Emission Color Change Research Articles

Structural Design of Hybrid Manganese(II) Halides for High Quantum Efficiency and Specific Response to Methanol.

Manganese(II) halides have been a new generation of optoelectronic materials due to their fascinating luminescent properties, however, lacking specific solvent-responsive analogues with high quantum efficiency. Herein, we prepared three single crystals, [Pr(MIm)2][MnBr4] ([Pr(MIm)2]2+ = 1,3-di(methylimidazolium)-propane, Compound 1), [Pr(EIm)2][MnBr4] ([Pr(EIm)2]2+ = 1,3-di(ethylimidazolium)-propane, Compound 2), and [Bu(MIm)2][MnBr4] ([Bu(MIm)2]2+ = 1,4-di(methylimidazolium)-butane, Compound 3), where different Bola-type cations were chosen as organic components to separate [MnBr4]2- tetrahedrons. All three compounds emitted bright green light with excellent quantum yields of 95.3, 80.0, and 96.2%, benefiting from the large Mn···Mn distance. More interestingly, Compound 3 showed a highly selective response to methanol in a series of tested organic solvents, with a rapid and reversible change in emission color from green to red. The single crystal of [Bu(MIm)2][MnBr4]·CH3OH with red emission proved that the luminescence switching was attributed to the adsorption of CH3OH molecules into the lattice space in the form of the O-H···Br hydrogen bonds. To our knowledge, for tetrahedrally coordinated Mn(II) species, the reversible emission color switching between green and red triggered by a solvent without the change of coordination number is achieved for the first time, providing promising applications for the specific detection of methanol.

Fluorescence Visualization Quantitative Detection of Tetracycline and Nitrofurantoin in Food and Natural Water by Zn2+@Eu-bpdc Composite.

Quantitative detection of tetracycline (TC) and nitrofurantoin (NFT) in food and water is of importance for food safety and environmental protection. Herein, Zn2+ was introduced into a europium metal-organic framework Eu-bpdc (H2bpdc = 2,2'-bipyridyl-5,5'-dicarboxylic acid) to prepare a composite of Zn2+@Eu-bpdc, which was developed as a fluorescence sensor for TC and NFT. The fluorescence mechanism concerns with bpdc2- ligand-to-Eu(III) charge transfer, and the detection mechanism is the inner filter effect. Zn2+@Eu-bpdc is a ratiometric fluorescence sensor for TC with the linear fitting equation of I520/I618 = 1.94 × 104 M-1CTC, whose limit of detection (LOD) is 0.148 μmol·L-1 (μM); it is also a fluorescence "turn-off" sensor for NFT with the fitting equation of (I0-I)/I = 3.62 × 104 M-1CNFT and LOD = 0.0792 μM. Zn2+@Eu-bpdc can detect TC or NFT in lake water, honey, and milk with high accuracy. The emission color changes of paper-based Zn2+@Eu-bpdc depending on CTC or CNFT reveal the visualization detections of TC and NFT. With the red and green values as input signals, smartphone-assisted on-site detection is utilized to recognize the antibiotic residuals of TC and NFT by a self-programmed APP. Zn2+@Eu-bpdc is promising in a smartphone-assisted intelligent platform for on-site detection of TC and NFT.

Photoluminescence Quenching in Metal Doped Graphitic Carbon Nitride: Possibilities Toward Metal Sensors

AbstractThe present work describes the synthesis of graphitic carbon nitride (GCN) via simple two‐step thermal decomposition of urea at a moderate temperature of 550 °C. The as‐synthesized GCN is further doped with transition metals like nickel, and both the pure and doped GCN are characterized by X‐ray diffraction (XRD), field emission scanning electron microscope (FESEM), X‐ray photoelectron spectroscopy (XPS), and Fourier transformed infrared (FTIR) spectroscopy. XRD shows the perfect phase formation in the pure GCN, which also remains in the doped sample but with much lesser crystallinity. FESEM shows that after doping, the small chips‐like structure of GCN gets transformed to an elongated one. XPS confirms the successful doping by keeping the signature of both nickel 2P1/2 and 2P3/2 oxidation states in the spectra, whereas FTIR gave an idea about different bonding present in the sample. The pure sample, when irradiated with an excitation wavelength of 350 nm, gives an intense peak at 457 nm, which gets considerably quenched in the case of the doped sample. However, a new peak appears in the photoluminescence (PL) spectra of the doped sample at 624 nm. The quenching of PL intensity in the doped sample is assumed to be due to the fact that the dopant‐induced state traps the electron, hindering them from immediate recombination. This quenching of PL intensity generates the possibilities of sensing the presence of different metals and thus taking measurable steps for removing them. The CIE chromaticity diagrams for the doped and undoped samples confirm that the emission color changes from blue to cyan region after the doping.

