RESUMO
Phosphorescence in carbon dots (CDs) from triplet exciton radiative recombination at room temperature has achieved significant advancement. Confinement and nanoconfinement, serving as valuable techniques, are commonly utilized to brighten triplet exciton in CDs, thereby enhancing their phosphorescence. However, a comprehensive and universally applicable physical description of confinement-enhanced phosphorescence is still lacking, despite efforts to understand its underlying nature. In this study, the dominance of entropy is revealed in triplet exciton emission from CDs through the establishment of a microscopic vibration state model. CDs with varying entropy levels are studied, indicating that in a low entropy system, the multi-energy triplet exciton emission in CDs exhibits enhanced brightness, accompanied by a corresponding increase in their lifetimes. The product of lifetime and intensity in CDs serves as a descriptor for their phosphorescence properties. Moreover, an entropy-dependent information variation system based on the CDs is demonstrated. Specifically, in a low-entropy system, information is retained, whereas the corresponding information is erased in a high-entropy system. This work elucidates the underlying physical nature of confinement-enhanced triplet exciton emission, offering a deeper understanding of achieving ultralong phosphorescence in the future.
RESUMO
Carbonized polymer dots (CPDs) with a circularly polarized fluorescence property have received increasing attention in recent years. However, it is still a great challenge to construct circularly polarized room-temperature phosphorescence (CPRTP) CPDs. Herein, a simple approach to the synthesis of intrinsically CPRTP CPDs for the first time by utilizing sodium alginate and l-/d-arginine as precursors under relatively mild reaction conditions is presented. Notably, the CPDs exhibit both chirality and green RTP in solid states. Furthermore, color-tunable CPRTP is successfully achieved by engineering chiral light-harvesting systems based on circularly polarized phosphorescence resonance energy transfer (C-PRET) where the CPDs with green RTP function as an initiator of chirality and light absorbance, and commercially available fluorescent dyes with different emission colors ranging from yellow to red serve as the terminal acceptors. Through one-step or sequential C-PRET, the light-harvesting systems can simultaneously furnish energy transfer and chirality transmission/amplification. Given the multicolor long afterglow, lifetime-tunable, and CPRTP properties, their potential applications in multiple information encryption are demonstrated.
RESUMO
Silicon nanocrystals (SiNCs) have attracted extensive attention in many advanced applications due to silicon's high natural abundance, low toxicity, and impressive optical properties. However, these applications are mainly focused on fluorescent SiNCs, little attention is paid to SiNCs with room-temperature phosphorescence (RTP) and their relative applications, especially water-dispersed ones. Herein, this work presents water-dispersible RTP SiNCs (UA-SiNCs) and their optical applications. The UA-SiNCs with a uniform particle size of 2.8 nm are prepared by thermal hydrosilylation between hydrogen-terminated SiNCs (H-SiNCs) and 10-undecenoic acid (UA). Interestingly, the resultant UA-SiNCs can exhibit tunable long-lived RTP with an average lifetime of 0.85 s. The RTP feature of the UA-SiNCs is confirmed to the n-π* transitions of their surface CâO groups. Subsequently, new dual-modal emissive UA-SiNCs-based ink is fabricated by blending with sodium alginate (SA) as the binder. The customized anticounterfeiting labels are also prepared on cellulosic substrates by screen-printing technique. As expected, UA-SiNCs/SA ink exhibits excellent practicability in anticounterfeiting applications. These findings will trigger the rapid development of RTP SiNCs, envisioning enormous potential in future advanced applications such as high-level anti-counterfeiting, information encryption, and so forth.
RESUMO
Metal nanoclusters (NCs) with atomic precision are growing into a fascinating class of building blocks for supramolecular chemistry. What makes it more interesting is the enhanced optical properties of the ordered structures, including aggregation-induced emission (AIE). However, algorithm dictating the self-assembly of metal NCs in multicomponent environment remains largely unknown, and effective means to manipulate the self-assembly is still lacking, especially under kinetic control. Herein, nanofibers which contain sub-1 nm nanowires and exhibit circularly polarized phosphorescence (CPP) are obtained from crystallization-induced self-assembly (CISA) of water-soluble, negatively charged silver NCs (Ag9 -NCs) in the presence of glutamic acid (Glu). By the introduction of a positively-charged additive (choline chloride, CC), the structure of the nanowires is modulated and the lateral interaction between adjacent nanofibers is adjusted, leading to simultaneous improvement of the phosphorescence and chirality which finally enhances CPP. Importantly, changing the time at which CC is introduced altered the kinetic pathway of the CISA, which enables to effectively manipulate both the final structures of the self-assembled Ag9 -NCs and the output of the optical signals.
