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Because ascorbic acid (AA) is one of the basic elements to maintain the normal physiological functions of human body, it is urgent to develop a material that can achieve efficient, rapid and in-situ detection for AA. A new fluorescence organic compound 4',4'''-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis([1,1'-biphenyl]-4-carboxylic acid) (H2BTBC) based on benzothiadiazole group has been synthesized, which can detect Fe3+ ions by fluorescence turn-off effect with a detection limit of 0.015 µM, as well as recognize linear amines by fluorescence turn-on effect. Moreover, a highly stable Tb(III) metal-organic framework has been solvothermally prepared with H2BTBC, namely {[(CH3)2NH2]2[Tb2(BTBC)4]âsolvents}n (JXUST-39), which can selectively detect AA among biological fluids by fluorescence enhancement effect with a detection limit of 0.077 µM. In addition, the mechanism for JXUST-39 detecting AA is possibly the cooperative effect of absorbance-caused enhancement and charge transfer between JXUST-39 and AA. Moreover, LED lamp beads, fluorescent films and fluorescent detection test paper based on JXUST-39 were prepared to achieve portable detection via fluorescence enhancement effect.
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Exploring low-cost visible light photocatalysts for CO2 reduction to produce proportionally adjustable syngas is of great significance for meeting the needs of green chemical industry. A S-Scheme CeO2/g-C3N4 (CeO2/CN) heterojunction was constructed by using a simple two-step calcination method. During the photocatalytic CO2 reduction process, the CeO2/CN heterojunction can present a superior photocatalytic performance, and the obtained CO/H2 ratios in syngas can be regulated from 1 : 0.16 to 1 : 3.02. In addition, the CO and H2 production rate of the optimal CeO2/CN composite can reach 1169.56 and 429.12â µmol g-1 h-1, respectively. This superior photocatalytic performance is attributed to the unique S-Scheme photogenerated charge transfer mechanism between CeO2 and CN, which facilitates rapid charge separation and migration, while retaining the excellent redox capacity of both semiconductors. Particularly, the variable valence Ce3+/Ce4+ can act as electron mediator between CeO2 and CN, which can promote electron transfer and improve the catalytic performance. This work is expected to provide a new useful reference for the rational construction of high efficiency S-Scheme heterojunction photocatalyst, and improve the efficiency of photocatalytic reduction of CO2, promoting the photocatalytic reduction of CO2 into useful fuels.
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The design and synthesis of a Gd(III) metal-organic framework with the formula [Gd4(BTDI)3(DMF)4]n (JXUST-40, H4BTDI = 5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)diisophthalic acid) are reported hererin. Interestingly, a reversible single-crystal-to-single-crystal transition between JXUST-40 and {[Gd4(BTDI)3(H2O)4]·6H2O}n (JXUST-40a) was achieved under the stimulation of heat and solvents. Both JXUST-40 and JXUST-40a exhibited good stability when soaked in common solvents and aqueous solutions with pH values of 1-12. Magnetic studies showed that JXUST-40a has a larger magnetocaloric effect with -ΔSmaxm = 26.65 J kg-1 K-1 at 2 K and 7 T than JXUST-40 due to its larger magnetic density. Structural analyses indicated that the coordinated solvent molecules play a crucial role in the coordination environment around the Gd(III) ions and the change in the framework, ultimately leading to the changes in the pore size and magnetism between JXUST-40 and JXUST-40a. In addition, both isomorphic [Dy4(BTDI)3(DMF)4]n (JXUST-41) and {[Dy4(BTDI)3(H2O)4]·6H2O}n (JXUST-41a) displayed slow magnetic relaxation behaviour.
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Due to their hazard to biological systems, it is urgent to develop materials that can rapidly and sensitively detect the concentration of H2PO4- and OCN- ions. In this work, a new CdII-based luminescent metal-organic framework with the formula [Cd(BTDB)(2,6-BBIP)]n (JXUST-47, H2BTDB = (benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid, 2,6-BBIP = 2,6-bis(benzimidazol-1-yl)pyridine) and sql topology was successfully synthesized using a mixed-ligand strategy. JXUST-47 shows good chemical and thermal stability. It also exhibits weak quenching and fluorescence blue shift for H2PO4- and red shift for OCN-, with the detection limits of 0.106 and 0.128 mM, respectively. In addition, considering the demand for H2PO4- and OCN- ion detection, by combining this with the functions of a smartphone, the chroma of photographs have been used to realize the consecutive visual detection of the concentration of these ions.
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Metal-organic frameworks (MOFs) are a novel class of hybrid porous multi-functional materials consisting of metal ions/clusters and organic ligands. MOFs have exclusive benefits due to their tunable structure and diverse properties. Luminescent MOFs (LMOFs) exhibit both porosity and light emission. They display abundant host and guest responses, making them conducive to sensing. Currently, LMOF sensing research is gaining more depth, with attention given to their device and practical applications. This work reviews recent advancements and device applications of LMOFs as chemical sensors toward ions, volatile organic compounds, biomolecules, and environmental toxins. Furthermore, the detection mechanism and the correlation between material properties and structure are elaborated. This analysis serves as a valuable reference for the preparation and efficient application of targeted LMOFs.
