Luminescence Changes Research Articles

Investigation of a bimetallic terbium(III)/copper(II) chemosensor for the detection of aqueous hydrogen sulfide

The chemosensor properties of a bimetallic terbium(III)/copper(II) complex functionalized with a 4-(2-pyridyl)-1,2,3-triazole ligand for the detection of Cu2+ ions and, aqueous and gaseous hydrogen sulfide was investigated. The 4-(2-pyridyl)-1,2,3-triazole ligand functions both as an antenna chromophore and a receptor for Cu2+ ions; the Cu2+ complex was shown to be a chemosensor for the detection of aqueous hydrogen sulfide. The chemosensor exhibited significant reversibility over multiple cycles, observed with the sequential addition of Na2S followed by Cu2+ ions. The limit of detection for aqueous hydrogen sulfide was 0.63 μM (20 ppb). No luminescent changes of the bimetallic terbium(III)/copper(II) complex were observed in the presence of gaseous hydrogen sulfide, and thus this sensor can only be used for the detection of aqueous hydrogen sulfide.

1D supramolecular assembly-induced emission and colorimetry toward precise onsite mercury(II) detection

Manipulation of the one-dimensional (1D) supramolecular assembly of platinum(II) terpyridyl complex is promising for achieving precise onsite mercury(II) detection in complex environments, but still challenging. Herein, by systematic molecular design of platinum(II) terpyridyl complex, chloride-mediated 1D supramolecular assembly has been successfully achieved, exhibiting not only improved recognition ability but also dual-visual signal, with turn-on red luminescence and high-contrast color change from pale-yellow to orange-red. The probe also shows excellent selectivity and anti-interference properties, fast response rate (< 1 s) and low detection limit, stretching to 20.6 fg when incorporated in a hydrogel matrix. Structure insight for the dual-visual response shows that this high detection performance derives from the ancillary ligand of -NCS, which endows the increase of ion-association ability between platinum(II) terpyridyl complex and [HgCl4]2−, leading that 1D packing mode with strengthened Pt-Pt interactions. In all, this work highlights a new strategy of 1D supramolecular assembly construction for high performance detection of heavy metal ions.

Temperature Changes in Luminescence of Mixed Complexes of Terbium and Samarium with Organic Ligands Based on 2,2-bipyridyldicarboxamides

Solutions in acetonitrile of three mixed complexes of rare earth elements (terbium and samarium) with organic ligands with various pyridine substituents were studied in this work. The ratios of ligands and metals in the resulting complexes were determined, and the stability constants of samarium complexes were calculated using the spectrophotometric titration method. Measurements of absorption, emission and excitation spectra of luminescence, luminescence kinetics of solutions of mixed complexes of rare earth elements with an excess of metal relative to the ligand were carried out at various temperatures in the range 298–328 K. An increase of luminescence intensity of a samarium ion in complex upon heating has been discovered for the first time. The dependences of the luminescence quantum yield and lifetime of mixed complexes on temperature were obtained. A thermometric parameter — the ratio of the integral luminescence intensities of samarium and terbium ions — was proposed, and the temperature sensitivity coefficient of this parameter was determined for different complexes.

Cl- skeleton modification and K+ charge compensation construct Eu2+ subcrystalline luminescent structure in NaAlSiO4

In this work, the highly homogeneous NaAlSiO4 structure was constructed by glass relaxation crystallization method. The evolution of the subcrystalline luminescence structure was examined by using Eu2+ as a structural probe. The optimization of luminescent properties and phase structure changes of Cl- substitution, Eu2+ occupancy and K+ charge compensation were studied by XRD, EDS, PL spectra, PLE spectra and luminescence thermal stability analysis. The research revealed the AB layer spacing of the crystal stretched and the hexatomix ring opened by Cl- directionally replace O2-(O5), inducing more Eu2+ to selectively occupy the Na+(I) site, resulting in local charge defects in the lattice. The transition emission efficiency of Eu2+ was increased by 50% with introducing K+ for directional charge compensation. In comparison with NaAlSiO4:2%Eu2+, the NaAlSiO3.96Cl0.04:2%Eu2+-8K+ phosphor showed a 20.82% increase in ΔE, indicating improved thermal sensitivity in this phosphor series, which holds promising potential for application in LED devices.