RESUMO
Room temperature phosphorescence (RTP) has emerged as an interesting but rare phenomenon with multiple potential applications in anti-counterfeiting, optoelectronic devices, and biosensing. Nevertheless, the pursuit of ultralong lifetimes of RTP under visible light excitation presents a significant challenge. Here, new phosphorescent materials that can be excited by visible light with record-long lifetimes are demonstrated, realized through embedding nitrogen doped carbon dots (N-CDs) into a poly(vinyl alcohol) (PVA) film. The RTP lifetime of the N-CDs@PVA film is remarkably extended to 2.1 s excited by 420 nm, representing the highest recorded value for visible light-excited phosphorescent materials. Theoretical and experimental studies reveal that the robust hydrogen bonding interactions can effectively reduce the non-radiative decay rate and radiative transition rate of triplet excitons, thus dramatically prolong the phosphorescence lifetime. Notably, the RTP emission of N-CDs@PVA film can also be activated by easily accessible low-power white-light-emitting diode. More significantly, the practical applications of the N-CDs@PVA film in state-of-the-art anti-counterfeiting security and optical information storage domains are further demonstrated. This research offers exciting opportunities for utilizing visible light-activated ultralong-lived RTP systems in a wide range of promising applications.
RESUMO
Room-temperature phosphorescent materials, renowned for their long luminescence lifetimes, have garnered significant attention in the field of optical materials. However, the challenges posed by thermally induced quenching have significantly hindered the advancement of luminescence efficiency and stability. In this study, thermally enhanced phosphorescent carbon nanodots (CND) are developed by incorporating them into fiber matrices. Remarkably, the phosphorescence lifetime of the thermally enhanced CND exhibits a twofold enhancement, increasing from 326 to 753 ms, while the phosphorescence intensity experienced a tenfold enhancement, increasing from 25 to 245 as the temperature increased to 373 K. Rigid fiber matrices can effectively suppress the non-radiative transition rate of triplet excitons, while high temperatures can desorb oxygen adsorbed on the surface of the CND, disrupting the interaction between the CND and oxygen. Consequently, a thermally enhanced phosphorescence is obtained. In addition, benefiting from the thermally enhanced phosphorescence property of CND, a warning indicator with an anti-counterfeiting function for monitoring cold-chain logistics is demonstrated based on CND.
RESUMO
Luminescent metal clusters have attracted great interest in current research; however, the design synthesis of Al clusters with color-tunable luminescence remains challenging. Herein, an [Al8 (OH)8 (NA)16 ] (Al8 , HNA = nicotinic acid) molecular cluster with dual luminescence properties of fluorescence and room-temperature phosphorescence (RTP) is synthesized by choosing HNA ligand as phosphor. Its prompt photoluminescence (PL) spectrum exhibits approximately white light emission at room temperature. Considering that halogen atoms can be used to regulate the RTP property by balancing the singlet and triplet excitons, different CdX2 (X- = Cl- , Br- , I- ) are introduced into the reactive system of the Al8 cluster, and three new Al8 cluster-based metal-organic frameworks, {[Al8 Cd3 Cl5 (OH)8 (NA)17 H2 O]·2HNA}n (CdCl2 -Al8 ), {[Al8 Cd4 Br7 (OH)8 (NA)16 CH3 CN]·NA·HNA}n (CdBr2 -Al8 ) and {[Al8 Cd8 I16 (OH)8 (NA)16 ]}n (CdI2 -Al8 ) are successfully obtained. They realize the color tunability from blue to yellow at room temperature. The origination of fluorescence and phosphorescence has also been illustrated by structure-property analysis and theoretical calculation. This work provides new insights into the design of multicolor luminescent metal cluster-based materials and develops advanced photo-functional materials for multicolor display, anti-counterfeiting, and encryption applications.