Achieving Controllable Thermochromic Fluorescence via Synergistic Intramolecular Charge Transfer and Molecular Packing

Thermochromic fluorescent materials (TFMs) have attracted significant attention due to their unique fluorescent colorimetric response to temperature. However, existing TFMs still suffer from weak stimulus responsiveness, broad temperature response ranges, uncontrollable emission color changes, and low quantum yields. In this study, we address these issues by designing and synthesizing three diketone‐boron complexes with distinct emission wavelengths (NWPU‐(2‐4)). Utilizing a molecular engineering strategy to manipulate intramolecular charge transfer transitions and molecular packing modes, our synthesized complexes exhibit efficient fluorescence emission in both solution and solid states. Moreover, their emission wavelengths are highly sensitive to environmental polarity. By incorporating these compounds into thermosensitive matrices of long‐chain alkanes, we produced TFMs with varied fluorescence emission peak variation ranges. Notably, the TFM based on NWPU‐4, owing to its strong charge transfer transitions and dense J‐aggregate packing configuration, not only exhibits intense fluorescence emission spanning the deep red to near‐infrared spectrum but also displays a remarkable 90 nm broad range of thermochromic properties. Ultimately, it was successfully applied to programmable, thermally controlled, multi‐level information encryption.

Achieving Controllable Thermochromic Fluorescence via Synergistic Intramolecular Charge Transfer and Molecular Packing.

Thermochromic fluorescent materials (TFMs) have attracted significant attention due to their unique fluorescent colorimetric response to temperature. However, existing TFMs still suffer from weak stimulus responsiveness, broad temperature response ranges, uncontrollable emission color changes, and low quantum yields. In this study, we address these issues by designing and synthesizing three diketone-boron complexes with distinct emission wavelengths (NWPU-(2-4)). Utilizing a molecular engineering strategy to manipulate intramolecular charge transfer transitions and molecular packing modes, our synthesized complexes exhibit efficient fluorescence emission in both solution and solid states. Moreover, their emission wavelengths are highly sensitive to environmental polarity. By incorporating these compounds into thermosensitive matrices of long-chain alkanes, we produced TFMs with varied fluorescence emission peak variation ranges. Notably, the TFM based on NWPU-4, owing to its strong charge transfer transitions and dense J-aggregate packing configuration, not only exhibits intense fluorescence emission spanning the deep red to near-infrared spectrum but also displays a remarkable 90 nm broad range of thermochromic properties. Ultimately, it was successfully applied to programmable, thermally controlled, multi-level information encryption.

Reversible Emission Color, Brightness, and Shape Changes of AIEgen‐containing Bulk Polymers

AbstractBulk polymers generally exhibit faster response, higher shape‐deformation speed, and stronger mechanical properties than the hydrogels. However, it still remains a formidable challenge to enable bulk polymers to exhibit reversible changes in shape and fluorescence simultaneously. Herein, for the first time, the temperature‐responsive reversible changes in fluorescence color, brightness, and shape of semi‐crystalline poly(ε‐caprolactone) (PCL) network doped with a D‐A based aggregation‐induced emission luminogen (AIEgen) is realized. The fabricated flower‐like and dragonfly‐shaped actuators show reversible blooming‐closing and wing fanning behaviors, respectively, as well as reversible fluorescence‐changing effects. Notably, the response and shape‐deformation speed as well as mechanical properties of the system is much better than the reported hydrogels. Moreover, a smart switch is developed to demonstrate the potential applications. The stick fabricated by the sample can lift and release an object 1000 times larger than its weight, serving as a color‐changing artificial muscle. This material design strategy may shine light on the design and preparation of other reversible shape‐deformation polymers in combination with stimuli‐responsive luminescence‐changing AIEgens, such as mechanochromic, thermochromic, and photochromic luminogens.

