Luminescence Properties Research Articles

Responsive Organic Fluorescent Aggregates Based on Ion-π Interactions Away from Fluorescent Conjugated Groups.

Responsive organic luminescent aggregates have a wide range of application fields, but currently there is still a lack of reasonable molecular design strategies. Introducing ion-π interactions into molecules can effectively alter their luminescent properties. However, current research typically focuses on ion localization at luminescent conjugated groups with the strong interaction forces. In this work, we introduce the flexible alkoxy chain spacers between fluorescent conjugated groups and ion-π interaction sites, and then adjust the fluorescence performance of the molecule by changing the strength of ion-π interactions. Bromine ion-based molecules with strong ion-π interactions exhibit high and stable fluorescence quantum yields in crystals and amorphous powders under the external stimuli. Hexafluorophosphate ion-based molecules with weak ion-π interactions have the high fluorescence quantum yield in crystals and very low fluorescence quantum yield in amorphous powders, showing variable fluorescence intensities under external stimuli. This demonstrates a new class of responsive organic luminescent solid-state materials.

From synthesis to applications of biomolecule-protected luminescent gold nanoclusters.

Gold nanoclusters (AuNCs) are a class of novel luminescent nanomaterials that exhibit unique properties of ultra-small size, featuring strong anti-photo-bleaching ability, substantial Stokes shift, good biocompatibility, and low toxicity. Various biomolecules have been developed as templates or ligands to protect AuNCs with enhanced stability and luminescent properties for biomedical applications. In this review, the synthesis of AuNCs based on biomolecules including amino acids, peptides, proteins and DNA are summarized. Owing to the advantages of biomolecule-protected AuNCs, they have been employed extensively for diverse applications. The biological applications, particularly in bioimaging, biosensing, disease therapy and biocatalysis have been described in detail herein. Finally, current challenges and future potential prospects of bio-templated AuNCs in biological research are briefly discussed.

Dual Challenge-Response Systems of a Three-Dimensional "Bionic" Fluorescent Physically Unclonable Function Label.

Inspired by the light and dark variations observed in natural cloud clusters under sunlight, we propose a three-dimensional (3D) "bionic" fluorescent physically unclonable function (PUF) label. The minimalist preparation process eliminates the need for expensive traditional instruments, thus offering new insight into the widespread adoption of 3D PUF labels. The Eu(CCA)3(H2O)2 powder, which is the first to propose its secondary building unit, was chosen as the fluorescent material. Its 3D morphology is preserved in the resin to mimic cloud-like structures. Furthermore, the luminescent properties are elucidated through experimental tests and first-principles calculations. To overcome the coding capacity limitation of traditional two-dimensional (2D) fluorescent PUF labels, a dual challenge-response system model is proposed. The shallow and deep models provide anticounterfeiting information from macro and micro perspectives, respectively. This successfully increases the encoding capacity from 210×10 to 2100×10000 for a 10 × 10 pixel binary code. Therefore, 3D "bionic" fluorescent PUF labels strike a balance between the simple usage of PUF labels and enhanced label security.

Water‐Assisted Synthesis of Layer‐Controlled CsPbBr3 Nanoplates Spontaneously Encapsulated in PbBr(OH)

AbstractCsPbBr3 nanoplates (NPs) have shown great potential in diverse optoelectronic applications. Despite the wonderful luminescence properties, the inherent instability of these NPs hinders their use in practical situations. Herein, a facile water‐assisted strategy is reported to synthesize highly stable blue emission CsPbBr3 NPs encapsulated in PbBr(OH). The introduction of water directly into the reaction mixture is pivotal, as it triggers the transformation of bulk CsPbBr3 nanocubes into 2‐D CsPbBr3 NPs within the PbBr(OH) matrix, resulting in the formation of CsPbBr3@PbBr(OH) microbricks. Remarkably, the water content in the reaction mixture allows the control of the number of perovskite layers in the NPs, thus enabling the emission color to be tuned from deep blue to green. The unconventional approach presented herein not only offers a cost‐effective pathway to synthesize blue‐emitting perovskites which are highly stable in a wide variety of polar and non‐polar solvents, but also holds immense potential for propelling the advancement of high‐performance LEDs and other optoelectronic devices. The findings underscore the significance of water in dictating the growth dynamics and emission characteristics of perovskite NPs, paving the way for their practical application.