RESUMO
Bright afterglow room-temperature phosphorescence (RTP) soon after ceasing excitation is a promising technique for greatly increasing anti-counterfeiting capabilities. The development of a process for rapid high-resolution afterglow patterning of crystalline materials can improve both high-speed fabrication of anti-counterfeiting afterglow media and stable afterglow readout compared with those achieved with amorphous materials. Here, the high-resolution afterglow patterning of crystalline materials via cooperative organic vapo- and photo-stimulation is reported. A single crystal of (S)-(-)-2,2'-bis(diphenylphosphino)-5,5',6,6',7,7'8,8'-octahydro-1,1'-binaphthyl [(S)-H8-BINAP] doped with (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [(S)-BINAP] shows green afterglow RTP. Crystals of (S)-BINAP-doped (S)-H8-BINAP changed to an amorphous state with no afterglow capability on weak continuous photoirradiation under dichloromethane (DCM) vapor. Photoirradiation induced oxidation of the (S)-H8-BINAP host molecule in the crystal. The oxidized (S)-H8-BINAP forms on the crystal surface strongly interacted with DCM molecules, which induces melting of the (S)-BINAP-doped (S)-H8-BINAP crystal and trigger formation of an amorphous state without an afterglow capability. High-resolution afterglow patterning of the crystalline film is rapidly achieved by using cooperative organic vapo- and photo-stimulation. In addition to the benefit of rapid afterglow patterning, the formed afterglow images of the crystalline film can be repeatedly read out under ambient conditions without DCM vapor.
RESUMO
Sustainable long-lived room temperature phosphorescence (RTP) materials with color-tunable afterglows are attractive but rarely reported. Here, cellulose is reconstructed by directed redox to afford ample active hydroxyl groups and water-solubility; arylboronic acids with various π conjugations can be facilely anchored to reconstructed cellulose via click chemistry within 1 min in pure water, resulting in full-color tunable RTP cellulose. The rigid environment provided by the BâO covalent bonds and hydrogen bonds can stabilize the triplet excitons, thus the target cellulose displays outstanding RTP performances with the lifetime of 2.67 s, phosphorescence quantum yield of 9.37%, and absolute afterglow luminance of 348 mcd m-2. Furthermore, due to the formation of various emissive species, the smart RTP cellulose shows excitation- and time-dependent afterglows. Taking advantages of sustainability, ultralong lifetime, and full-color tunable afterglows, et al, the environmentally friendly RTP cellulose is successfully used for nontoxic afterglow inks, delay lighting, and afterglow display.
RESUMO
The development of organic materials that deliver room-temperature phosphorescence (RTP) is highly interesting for potential applications such as anticounterfeiting, optoelectronic devices, and bioimaging. Herein, a molecular chaperone strategy for controlling isolated chromophores to achieve high-performance RTP is demonstrated. Systematic experiments coupled with theoretical evidence reveal that the host plays a similar role as a molecular chaperone that anchors the chromophores for limited nonradiative decay and directs the proper conformation of guests for enhanced intersystem crossing through noncovalent interactions. For deduction of structure-property relationships, various structure-related descriptors that correlate with the RTP performance are identified, thus offering the possibility to quantitatively design and predict the phosphorescent behaviors of these systems. Furthermore, application in thermal printing is well realized for these RTP materials. The present work discloses an effective strategy for efficient construction of organic RTP materials, delivering a modular model which is expected to help expand the diversity of desirable RTP systems.
RESUMO
Herein, a type of light- and heat-driven flexible supramolecular polymer with reversibly long-lived phosphorescence and photochromism is constructed from acrylamide copolymers with 4-phenylpyridinium derivatives containing a cyano group (P-CN, P-oM, P-mM), sulfobutylether-ß-cyclodextrin (SBCD), and polyvinyl alcohol (PVA). Compared to their parent solid polymers, these flexible supramolecules based on the non-covalent cross-linking of copolymers, SBCD, and PVA efficiently boost the phosphorescence lifetimes (723.0 ms for P-CN, 623.0 ms for P-oM, 945.8 ms for P-mM) through electrostatic interaction and hydrogen bonds. The phosphorescence intensity/lifetime, showing excellent responsiveness to light and heat, sharply decreased after irradiation with a 275 nm flashlight or sunlight and gradually recovered through heating. This is accompanied by the occurrence and fading of visible photochromism, manifesting as dark green for P-CN and pink for P-oM and P-mM. These reversible photochromism and phosphorescence behaviors are mainly attributed to the generation and disappearance of organic radicals in the 4-phenylpyridinium derivatives with a cyano group, which can guide tunable luminescence and photochromism.