Multicolor Electrochemiluminescence of Binary Microcrystals of Iridium and Ruthenium Complexes.

We here report the multicolor electrochemiluminescence (ECL) of binary microcrystals prepared from a blue-emissive iridium complex 1 and an orange-emissive ruthenium complex 2. These materials display a plate-like morphology with high crystallinity, as demonstrated by microscopic and powder X-ray diffraction analyses. Under light excitation, these microcrystals exhibit gradient emission color changes as a result of the efficient energy transfer between two complexes. When modified on glass carbon electrodes, these microcrystals exhibit tunable ECLs with varied emission colors including sky-blue, white, orange, and red, depending the doping ratio of complex 2 and the applied potential. Furthermore, organic amines with different molecular sizes are used as the co-reactant to examine their influences on the ECL efficiency of the porous microcrystals of 1. The analysis on the luminance and RGB values of ECL suggests the existence of energy transfer in the generation of multicolor ECLs in these binary crystals.

A novel Y/Eu co-doped Ln-MOF for ratiometric luminescent thermometer of high sensitivity

Lanthanide metal-organic frameworks (Ln-MOFs) co-doped by mixed lanthanide ions is a preeminent candidate for ratiometric luminescence thermometers. In recent years, there are few studies on the synthesis of such MOFs by introducing Ln3+ ions of no luminescent properties such as Y3+. Herein, a novel Y/Eu co-doped Ln-MOF (Y0.95Eu0.05NDPA, H4NDPA = 5,5′-naphthalene-1,4-diyl-diisophthalic acid) was synthesized via solvothermal methods, which showed good phase purity and thermal stability. Compared with EuNDPA, the Y3+ ions in Y0.95Eu0.05NDPA dilute the molar concentration of Eu3+, causing the emerge of ligand emission band. The luminescence intensity ratio of organic ligands and Eu3+ owns a good exponential dependence on temperature variation. As investigated, Y0.95Eu0.05NDPA owns the merits including a wide temperature sensing range (303–423 K), high relative sensitivity (3.04 %·K-1 at 423 K), good spectral repeatability (>92 %) and distinct emission color change from red to blue. This novel Y0.95Eu0.05NDPA ratiometric thermometer is expected to promote the application and development of dual-emission MOF materials in the field of microelectronic temperature measurement.

Excited-State Dynamics of a Bright Fluorescent Dye with Precise Control of Emission Color Using Acid-Base Equilibrium, Intramolecular Charge Transfer, and Host-Guest Chemistry.

A fluorescent dye, a dithiophene-conjugated benzothiazole derivative (DTBz), was prepared to have high fluorescence emission quantum yields (ΦF) across various organic solvents. Its emission color modulation, from bright blue to deep red, was achieved through intramolecular charge transfer (ICT), acid-base equilibrium, and host-guest chemistry. Although it exhibits a weak solvatochromic effect, DTBz exhibited a bright fluorescence emission around 480 nm upon excitation at 390 nm in most solvents. In polar solvents, such as MeOH (methanol), EtOH (ethanol), DMF (N,N-dimethylforamide), and DMSO (dimethyl sulfoxide), an additional ICT emission band emerged around 640 nm, notably intense in DMSO, resulting in a bright greenish-white emission (ΦF = 0.67). The addition of 1,8-diazabicyclo[5,4.0]undec-7-ene (DBU) altered emission characteristics, reducing emission from the local excited (LE) state and enhancing ICT state emission. The degree of emission spectral change saturation with DBU addition varied with the solvent nature. Polar solvents with high dielectric constants, like DMSO and DMF, saw a complete disappearance of LE state emission with 5 equiv of DBU, resulting in a deep red emission (ΦFs of 0.53 and 0.48, respectively). Femtosecond transient absorption spectroscopy and time-resolved photoluminescence measurements elucidated the excited-state dynamics, revealing a long-lived excited state (τ-H = 10.3 ns) at a lower energy emission (640 nm), identified as DTBz-*, supported by transient absorption spectra analysis. Further analysis, including time-resolved fluorescence decay measurements and time-dependent density-functional theory (TD-DFT) calculations, underscored the role of deprotonation of DTBz's hydroxyl group in promoting the ICT process. The CIE coordination plot demonstrated wide linear emission color changes upon successive DBU additions in all solvents, while emission color precision was achieved through host-guest chemistry. Emission changes induced by DBU were reverted to the original state upon beta-cyclodextrin (β-CD) addition, with the 1H NMR study revealing the competition between acid-base equilibrium and host-guest complex formation as the cause of emission color change.