Preparation of F/Mn-Doped CsPb(Br/Cl)3 Quantum-dot glass and their Luminescence Properties

Preparation of F/Mn-Doped CsPb(Br/Cl)₃ Quantum-dot glass and their Luminescence Properties

Evidence and Practical Applications of Site Occupancy Theory (SOT) of Eu3+ in Scheelite Compounds.

The determination of the site occupancy of activators in phosphors is essential for precise synthesis, understanding the relationship between their luminescence properties and crystal structure, and tailoring their properties by modifying the host composition. Herein, one simple method was proposed to help determine the sites at which the doping of rare earth ions or transition metal ions occupies in the host lattice through site occupancy theory (SOT) for ions doped into the matrix lattice. SOT was established based on the fact that doping ions preferentially occupy the sites with the lowest bonding energy deviations. In order to provide detailed experimental evidence to prove the feasibility of SOT, several scheelite-type compounds were successfully synthesized using a high-temperature solid-phase method. When Eu3+ ions occupy a similar surrounding environment site, the photoluminescence spectra of the activators Eu3+ are similar. Therefore, by comparing the intensity ratio of photoluminescence spectra and the mechanism of all transitions of KEu(WO4)2, KY(WO4)2:Eu3+, Na5Eu(WO4)4, and Na5Y(WO4)4:Eu3+, it was proved that SOT can successfully confirm the site occupation when doped ions enter the matrix lattice. SOT was further applied to the sites occupied by Eu3+ ion-doped LiAl(MoO4)2 and LiLu(MoO4)2.

Natural Light Rechargeable Night Peal-like Coatings for Expressway

Traditional roadway lighting is intended to provide safe guidance for drivers and pedestrians, but the large-scale application of roadway lighting has resulted in significant energy consumption and light pollution. However, road markings prepared by luminous coating are a kind of multi-functional road marking that can meet the needs of highway lighting at night and save energy. Here, CaAl2O4:Eu2+,Nd3+,Gd3+ blue long-afterglow phosphor is obtained by the high-temperature solid-state method, and the blue luminescent coating is synthesized by the blending method. The phase composition, microscopic morphology, luminescence properties and water resistance of the phosphor and luminescent coatings are characterized. The best components and processes of the luminescent coating are explored to meet the application of an expressway. Considering the afterglow’s performance, the optimal calcination temperature of the phosphor is determined to be 1300 °C. The afterglow of the phosphor can be over 8 h after 2 h of daylight excitation. The addition of 1.25% SiO2 to the luminescent coating improves the uniformity of the components, and the incorporation of 3.5% CaCO3 improves the denseness of the coating. When the coating thickness is 0.8mm, the luminescent coating can achieve the best luminous effect. After 120 h of immersion in water, the afterglow intensity of the luminescent coating reduced to 70% of the original, which has excellent water resistance. The blue luminescent coating with the addition of appropriate amounts of CaCO3 and SiO2 improves the dispersion as well as the densification of the components in the coating to achieve the best luminescent effect. In the Shenyang area, different weather conditions (cloudy, sunny, rainy) have no significant effect on the afterglow performance of the luminescent coatings, all of which can achieve over 5 h of afterglow and are suitable for expressways.

Optimization of the structure, morphology and luminescent properties of NaYF4 upconversion nanoparticles

Optimization of the structure, morphology and luminescent properties of NaYF4 upconversion nanoparticles

Phase Transition and Luminescent Property Change Induced by Different Organic Cations in One-Dimensional Double Perovskites.