RESUMO
Hour-level persistent room temperature phosphorescence (RTP) phenomena based on multi-confinement carbon dots (CDs) are reported. The CDs-based system reported here (named Si-CDs@B2O3) can be efficiently synthesized by a simple pyrolysis method compared to the established persistent RTP systems. The binding modes of CDs, silica (SiO2), and boron oxide (B2O3) are deduced from a series of characterizations including XRD, FT-IR, and TEM characterization. Further studies show that the formation of covalent bonds between B2O3, SiO2, and CDs play a key role in activating the persistent RTP and preventing its quenching. This is a rare example of a persistent RTP system that exhibits hourly persistent RTP under environmental conditions. Finally, the applications of Si-CDs@B2O3 are demonstrated for anti-counterfeiting, long-duration phosphorescence imaging, and fingerprinting. This synthetic strategy is expected to provide strong technical support for the preparation of persistent RTP CDs and pave the way for the synthesis of persistent RTP CDs in the future.
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.
RESUMO
Carbon dots (CDs) based room temperature phosphorescence (RTP) materials can be prepared via facile procedures and exhibit excellent photostability and biocompatibility. Furthermore, doping of hetero-atoms into CDs can afford multiple triplet levels. The RTP emission generated from the resultant CDs always displays outstanding dynamic behaviors and even can be efficiently excited by visible light. Given this, CDs-based RTP materials not only can be used for anti-counterfeiting but also exhibit great application potential in signage and illumination fields. In this contribution, a type of B, N, and P co-doped CDs are prepared in hectogram scale. Upon excitation by UV lamp and white LED, the obtained CDs emit green and yellow RTP, respectively, the lifetime of which are 851 and 481 ms, respectively. It is found that the luminescence color of the CDs can be further tuned. By controlling the degree of carbonization, the RTP color of the CDs can be facilely tuned from green to orange-red. Based on an energy transfer strategy, the luminescence color can be further tuned to red. Benefited from the dynamic and visible-excited colorful RTP emission, the application of these obtained CDs in anti-counterfeiting, fingerprint collection, and luminescent traffic signage are also explored.
RESUMO
Room temperature phosphorescent (RTP) materials with long-lived, excitation-dependent, and time-dependent phosphorescence are highly desirable but very hard to achieve. Herein, this work reports a rational strategy of multiple wavelength excitation and time-dependent dynamic RTP color by confining silane-functionalized carbon dots (CDs) in a silica matrix (Si-CDs@SiO2). The Si-CDs@SiO2 possesses unique green-light-excitation and a change in phosphorescence color from yellow to green. A slow-decaying phosphorescence at 500 nm with a lifetime of 1.28 s and a fast-decaying phosphorescence at 580 nm with a lifetime of 0.90 s are observed under 365 nm of irradiation, which originated from multiple surface triplet states of the Si-CDs@SiO2. Given the unique dynamic RTP properties, the Si-CDs@SiO2 are demonstrated for applications in fingerprint recognition and multidimensional dynamic information encryption. These findings will open an avenue to explore dynamic phosphorescent materials and significantly broaden their applications.
RESUMO
The synthesis, crystal structure and room-temperature phosphorescence (RTP) of a 2D metal-free inorganic covalent framework ((H2en) [B5O8(OH)], named as CityU-12, and en represents for ethylenediamine) are reported. The precise structure information of CityU-12 has been disclosed through both single-crystal X-ray diffraction (SCXRD) analysis and low-dose high-resolution transmission electron microscopy (LD-HRTEM) study. The SCXRD results show that CityU-12 composes of 2D anionic BâO-based covalent inorganic frameworks with protonated ethylenediamine locating in the pore sites of 2D BâO layers while LD-HRTEM suggests that CityU-12 has an interplanar distance of 0.60 nm for (00 2 ¯ $\bar{2}$ ) crystal plane and 0.60 nm for (10 1 ¯ $\bar{1}$ ) crystal plane. The optical studies show that CityU-12 is an excellent nonconventional RTP material with the emission peak at 530 nm and a lifetime of 1.5 s. The quantum yield is 84.6% and the afterglow time is as long as 2.5 s. This work demonstrates that metal-free BâO frameworks can be promising nonconventional phosphors for RTP.