Mechanochromic luminescent material with high quantum yield for multi-mode anti-counterfeiting applications

The multi-mode anti-counterfeiting materials, constructed by mechanochromic luminescent materials with high quantum yield, can effectively prevent illegal counterfeiting, but their design and construction still present significant challenges. Herein, a twisting D-A-D conjugated molecule, FBtF, is obtained with a special hybridized local and charge transfer excited state, and shows approximately 100 % photoluminescence quantum yield in the coating film. The self-assembled FBtF microplates exhibit bathochromic-shifted emission from green to orange, accompanied by the photoluminescence quantum yield increase from 47.8 % to 89.0 % upon grinding, which is the highest in reported MCL materials, to the best of our knowledge. In contrast, a D-π-D type molecule (FBenF) and a D-D’-D molecule (FAnF) maintain the blue-emission after grinding. Through mechanistic investigation, the force-induced molecular conformational planarization and the breakage of the intermolecular charge transfer collaboratively lead to the emission-color change and photoluminescence quantum yield increase. The FBtF microplates are designed as ink for anti-counterfeiting applications based on multi-mode output signals, including the UV light-excited image and the grinding-induced emission color change together with the photoluminescence quantum yield increase. The written tags exhibit high stability in various harsh environments, and demonstrate superior anti-counterfeiting performance in practical applications, such as medicine anti-counterfeiting.

A fluorescence-enhanced method specific for furfural determination in Chinese Baijiu based on luminescent carbon dots and direct surface reaction

Detecting the furfural concentration in Baijiu can be used to assess the quality of Baijiu, allowing for the optimization of processing techniques and the enhancement of overall quality. In this paper, a fluorescence-enhanced method based on carbon dots (o-CDs) is developed for the furfural determination in Chinese Baijiu. In an environment full-filled with ·SO4‐ and ·OH, furfural undergone a direct surface reaction with the ortho-diamino groups at o-CDs. The created furan-based imidazole increased the surface electron density, leading an emission enhancement and color changes from orange to green. Thereby, a linear fluorescence response of o-CDs-TA to furfural is established in water with a detection limit of 30.5 nM. Finally, after ethanol correction it is used to determine furfural in Chinese Baijiu with high precision and reproducibility, providing a new strategy with low-cost and high sensitivity. In particular, the idea of covalently connecting target molecule to the CDs surface via the assistance of free radical opens a new avenue to merge the nanoscale and molecular realms through implementing chemical role into carbon nanostructures.

A Ratiometric Fast-Response Fluorescent Probe Based on Dicyanoisophorone for Monitoring HClO in Paper Test Strips and Living Mice.

A new dicyanoisophorone-based ratiometric fluorescent probe NOSA was synthesized and characterized. It showed a fast fluorescence response to HClO with the emission color change from dark green to bright red. NMR, IR, and HRMS suggested that the detection of NOSA to HClO may originate from the hydroxyl deprotection reaction by HClO on the molecule NOSA, which caused a red-shift of fluorescence. The probe NOSA displayed high selectivity and excellent anti-interference performance with a limit of detection at 3.835 × 10-7M. The convenient paper test strips were successfully obtained and applied to the detection of HClO based on fluorescence color change with the varied NaClO concentration. Moreover, spiked recovery experiments in real water samples indicated that the probe NSOA could quantitatively detect HClO, and the fluorescence bio-imagings in vivo were carried out, and HClO detection in biosystems using NOSA was realized.

