are described based on electronic and/or geometrical conditions under which the phenomenon occurs. Before we present it in categories, related photophysical and photochemical foundations are introduced. This systematic overview will provide a clear approach to designing multicolour luminescence materials for special applications.

20.
Chem Commun (Camb) ; 58(95): 13266-13269, 2022 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-36373264

RESUMO

We present a novel series of neutral photo-acid generators (PAGs) based on carbazole derivatives. A photo-induced 6π-electrocyclization reaction of carbazole derivatives triggers the subsequent release of halogen acids. With UV irradiation, PAGs spontaneously release acid molecules quantitatively forming polyaromatic compounds. To our knowledge, it is considered the highest quantum yield (over 85%) among Brønsted PAGs.

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