Enhancing Optical Properties of Zn-Mn Solid Solution Hybrid Halides for Wide Color Gamut Backlight Displays.

Hybrid metal halides display a range of optical properties and hold promise for various applications such as solid-state lighting, anti-counterfeiting measures, backlight displays, and X-ray detection. The incorporation of zinc into (C13H26N)2MnBr4 aims to enhance its structural rigidity and improve its narrow band green light emission properties. The resulting (C13H26N)2ZnBr4 compound exhibits an identical crystal structure to (C13H26N)2MnBr4, indicating the potential for a solid solution of varying Zn and Mn ratios within this structural framework. (C13H26N)2Zn0.2Mn0.8Br4 exhibits significantly enhanced properties, including a photoluminescence quantum yield of 92%, a minimum full width at half maximum of 43nm, and 85% retention of room temperature emission at 420K. Additionally, crystals of (C13H26N)2ZnCl4 and (C7H18N)2ZnX4 (X = Br, I) are synthesized, with (C7H18N)2ZnBr4 displaying luminescent color changes dependent on excitation. (C7H18N)2Zn0.2Mn0.8Br4 demonstrates reversible phase transitions and alterations in optical properties. A white light-emitting diode utilizing (C13H26N)2Zn0.2Mn0.8Br4 and commercial phosphors exhibited a color gamut of 112.2% of the National Television Standards Committee 1931 Standard. This investigation introduces a stable and highly efficient narrow-band green phosphor suitable for displays.

Fluorescence Light‐Up Electrospun Membrane Incorporated with PbBr2 as a Highly Selective Fluorescence Probe for the Detection of Cs+

AbstractThis study introduces a novel fluorescent light‐up electrospun membrane, integrating PbBr2, which serves as an exceptionally selective probe for the detection of cesium ions (Cs+). Leveraging the superior optical properties of CsPbBr3 perovskite nanocrystals (PNCs), the researchers employ electrospinning technology to fabricate a test strip, namely PbBr2@polyacrylonitrile (PbBr2@PAN) nanofiber membranes, capable of swiftly detecting Cs+ in water merely by observing changes in the nanocrystals' luminescence with the naked eye. By the introduction of NH4+‐modified montmorillonite (NH4+‐MMT), PbBr2‐MT@PAN nanofiber membranes is obtained. The selectivity and sensitivity to Cs+ can be further improved because NH4+‐MMT endows PbBr2‐MT@PAN nanofiber membranes with the hydrophilic property and selective adsorption toward Cs+ ions. The membrane's fabrication is simple, scalable, and cost‐effective, with high cesium selectivity and sensitivity down to 44 ppb. This innovation enables efficient, on‐site cesium monitoring critical for environmental safety and nuclear waste management.

Photoresponsive lanthanide-dianthracene framework: Introduction of photoactive anthracene pairs by controlling the synthesis temperature

Metal-organic frameworks (MOFs) containing face-to-face π-π interacting anthracene groups are promising photoresponsive materials because of their rich photophysical properties and their ability to undergo reversible [4+4] photocycloaddition reaction, but it is extremely challenging to obtain such materials. Herein, we propose a generalized method to accomplish photoresponsive MOFs by introducing anthracene pairs into the framework of the dianthracene-phosphonate-based MOFs by controlling the synthesis temperature. Compounds Dy2(ampH)2x(amp2H2)3-x(H2O)6∙4H2O [x = 0.01, Dy-70; x = 0.02, Dy-80; x = 0.037, Dy-90; amp2H4 = pre-photodimerized 9-anthracenemethylphosphonic acid (ampH2)] were obtained by the reaction of DyCl3 and amp2H4 in water at 70, 80, and 90 °C, respectively. They all show excimer emission of paired anthracenes at ca. 555 nm. Detailed studies of Dy-90 have shown that it undergoes a reversible photodimerization reaction under 365 nm and then 280 nm illumination, accompanied by luminescence changes. This property further enables Dy-90 to be used for optical anti-counterfeiting.