Binary and heterostructured microplates of iridium and ruthenium complexes: Preparation, characterization, and thermo-responsive emission

Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing, information encryption, and microelectronics. We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties. Depending on the assembly conditions, lateral or longitudinal triblock heterostructures with a microplate shape are obtained, which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer. In addition, branched heterostructures are prepared by a stepwise assembly. The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined. This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.

Bioinspired Hg2+-sensing fluorogenic probe based on amino acid–functionalized rhodamine

Inspired by the suitability of rhodamine spirolactam switching for superresolution imaging and fluorescent probe development, we herein synthesized rhodamine-based probes with sulfur-bearing amine and amino acid moieties and screened their abilities to respond to Hg2+ in the presence of other metal ions. The probe based on S-methylcysteine methyl ester–substituted rhodamine 6G (Rho6G-6) was identified as optimal because of its straightforward synthesis and rapid, selective, and sensitive (detection limit = 8 × 10–9 M) response to Hg2+ manifested by absorption spectrum and emission color changes. The complexation of Hg2+ by Rho6G-6 was examined by absorbance and fluorescence analyses, electrospray ionization–mass spectrometry, and 1H nuclear magnetic resonance (NMR) titration experiments. Furthermore, the practical applicability of the above probe was demonstrated by naked-eye colorimetric Hg2+ detection using paper test strips and the fluorescence-based qualitative mapping of the Hg2+ distribution in living HeLa cells and the organs of live mice. Thus, unlike other probe design strategies, the use of flexible S-methyl amino acids for Hg2+ binding provides new opportunities and strategies for photopromoting the ring switching of the rhodamine spirothiolactam.

Emission Color Tuning of Inverse Type Diarylethene Crystals

AbstractOrganic luminescent solid materials have attracted much attention due to practical applications such as sensor materials and optical waveguides. We have previously reported that inverse type diarylethenes exhibit strong emission in crystal without causing aggregation‐caused quenching. However, the emission color was limited to mainly green. To tune the emission color, in this work, we newly synthesized inverse type diarylethenes having a shortened π‐conjugation length or a polar substituent and investigated their fluorescence properties in solutions and crystals. The crystals exhibited various emission colors from blue, green, yellow to red depending on the molecular structure. The emission color changes of the crystals were induced by the intermolecular interactions such as CH‐π interactions in addition to the shortened π‐conjugation length and the intramolecular charge transfer character.

Synthesis, optical properties, and dual‐color halochromic fluorescence of novel π‐conjugated polymers bearing coumarin unit in the main chain

AbstractA series of novel π‐conjugated polymers bearing alternating coumarin and phenylene units in the main chain backbone was synthesized via Sonogashira coupling reaction. The red‐shifts in the absorption maxima of the polymers indicate the expansion of π‐conjugated system in the polymer main chains. These polymers exhibited strong green fluorescence in organic solvents. Clearly perceptible dual‐color halochromic fluorescence was confirmed for the polymers by the significantly reversible changes of emission color from green to blue during alkalization and acidification processes. The lactone ring opening and closing property in the coumarin molecule functioned as a controllable switch, broadening the applications of the coumarin‐based π‐conjugated polymers as acid–base responsive fluorescence materials.

Responsive organic room-temperature phosphorescence materials for spatial-time-resolved anti-counterfeiting

Stimulus-responsive room-temperature phosphorescence (RTP) materials have gained significant attention for their important optoelectronic application prospects. However, the fabrication strategy and underlying mechanism of stimulus-responsive RTP materials remain less explored. Herein, we present a reliable strategy for achieving pH-responsive RTP materials by integrating poly(vinyl alcohol) (PVA) with carboxylic acid or amino group functionalized terpyridine (Tpy) derivatives. The resulting Tpy derivatives-based RTP materials displayed reversible changes in emission color, intensity, and lifetime of both prompt and delayed emission. Notably, the RTP emission undergoes a significant diminish upon exposure to acid due to the protonation of Tpy units. Taking advantage of the decent RTP emission and pH-responsiveness of these RTP films, a spatial-time-resolved anti-counterfeiting application is demonstrated as a proof-of-concept for largely enhancing the security level. This study not only provides new prospects for developing smart RTP materials but also promotes the advancement of optical anti-counterfeiting applications.