Double perovskites (DPs) have attracted attention in the field of luminescence due to their inherent broadband emission of self-trapping excitons. In this work, we choose [(CH3)3NCH2CHCH2]+ and [CH3CHOHCH2NH2]+ as organic cations to synthesize two new organic-inorganic hybrid DPs, [(CH3)3NCH2CHCH2]2KInCl6 (1) and [CH3CHOHCH2NH2]2KInCl6 (2). The [KCl6]3- and [InCl6]3- octahedra are interchangeably connected by sharing two opposite faces, forming a one-dimensional coordination chain. Each K atom coordinates with six chlorine atoms in 1, while it coordinates with two oxygen atoms in addition to the six chlorine atoms in 2. The coordination between ions K and O in compound 2 may have significantly reduced its luminescence. As a result, compound 1 shows bright-yellow light with a quantum yield of more than 90%, while 2 shows weak blue light with a quantum yield of only 0.98%. In addition, different from no phase transition found in 2, 1 undergoes a reversible phase transition at 324/307 K in the heating-cooling cycle. Through structural and spectral analysis and density functional theory calculation, we conclude that the larger degree of [InCl6]3- octahedral distortion and the larger anion distance (In···In) also cause the PLQY of compound 1 to be higher than that of compound 2.

Introduction of Organic Dyes into Cadmium(II) MOF for Tunable Light Emission and Highly Sensitive Probing Antibiotics

A honeycomb porous cadmium(II) metal–organic framework {[Cd(L)(H2O)]·NMP·5H2O}n (1, H2L = 1‐(4‐carboxyphenyl)‐1H‐pyrazole‐3‐carboxylic acid and NMP = 1‐methyl‐2‐pyrrolidinone) was obtained using the solvothermal method. The luminescent molecules rhodamine B (RhB) and fluorescein (FL) were encapsulated in 1 using the immersion method to prepare RhB@1 and FL@1 dual emission composites. Additionally, a series of RhBx/FL1‐x@1 composites with varying luminescence properties were generated by altering the molar ratio of RhB to FL. Furthermore, the photoluminescence of RhB@1 and FL@1 was demonstrated to be caused by photoelectron transfer and fluorescence resonance energy transfer from 1 to the encapsulated guest module. Notably, RhB@1 showed the considerable improvement in fluorescence selectivity and detection limit (10‐6 M) for metronidazole and dimetronidazole with remarkable recyclability.

Efficient Deep-Blue Multiple-Resonance Emitters Based on Azepine-Decorated Ν-DABNA for CIEy below 0.06.

Ultrapure deep-blue emitters are in high demand for organic light-emitting diodes (OLEDs). Although color coordinates serve as straightforward parameters for assessing color purity, precise control over the maximum wavelength and full-width at half-maximum is necessary to optimize OLED performance, including luminance efficiency and luminous efficacy. Multiple-resonance (MR) emitters are promising candidates for achieving ideal luminescence properties; consequently, a wide variety of MR frameworks have been developed. However, most of these emitters experience a wavelength displacement from the ideal color, which limits their practical applicability. Therefore, a molecular design that is compatible with MR emitters for modulating their energy levels and color output is particularly valuable. Here, we demonstrate that the azepine donor unit induces an appropriate blue-shift in the emission maximum while maintaining efficient MR characteristics, including high photoluminescence quantum yield, narrow emission, and a fast reverse intersystem crossing rate. OLEDs using newly developed MR emitters based on the ν-DABNA framework simultaneously exhibit a high quantum efficiency of ∼30%, luminous efficacy of ∼20lm W-1, exceptional color purity with Commission Internationale de l'Éclairage coordinates as low as (0.14, 0.06), and notably high operational stability. These results demonstrate unprecedentedly high levels compared with those observed in previously reported deep-blue emitters. This article is protected by copyright. All rights reserved.

Tunable Narrow‐Band Cyan‐Emission of Eu2+‐doped Nitridomagnesophosphates Ba3−xSrx[Mg2P10N20] : Eu2+ (x=0–3)

AbstractTetrahedron‐based nitrides offer a wide range of properties and applications. Highly condensed nitridophosphates are examples of nitrides that exhibit fascinating luminescence properties when doped with Eu2+, making them appealing for industrial applications. Here, we present the first nitridomagnesophosphate solid solution series Ba3−xSrx[Mg2P10N20] : Eu2+ (x=0–3), synthesized by a high‐pressure high‐temperature approach using the multianvil technique (3 GPa, 1400 °C). Starting from the binary nitrides P3N5 and Mg3N2 and the respective alkaline earth azides, we incorporate Mg into the P/N framework to increase the degree of condensation κ to 0.6, the highest observed value for alkaline earth nitridophosphates. The crystal structure was elucidated by single‐crystal X‐ray diffraction, powder X‐ray diffraction, energy‐dispersive X‐ray spectroscopy (EDX), and solid‐state NMR. DFT calculations were performed on the title compounds and other related highly condensed nitridophosphates to investigate the influence of Mg in the P/N network. Eu2+‐doped samples of the solid solution series show a tunable narrow‐band emission from cyan to green (492–515 nm), which is attributed to the preferred doping of a single crystallographic site. Experimental confirmation of this assumption was provided by overdoping experiments and STEM‐HAADF studies on the series as well on the stoichiometric compound Ba2Eu[Mg2P10N20] with additional atomic resolution energy‐dispersive X‐ray spectroscopy (EDX) mapping.