Multi-stimuli responsive Pt(II) complexes for information storage and anti-counterfeiting

Information encryption plays a crucial role, and various optical materials based on intricate chromophores have been investigated for anti-counterfeiting purposes. In this study, we designed and synthesized two luminescent Pt(II) complexes by concisely introducing different spatial steric hindrances. The complexes adopt distinct head-to-tail and head-to-head dimeric subunits, respectively, which further stack into one-dimensional (1D) chains and three-dimensional (3D) networks in turns. By doping into polymers, we have developed high-performance optical encryption and anti-counterfeiting materials. The authenticity of documents or products can now be verified through changes in luminescence induced by external stimuli, providing an enhanced level of security owing to the complexity of the chromophores and their unique response to various stimuli. The responsiveness of these materials to different types of external stimuli enables the creation of advanced security features that can be utilized in a variety of applications. The use of luminescent Pt(II) complexes in anti-counterfeiting materials offers a novel approach to verifying the authenticity of documents or products.

Multiple Stimulus Response Material Based on Sr-tcbpe MOF for Mechanochromism, Visualization Labeling, and Etching Toward TNP.

The abuse and excessive discharge of organic pollutants such as nitroaromatic compounds (NACs) have become a hot topic of concern for all humanity and society, and the development of fast, effective, and targeted technical means for detecting NACs also faces many challenges. Here, we reported a strontium-based metal-organic framework (MOF) {[Sr2(tcbpe)(H2O)4]}n (Sr-tcbpe), in which tcbpe represents deprotonated 4',4‴,4″‴,4‴‴-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1'biphenyl]-4-carboxylic acid)). In Sr-tcbpe, Sr-O polyhedron and deprotonated tcbpe4- ligand have a staggered connection to form a self-assembled three-dimensional network structure. In addition, it is found that Sr-tcbpe undergoes no luminescent color change when grinding under solvent protection, while mechanochromic fluorescence behavior is observed when grinding directly, leading to luminescent color changes from cyan to green (Sr-tcbpe-G). Additionally, Sr-tcbpe and Sr-tcbpe-G could selectively detect PNP, DNP, and TNP, and Sr-tcbpe achieves visual fluorescence sensing detection toward TNP at a limit of detection as low as 2.25 μM. Moreover, during the detection process, unexpectedly, TNP exhibits a selective etching effect on Sr-tcbpe, which could drill nano holes with different sizes on the surface area of MOF materials to a certain extent, achieving the conversion of chemical energy to mechanical energy. In addition, the successful preparation of a portable sensor Sr-tcbpe@gypsum block provides a platform for the perfect combination of mechanochromic fluorescence behavior and visualization detection toward TNP. It lays the foundation for the practical application of MOF materials in daily life.

Temperature Changes in Luminescence of Mixed Complexes of Terbium and Samarium with Organic Ligands Based on 2,2$${}^{\boldsymbol{\prime}}$$-bipyridylcarboxamides

Temperature Changes in Luminescence of Mixed Complexes of Terbium and Samarium with Organic Ligands Based on 2,2$${}^{\boldsymbol{\prime}}$$-bipyridylcarboxamides

Organic Mechanochromic Luminescent Materials with Self-Recovering Characters.