Electricity/light-heat-hygro multi-responsive soft luminescent systems for rewritable and programmable information display

Rewritable luminescent materials are attracting widespread attention for information storage and display as they can help to reduce environmental wastes caused by the abuse of single-use and transient systems. Nevertheless, since most reported systems are chemical-stimuli-responsive and single-stimuli-responsive, it remains challenging to achieve the rewritable and programmable display of multiple information in one single system, which is essential to enhance information richness and display intelligence. In this work, an ideal kind of multi-responsive soft luminescent display systems are reported, which consist of heat/humidity-responsive fluorescence-phosphorescence dual-emission film and stacked graphene assembly (SGA) film by using thin poly (dimethyl siloxane) (PDMS) as middle connecting layer. In such multilayer structure, the heat generated by electricity connection or light illumination of bottom SGA film can be instantly transferred across the middle PDMS layer to cause heat-triggered red-to-blue emission color change, or to evaporate water for blue-to-red emission color recovery. Owing to the “residual-free” nature of these electricity, light and water stimuli, multi-responsive rewritability is guaranteed to enable the reversible writing and complete erasure of various letter/pattern information. On this basis, robust electricity/light-heat-hygro multi-responsive soft luminescent display systems are demonstrated, in which diverse letter/pattern information could be facilely programmed to be successively displayed and then completely reset to enable another data writing/erasing cycle by sequential modulation of different environmental stimuli. This study brings programmable merit for rewritable luminescent display systems and is expected to inspire more intelligent ones.

Eu3+-doped manganese tungstate for multiparametric and colorimetric luminescence thermometry

Improvement of luminescent thermometers requires not only the search for high-sensitivity thermometric outputs, but also availability of multiple thermometric parameters affording a combined and reliable response. We hereby detail for the first time the luminescence of Eu3+ in manganese tungstate (Eu3+:MnWO4) solids obtained by coprecipitation under ultraviolet excitation and how this material provided an optical thermometric response from 77 K to 373 K via excitation and emission spectra. Processing of up to five thermometric parameters, namely bandwidths, band positions, band shifts and luminescence intensity ratios, resulted in relative thermal sensitivities as high as 1.56% K−1 and temperature uncertainties between 0.01 and 2 K depending on the choice of the spectral parameter. In addition, we demonstrate that Eu3+:MnWO4 also act as a qualitative colorimetric thermosensor because of progressive change of emission color to greenish-yellow to bluish-green upon heating under UV excitation. Therefore, our results show that the combination of broadband tungstate emissions with the 4f-4f narrow emissions of Eu3+ is an effective approach to achieve a multiparametric luminescent thermal response via emission, excitation and visual observation, which makes Eu3+:MnWO4 a promising candidate for advanced thermometry applications.

Synthesis and performance of a nanosensing platform for homocysteine detection: A series of iridium(III) complexes containing aldehyde group as probe and MOF as supporting substrate

The low cost and simple detection method for Hcy (homocysteine) is highly desired in analytical and biological fields since Hcy has been regarded as a bio-marker for multiple diseases. In this work, five Ir(C^N)2(N^N)+ compounds having –CHO group in their C^N or N^N ligand were synthesized and tried for Hcy sensing. Electron-donating groups such as –NH2 and –CH3 were incorporated into the C^N or N^N ligand. Their geometric structure, electronic structure, and optical parameters (with or without Hcy) were analyzed and compared carefully to explore their Hcy sensing potential. The sensing mechanism was revealed by NMR titration and theoretical simulation as a cyclization reaction between the –CHO group and Hcy. The optimal compounds, which showed increased emission quantum yield (2.5-fold) and emission blue-shift (by ∼ 100 nm) upon Hcy, were then covalently grafted into a porous host bio-MOF-1. Linear working plots were fitted, with good selectivity, LOD of 0.15 μM, and response time of 33 s. The novelty of this work was the eye-sensitive emission color change of this nanosensing platform from red (without Hcy) to green (with Hcy).