Fe3+-activated magnetoplumbite persistent luminescence phosphor by modulating the oxygen vacancy.

Broadband near-infrared (NIR) spectroscopy has gained significant attention due to its versatile application in various fields. In the realm of NIR phosphors, Fe3+ ion is an excellent activator known for its nontoxic and harmless nature. In this study, we prepared an Fe3+-activated SrGa12O19 (SGO) NIR phosphor and analyzed its phase and luminescence properties. Upon excitation at 326 nm, the SGO:Fe3+ phosphor exhibited a broadband emission in the range 700-1000 nm, peaking at 816 nm. The optical band gap of SGO:Fe3+ was evaluated. To enhance the long-lasting phosphorescence, an oxygen vacancy-rich SGO:Fe3+ (VO-SGO:Fe3+) sample was prepared for activation. Interestingly, the increase in the oxygen-vacancy concentration indeed contributed to the activation of persistent luminescence of Fe3+ ions. The VO-SGO:Fe3+ sample has a long duration and high charge storage capacity, allowing it to perform efficiently in various applications. This work provides the foundation for further design of Cr3+-free PersL phosphors with efficient NIR PersL.

Why are the luminescent properties of the mononuclear and binuclear Eu/Tb-2-hydroxybenzoate complexes with 1,10-phenanthroline so different? An experimental-theoretical study

This study presents a comprehensive investigation into the structural and luminescent properties of lanthanide 2-hydroxybenzoate compounds, focusing on Eu3+ and Tb3+ ions in both single and mixed systems. The X-ray structures of (Hphen)2[Eu2(2-OHBz)8(H2O)2]·2H2O (1a·2H2O) and [Eu(2-OHBz)3(phen)2]·PhMe (2a·PhMe) were determined, where 2-OHBz: 2-hydroxybenzoate and phen: 1,10-phenantroline, revealing triclinic crystal structures with distinct coordination geometries. Compound 1a·2H2O displayed a centrosymmetric dinuclear anion with a coordination number of eight for each Eu3+ center, while compound 2a·PhMe exhibited a neutral mononuclear complex with a decacoordinated Eu3+ center. A comparative analysis of luminescent properties between these compounds unveiled significant differences in the nonradiative decay rates of the 5D0 level of Eu3+ ions, suggesting potential luminescence-quenching channels. The investigation is extended to mixed Eu3+-Tb3+ systems, demonstrating efficient Tb3+ to Eu3+ energy transfer, especially at room temperature. Three models, including two novel ones proposed in this study, were considered to rationalize energy transfer in the mixed systems. Our theoretical-experimental investigation reveals that variations in lifetimes of the emitting level 5D0 of Eu-2-OHBz mononuclear and binuclear complexes, or mixed Eu/Tb-2-OHBz complexes, with 1,10-phenanthrolines, primarily result from multiphonon decay processes; however, low-energy ligand-to-metal charge transfer (LMCT) states play a key role in suppressing luminescence in the binuclear complex compare to the mononuclear ones.