Recently, applied research on stimuli-responsive materials with luminescence-switching characteristics has been conducted in various fields. A representative phenomenon of stimuli-responsive luminescent materials is mechanochromic luminescence (MCL), which exhibits luminescent color change induced by mechanical stimuli such as grinding. These materials are among the most prominent candidates for security and sensing applications. Interestingly, some mechanochromic luminescent materials have shown self-recovery character, in which their original luminescent color can be recovered by just standing under ambient conditions after grinding. Although there are more and more reports of such materials in recent years, the fundamental principles of molecular design still remain elusive. In this concept, we summarize distinctive advances in mechanochromic luminescent materials with self-recovery according to the core structures of luminescent molecules. Controlling amorphous state by introducing substituents such as alkyl or polar groups is effective method to provide self-recovering properties.

Colour change and long-persistent properties of a new phosphor YBaZn3GaO7:Bi3+/Eu3+

Ion doping is one of the most effective strategies to induce interesting luminescence properties of materials. In this work, the Bi3+ and Eu3+ are introduced into a ‘114’ host material YBaZn3GaO7 (YBZG) to generate photoluminescence (PL), long-persistent luminescence (LPL) and colour change properties. The co-doped YBZG:0.003Bi3+/yEu3+ can generate multi-color emissions from green, through yellow to orange with the increasing of Eu3+ concentration. There are F-like color centers around conduction band (CB) of YBZG host with shallow or deep energy levels. The electrons trapped by deep levels response to the PC properties, whereas these for shallow levels response to the LPL properties. The PC process from white to apricot is reversible. By alternating thermal treatment and irradiation, YBZG:0.003Bi3+ was proved to have a good fatigue resistance of 3.1 %. For YBZG:0.003Bi3+/0.05Eu3+, it shows bright orange LPL emission when the irradiation is removed after 24 min. The achievement of this paper provides a design idea that if the host structure of a phosphor is of flexible and easy to occur defect, not only PL property, but also PC and LPL properties are probably able to realize.

Uncover the Unusual Near‐Infrared Luminescence in Stannates – Interplay of Cr3 + with Codopants

AbstractThe unintentional incorporation of various unknown trace amounts of impurities poses challenges and controversies in identifying luminescent mechanisms of certain systems. A common approach to confirm or exclude the involvement of a certain activation center is to monitor the changes in luminescence by intentionally doping the inferred species into the crystal. Here, an intriguing luminescent phenomenon resulting from the hidden interplay between the dopants and trace impurities, is presented. In alkaline‐earth stannate perovskites, near‐infrared luminescence is observed. By combining density‐functional calculations with the well‐designed doping and codoping experimental strategies, the mechanisms behind this anomaly is successfully uncovered. It originates from the stabilization of Cr3 + by codopants such as Bi and rare‐earth (RE) ions, acting as electron donors. The luminescence is almost unobservable when chromium is doped alone, and thus the traditional identification method does't work. This work emphasizes the important role of trace impurity in materials, especially the subtle change of valence state of trace impurity upon doping, which provides enlightening insights and prompts reassessments of numerous reported anomalous luminescent phenomena.

Iron protoporphyrin IX-hyaluronan hydrogel-supported luminol chemiluminescence for the detection of nitric oxide in physiological solutions

Due to its role as a free radical signal-transducing agent with a short lifespan, precise measurement of nitric oxide (●NO) levels presents significant challenges. Various analytical techniques offer distinct advantages and disadvantages for ●NO detection. This research aims to simplify the detection process by developing a hydrogel system using iron(III)-protoporphyrin IX (hemin)-loaded hyaluronan for the detection of ●NO in solution. Various hydrogel formulations were created, and the effects of their components on hydrogel-supported luminol chemiluminescence (CL) kinetics, radical scavenging, and physicochemical properties were analysed through factorial analysis. The candidate formulations were then evaluated using two ●NO donors. An increase in the degree of crosslinking in unloaded formulations enhanced interactions with the CL reaction components, hydrogen peroxide (H2O2) and luminol, thereby affecting light generation. However, hemin loading negated these effects, resulting in more prominent luminescence kinetics in formulations with lower crosslinking degrees. Similarly, ●NO influenced the kinetics differently, interacting with both the CL reaction and hydrogel components. Hemin-loaded formulations exhibited enhanced signal propagation when exposed to ●NO, followed by H2O2 and luminol, whereas reversing the order of addition inhibited this propagation. The magnitude of these luminescence changes depended on the type and concentration of the ●NO donor, demonstrating greater sensitivity to ●NO levels compared to amperometric sensing. These findings suggest that the studied hydrogel platform has potential for the facile and accurate detection of ●NO in solution, requiring minimal sample sizes.