RESUMO
A new methodological design is proposed for carbon dots (CDs)-based crystallization-induced phosphorescence (CIP) materials via one-step self-assembled packaging controlled by NH4 +. O-phenylenediamine (o-PD) as a nitrogen/carbon source and the ammonium salts as oxidants are used to obtain CDs supramolecular crystals with a well-defined staircase-like morphology, pink fluorescence and ultralong green room-temperature phosphorescence (RTP) (733.56 ms) that is the first highest value for CDs-based CIP materials using pure nitrogen/carbon source by one-step packaging. Wherein, NH4 + and o-PD-derived oxidative polymers are prerequisites for self-assembled crystallization so as to receive the ultralong RTP. Density functional theory calculation indicates that NH4 + tends to anchor to the dimer on the surface state of CDs and guides CDs to cross-arrange in an X-type stacking mode, leading to the spatially separated frontier orbitals and the through-space charge transfer (TSCT) excited state in turn. Such a self-assembled mode contributes to both the small singlet-triplet energy gap (ΔEST) and the fast inter-system crossing (ISC) process that is directly related to ultralong RTP. This work not only proposes a new strategy to prepare CDs-based CIP materials in one step but also reveals the potential for the self-assembled behavior controlled by NH4 +.
RESUMO
Phosphorescent materials with time-dependent phosphorescence colors (TDPCs) have great potential in advanced optical applications. Synthesis of such materials is attractive but challenging. Here, a series of carbon dot-porous Al2 O3 composites exhibiting distinctive TDPC characteristics is prepared by high-temperature pyrolysis of Al-based metal-organic frameworks NH2 -MIL-101(Al). The composite synthesized at 700 °C (CDs@Al2 O3 -700) shows an obvious change in phosphorescence color from blue to green after removing the excitation light of 280 nm. Photophysical analysis reveals that two emission centers in CDs, namely carbon core and surface states, are responsible for the short-lived blue phosphorescence (96 ms) and long-lived green phosphorescence (911 ms), respectively. The combination of blue and green phosphorescence with different decay rates triggering the interesting TDPC phenomenon. CDs@Al2 O3 -700 has a significantly high phosphorescence quantum yield of up to 41.7% and possesses an excellent optical stability against water, organic solvents, and strong oxidants, which benefits from the multi-confinement of CDs by the porous Al2 O3 matrix through rigid network, strong space constraint, and stable covalent bonding. Based on the TDPC property, multilevel coding patterns composed of CDs@Al2 O3 are successfully fabricated for advanced dynamic information encryption.
RESUMO
Circularly polarized room-temperature phosphorescence (CPRTP) simultaneously featuring multiple colors and extremely high dissymmetry factor (glum) is crucial for increasing the complexity of optical characteristics and advancing further development, but such a type of CPRTP is still unprecedented. The present work develops an effective and universal strategy to achieve full-color CPRTP with ultra-high glum factors in a polymeric cholesteric superhelix network, which is constructed by cholesteric liquid crystal polymer and chiral helical polymer (CHP). Taking advantage of the high helical twisting power of CHP, the resulting polymeric cholesteric superhelix network exhibits remarkable optical activity. Significantly, by adopting a simple double-layered architectures consisting of the cholesteric superhelix film and phosphorescent films, blue-, green-, yellow-, and red-CPRTP emissions are successfully obtained, with maximum |glum| values up to 1.43, 1.39, 1.09 and 0.84, respectively. Further, a multilevel information encryption application is demonstrated based on the multidimensional optical characteristics of the full-color double-layered CPRTP architectures. This study offers new insights into fabricating polymeric cholesteric superhelix with considerable CPRTP performance in advanced photonic applications.
RESUMO
Novel platinum(II) complexes, derived from the spiro[fluorene-9,9'-xanthene] (SFX) motif, were synthesized and combined with different auxiliary ligands such as acetylacetonate (acac), bis(2,4,6-trimethylphenyl)propane-1,3-dionate (mesacac) and dihydrobis(3,5-dimethylpyrazole-1-yl) borate. The final products were obtained in yields of up to 36 % and characterized by NMR, X-ray and combustion analysis. These complexes have structured green-blue emission spectra with Commission Internationale de l'Éclairage (CIExy) coordinates of (0.21;0.46). Excellent photoluminescence quantum yields (PLQYs) ranging from 87 %-91 % were found. The emission lifetimes vary from 33â µs to 43â µs. Calculations on the B3LYP/6-311++G** level of theory reveal, that the nature of the emissive state is dependent on the positional regioisomerism of the SFX motif. The 2-SFX complexes demonstrate ligand-centered (3LC) emission, while the 2'-SFX regioisomer with the mesacac ligand shows a strong 3MLCT character.