Reduction mechanism and energy transfer between Eu3+ and Eu2+ in Eu-doped materials synthesized in air atmosphere

Abstract This article critically examines the reduction mechanisms and energy transfer processes between trivalent europium ions (Eu3+) and divalent europium ions (Eu2+) in materials synthesized in an air atmosphere. It also encompasses various materials and conditions, including a critical analysis of the reduction mechanism and energy transfer between Eu3+ and Eu2+ in Eu-doped materials. Specific investigations include exploring the reduction process in BaMgSiO4:Eu, focusing on factors influencing the reaction. The article also covers low-temperature self-reduction, addressing conditions and mechanisms such as the charge compensation model and laser-induced reduction. Additionally, it explores the influence of charge compensation on luminescent properties, emphasizing enhancements in red emission. Investigations into the role of oxygen vacancies in the reduction of Eu3+ and their implications on material properties are presented. This article further digs into abnormal reduction processes and the formation of defect centers in Eu3+-doped pollucite, proposing a substitution defect model for the self-reduction of europium ions in silicate Ba(Eu)MgSiO4 phosphors. Unusual reduction phenomena, such as reduction via boiling water in Yb2Si2O7:Eu3+ phosphors, and reductions in various glass systems, including porous glass, ZnO–B2O3–P2O5 glasses, aluminoborosilicate glasses, europium-doped Li2B4O7 glass, and aluminosilicate oxyfluoride glass (AOG), are also thoroughly examined.

Exploring innovative applications of Sr2MgSi2O7:Fe3+ luminescent system in surface-triggered fingerprint divergence and cheiloscopy screening

In this study, we employ a cost-effective combustion method to synthesize (1-11 mol %) Fe3+ doped Sr2MgSi2O7 nanophosphors (SMSO NPs) and conduct a comprehensive investigation into their structural and luminescent properties. The impact of iron concentration on the structural and optical characteristics is thoroughly analysed, revealing a tetragonal crystal structure with space group P-421m through Rietveld refinement and X-ray Diffraction (XRD) patterns. Scanning electron microscopy showcases the random dispersion of agglomerated particles with non-uniform dimensionality. Energy Dispersive X-ray analysis (EDS) assesses the nominal composition of Sr, Mg, Si, Fe, and O, while X-ray Photon Spectroscopy (XPS) confirms the direct incorporation of Fe3+ ions into the SMSO lattice. Photoluminescence (PL) emission spectra exhibit a UV emission band at 345 nm and a deep red emission band at 718 nm. The residual luminescence intensity of SMSO: Fe3+ at 200 °C is 91 %. Under 365 nm UV light, the optimized SMSO: Fe3+ NPs displays easily identifiable levels I-III fingerprints (FPs) features with good resolution and contrast. The resilient luminescence and nano-regime of the phosphor reveal well-defined type I–V groove patterns in latent lip prints (LLPs) on various non-porous surfaces, unaffected by background interference or colour distraction. This study highlights SMSO: Fe3+ NPs as a promising option for individualizing and detecting latent fingerprints (LFPs) and lip prints (LPs).

Luminescence and energy transfer properties of color-tunable Dy3+, Eu3+ co-activated NaGdSiO4 phosphor for WLED with great thermo-stability.

A series of NaGd1-x-ySiO4: y Dy3+ - x Eu3+ phosphors were synthesized by a high-temperature solid-phase method. The optimal doping ion concentration of Dy3+ ions for this phosphor was determined to be 1% from the emission spectra. The energy transfer between Dy3+ and Eu3+ ions at 351 nm was investigated by photoluminescence spectra and fluorescence decay curves. At the excitation wavelengths of 275 nm, 351 nm, 366 nm, and 394 nm, a change from yellow to white to red light can be realized by adjusting the doping concentration of Eu/Dy ions. Particularly, by testing the temperature-dependent fluorescence spectrum of the phosphor, it can be found that the luminous intensity of the phosphor is as high as 96% when 394 nm excitation is employed at 413 K. It was the maximum at this temperature comparing with other phosphors as far as we know. The color coordinate values show that the NaGd1-x-ySiO4: x Dy3+ - y Eu3+ phosphors are very close to the white light color coordinates (x = 0.33, y = 0.33) under 351 nm excitation. Meanwhile, the correlated color temperature is between 5062 - 7104 K. These results indicate that this phosphor is a promising candidate for high-quality WLED.