Ratiometric visualization fluorescence temperature sensing based on dual-lanthanide metal-organic frameworks

High-performance optical temperature sensors play an important role in various fields, and lanthanide metal-organic frameworks (Ln-MOFs) are expected to be luminescent temperature sensors due to their distinctive luminescent properties. Herein, a new three-dimensional (3D) Ln-MOF [Tb(TCA)(Phen)]·DEF (1) (H3TCA = 4,4′,4′'-nitrilotribenzoic acid, Phen = 1,10-phenanthroline, DEF= N, N-diethylformamide) is constructed with a rtl topology based on {Tb2(COO)4} secondary building units (SBUs). Meanwhile, dual-lanthanide Ln-MOFs [TbxEu1-x(TCA)(Phen)]·DEF (2-6) are also synthesized by varying the ratio of Tb3+: Eu3+ in the reaction mixture, which can be applied in practical LED applications originating from their visual luminescent color changes. Among them, 4 is an efficient ratiometric fluorescent thermometer over a wide temperature range from 283 to 393 K and has a large relative sensitivity Sr of 4.2407 % K−1 at 393 K with good repeatability. Furthermore, the emission color of 4 gradually changes from yellow (283 K) to orange-red (393 K) as temperature increases for visual colorimetric temperature measurements, which attributed to the energy transfer between Tb3+ and Eu3+ ions.

Micrometric patterning of a borogermanate glass containing terbium by thermal poling to manage luminescence and second order optical properties

Borogermanate glasses containing terbium ions are interesting materials due to their luminescent and magnetic properties. Terbium can present two different oxidation states and the thermal poling technique can be a pertinent way to modulate spatially the oxidation state of these ions. In this work, we demonstrate using a thermo-electrical imprinting process the transfer of micro scaled motifs on the surface of a borogermanate glass containing Tb3+ resulting in a micrometric structuring of the oxidation state of Tb3+/Tb4+ ions. A large change in absorption and luminescence optical properties is observed, arising from the distinct properties of trivalent and tetravalent terbium ions. Correlative micro luminescence, Raman and second harmonic generation measurements were carried out on the patterned poled glass surface. This has demonstrated an accurate concomitant modification of the glass structure accompanying large luminescence changes and the appearance of a second order optical response which could be attributed to a localized space charge implantation. These original results demonstrate how a simple electrical process allows managing multi optical properties but also paves the way to induce static electrical functionalities in a magnetic optical glassy system.

Utilizing a water-stable terbium (III) metal-organic framework for luminescent sensing of nitroimidazole antibiotics

A new 3D terbium (III)-based metal–organic framework, [Tb(TDC)(µ2-CH3COO)(H2O)] (Tb-MOF, H2TDC = 2,5-thiophenedicar-boxylic acid), was obtained with Tb3+ ions as metal source and TDC ligands as the auxiliary ligand through self-assemble mode. The Tb-MOF features a 3D network constructed by bridging a 2D wave-like network connected by TDC ligands with monodentate coordination mode, which results in the formation of a 3D net framework. The luminescent properties and sensing antibiotics experiments were extensively investigated for the Tb-MOF. Remarkably, the Tb-MOF exhibits a substantial quantum yield (QY) at 55.0 % and an average photoluminescence lifetime of 534 µs. Furthermore, the Tb-MOF shows selective luminescence quenching for nitroimidazole antibiotics, including metronidazole (MDZ), dimetridazole (DTZ), and ornidazole (ODZ), with a particularly strong response for MDZ (Ksv = 5.49 × 104 M−1, LOD value is 7.9 × 10−5 M). Finally, the Tb-MOF enables a simple and convenient test paper that allows luminescent color changes to be observed with the naked eye for detecting MDZ.