Bi3+/Mn4+ co-doped Y2MgTiO6 dual-emitting phosphors for plant growth lighting and temperature sensor

Novel Bi3+/Mn4+ co-doped Y2MgTiO6 dual-emitting phosphors were synthesized using a high-temperature solid-phase method. The crystal structure and luminescence properties of phosphors were systematically investigated by experimental characterization and theoretical calculation. Under excitation at 375 nm, Y2MgTiO6:Bi3+, Mn4+ phosphors exhibit two emission bands located at 410 nm and 696 nm (blue and red), which can well be matched with the absorption bands of chlorophylls a, b and phytochrome. The Y2MgTiO6: Bi3+, Mn4+ luminescence remains at 66.2% intensity at 423 K and quantum yield is 52.06%. Optical temperature properties of Y2MgTiO6:Bi3+, Mn4+ were investigated using fluorescence intensity ratio (FIR) analysis and were found to reach a maximum relative sensitivity of 2.93% K-1 at 498 K. The study suggests that this material could be a potential option for indoor plant culture and optical temperature sensing.

Novel fluorescent sensor based on triazole-pyridine derivative for selective detection of mercury (II) ions in different real water samples: Experimental and DFT calculations

Toxic heavy metals, particularly mercury II ions, must be selectively detected in industrial effluent to restrict their percentage and thereby aid in environmental protection. The present study describes the synthesis of 6-(4-(4-(5-cyano-6-oxo-4-styryl)-1,6-dihydropyridin-2-yl)-5-methyl-1H-1,2,3-triazol-1-yl)phenyl)-2-oxo-4-styryl)-1,2-dihydropyridine-3-carbonitrile (TOHC) and its ability as a novel selective fluorescent probe for the detection of mercury II ions in different real water samples. The structure of the prepared TOHC was confirmed by both FTIR and 1HNMR analysis, while crystal structure and thermal stability was investigated using XRD and TGA techniques. The optical properties of TOHC were investigated using both UV–vis and fluorescence spectroscopy at different pH values. Its luminescent properties obtained when TOHC is excited by a wavelength equal to 424 nm, where a maximum emission peak has observed at a wavelength equal to 466.6 nm. Moreover, using Stern-Volmer equation indicate that there is a good correlation between the concentration of Hg2+ ions and the fluorescence intensity of TOHC accompanied with high quenching rate equal to 2.24 x 104 mol−1.L. Selectivity of TOHC toward Hg2+ ions was confirmed by the assistance of fifteen different metal cations. In addition, Job’s Plot method and UV–vis spectroscopy were used to estimate the stoichiometry as well as understand the quenching mechanism between TOHC sensor and Hg2+ ions. The applicability of TOHC sensor for the detection of Hg2+ ions in real samples was further validated using five different real water samples and exhibited excellent results. Lastly, DFT calculations were conducted to provide atomistic insights into the chemical interaction between Hg(II) and TOHC.

Synthesis of 1, 2, 3-triazole linked 5 fluorouracil - carbon dots -folate conjugates for target specific anticancer activity and cell imaging applications

This work provides a unique strategy to anchor the individual properties of fluorophores, pharmacophores and receptors in a single platform using a copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC). Notably, this approach counters the long-term dispute associated with the target-specific drug delivery of 5 fluorouracil and its intracellular tracing. Significantly, the luminescence property of the carbon dots (CDs) and the anticancer activity of the 5 fluorouracil drug are well preserved, even after their structural modification. The resulting nano-hybrid conjugate shows good thermal stability, photo-stability and can selectively guide the drug molecule toward cancer cells and remain nontoxic to noncancerous (hFB) cells. The conjugation of folic acid to the nanohybrid surface promoted the folate receptor-facilitated endocytosis to the folate-positive (HeLa) cell lines over the folate-negative (MCF-7) cells, which enhanced cellular uptake and corresponding better cell apoptosis results. Around 18.2% of cell apoptosis (late + early) values were recorded for the folate-conjugated formulation compared to the folate-less formulation (12.3%) and pure 5 FU drug (7.9%) by a flow cytometry study. Cell cycle analysis confirmed that the populations of HeLa cells in the S phase were around 18.20% and 29.8% for the folate-less formulation and the folate-conjugated formulation, indicating all the formulations can hinder the DNA replication and thymidylate synthesis by introducing cell cycle arrest in the S phase, just like the pure 5 FU drug. Also, the location of the drug molecule can be simultaneously traced because of the luminescent nature of the CDs. Therefore, the developed system has potential in target-specific drug delivery and long-term drug molecule tracking applications.