Guest-Responsive Near-Infrared-Luminescent Metal-Organic Cage Organized by Porphyrin Dyes and Yb(III) Complexes.

Metal-organic cages (MOCs) with luminophores have significant advantages for the facile detection of specific molecules based on turn-on or turn-off luminescence changes induced by host-guest complexation. One important challenge is the development of turn-on-type near-infrared (NIR)-luminescent MOCs. In this study, we synthesized a novel MOC consisting of two porphyrin dyes linked by four Yb(III) complexes, which exhibit bimodal red and NIR fluorescence signals upon photoexcitation of the porphyrin π system. Single-crystal X-ray structural analysis and computational molecular modeling revealed that planar aromatic perfluorocarbons were intercalated into the MOC. The tight packing between the MOC and guests enhanced the NIR fluorescence of Yb(III) by suppressing energy transfer from the photoexcited porphyrin to oxygen molecules. Guest-responsive turn-on NIR fluorescence changes in an MOC were successfully demonstrated.

A Ratiometric Green Fluorescent Carbazole-Bis(hydrazinobenzothiazole) Probe for the Selective Detection of Toxic Hg2+ Ions in Real Water Samples.

A dyad Carbazolyl-bis(hydrazinobenzothiazole) was designed to form a symmetrical structure that containing two-arm active binding sites facilitates coordination with Hg2+ ion. This sensor has imparted a colorimetric and fluorometric changes in presence of Hg2+ ions. The ligand showed a selective blue shift in presence of Hg2+even in co-existence with heavy metal ions with luminescence change from colorless to blue and colorless to green under day light. Enhanced Intramolecular charge transfer process is responsible for fluorescence transformation when ligand interacts with Hg2+ ion. The emission spectra showed a ratiometric response to increasing addition of Hg2+ ions. The sensor is capable of detecting above the lower concentration of 6.8025×10-8 M. The fluorescence efficiency of CBT-2 with Hg2+ ion is quite stable under different co-metal ions and wide range of pH 6 to 9. The sensor CBT-2 forms a 1 : 1 stoichiometric complex with Hg2+ ions and the binding nature is confirmed from the 1H-NMR, FTIR, and mass spectroscopic studies. The sensor CBT-2 and its Hg2+ complex possess good binding nature to protein in Bovine Serum Albumin which could be good in biological applications. Additionally, wedevelop a practical application in real water sample analysis and electrochemical detection via oxidation potential discrimination.

Hybrid MPA-CdSe quantum dots-based luminescent hydrogel: White light emission regulation and Cu2+ recognition

In this study, a novel CdSe@PEI-PVP luminescent hydrogel was constructed by using MPA-CdSe quantum dots (QDs) as a single emitter and hydrogen bond cross-linking network between highly branched polyethyleneimine (PEI) and polyvinylpyrrolidone (PVP) as a hydrogel skeleton, in which PEI also works as a passivation ligand for MPA-CdSe quantum dots. Utilizing the dual emission of MPA-CdSe quantum dots and adjusting the surface state of MPA-CdSe with PEI and Cd2+, CdSe@PEI-PVP hydrogel can emit bright white light as a whole. Furthermore, CdSe@PEI-PVP shows specific recognition for Cu2+, luminescent color changes from bright white to orange when Cu2+ is added, which enables CdSe@PEI-PVP hydrogel to serve as a fluorescent probe for ion detection. The luminescent hydrogel has great self-healing ability and reversible morphological thermal responsiveness, existing as a white luminescent hydrogel at room temperatures and transforming into a pale green luminescent solution at high temperatures.