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At present, many researchers are focusing on trivalent lanthanide (Ln3+)-doped thermally enhanced upconversion luminescent (UCL) materials with negative thermal expansion (NTE) properties. However, selective anti-thermal quenching downshifting emissions of the activator and thermal quenching of the sensitizer in a phosphor with NTE properties are not implemented. Herein, Tb3+/Eu3+ co-doped Sc2(WO4)3 phosphors synthesized by the solid-state method are explored in selectively enhanced red emission (Eu3+:5D0 â 7F2) due to the energy-transfer efficiency from Tb3+ to Eu3+ and the promoted radiative transition probability. The selective thermally quenched green emission (Tb3+:5D4 â 7F5) is owing to the change of energy transfer from Tb3+ to Eu3+ as the temperature increased. Moreover, under ultraviolet 365 nm excitation, the thermally stimulated color emission tuned from yellow to red with the increase in temperature. Based on the radically different thermal response downshifting the luminescence of the activator and sensitizer, the luminescence intensity ratio (LIR) of non-thermally coupled levels (NTCLs) for 5D0 (Eu3+) and 5D4 (Tb3+) is adopted for optical temperature sensing. The optimal relative sensitivity of temperature sensing in the Sc2(WO4)3:25%Tb3+/3%Eu3+ sample could reach 2.94% K-1 at 347 K. All these indicate that this Sc2(WO4)3:Tb3+/Eu3+ material is a promising candidate for high-sensitivity optical temperature sensing.
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Revealing the stimuli-responsive mechanism is the key to the accurate design of stimuli-responsive luminescent materials. We report herein the multistimuli-responsive multicolor solid-state luminescence of a new dicopper(I) complex [{Cu(bpmtzH)}2(µ-dppa)2](ClO4)2 (1), and the multistimuli-responsive mechanism is clarified by investigating its four different solvated compounds 1·2CH3COCH3·2H2O, 1·2DMSO·2H2O, 1·4CH3OH, and 1·4CH2Cl2. It is shown that luminescence mechanochromism is associated with the breakage of the hydrogen bonds of bmptzH-NH with counter-ions such as ClO4- induced by grinding, while luminescence vapochromism is attributable to the breaking and forming of hydrogen bonds of dppa-NH with solvents, such as acetone, dimethylsulfoxide, and methanol, caused by heating and vapor fuming. In addition, those results might provide new insights into the design and synthesis of multistimuli-responsive multicolor luminescent materials by using various structure-sensitive functional groups, such as distinct N-H ones, to construct switchable hydrogen bonds.
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Lanthanide-based metal-organic frameworks show good potential for applications due to their unique structures and functional properties. A highly thermally and acid-base stable Eu-MOF was synthesized by a solvothermal method with the molecular formula {[(CH3)2NH2]2[Eu2(NDDP)2(H2O)2]·H2O}n (Eu-MOF, H4NDDP = 5,5'-(naphthalene-2,6-diyl)diisophthalic acid). Eu-MOF takes a three-dimensional (4,4,8)-connected topology. The water molecules involved in the coordination, free water molecules, and [(CH3)2NH2]+ cations in the pore can be used as proton carriers. The proton conductivity attains 1.25 × 10-4 S cm-1 at room temperature and 2.42 × 10-3 S cm-1 at 70 °C and 98% relative humidity. Combined with the dual-emission properties from the ligands and Eu(III) ions enables Eu-MOF to be used as a ratiometric fluorescent sensor for phosphate efficiently and rapidly, with a limit of detection of 0.12 µM in the Tris-HCl buffer solution. These results provide a new approach for the construction of MOFs with high proton conductivity and a ratiometric fluorescence response.
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Multifunctional materials with a coexistence of proton conduction properties, single-molecule magnet (SMM) behaviors and magneto-optical Faraday effects have rarely been reported. Herein, a new pair of Cu(II)-Dy(III) enantiomers, [DyCu2(RR/SS-H2L)2(H2O)4(NO3)2]·(NO3)·(H2O) (R-1 and S-1) (H4L = [RR/SS] -N,N'-bis [3-hydroxysalicylidene] -1,2-cyclohexanediamine), has been designed and prepared using homochiral Schiff-base ligands. R-1 and S-1 contain linear Cu(II)-Dy(III)-Cu(II) trinuclear units and possess 1D stacking channels within their supramolecular networks. R-1 and S-1 display chiral optical activity and strong magneto-optical Faraday effects. Moreover, R-1 shows a zero-field SMM behavior. In addition, R-1 demonstrates humidity- and temperature-dependent proton conductivity with optimal values of 1.34 × 10-4 S·cm-1 under 50 °C and 98% relative humidity (RH), which is related to a 1D extended H-bonded chain constructed by water molecules, nitrate and phenol groups of the RR-H2L ligand.
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Four new isostructural rare earth metal-organic frameworks (RE-MOFs) were synthesized and full characterized, namely, {[(CH)2NH2]3[RE2(BTDBA)2(HCOO)]·5H2O·2DMF}n (H4BTDBA = (4',4'''-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid); RE = Eu (JXUST-34), Gd (JXUST-35), Tb (JXUST-36), and Dy (JXUST-37)). The single-crystal structures analysis shows that JXUST-34-37 are chain-based three-dimensional structures. Importantly, JXUST-34 exhibits excellent water, organic solvents, and acid-base stability, which can be used as a fluorescence sensor for folic acid and Al3+ with detection limits of 0.02 mM and 0.05 µM, respectively. The presence of free [(CH)2NH2]+ cations in the channels can engage the proton carrier during proton conduction. JXUST-34-37 display good proton conductivity, and the conductivities vary with relative humidity and temperatures, among which JXUST-37 has the highest conductivity of 9.66 × 10-3 S·cm-1 at 60 °C and 98% RH. The magnetic studies show that the -ΔSm of JXUST-35 reaches 16.13 J kg-1 K-1 at 2 K and ΔH = 7 T. JXUST-34-37 show multifunctional properties of fluorescence sensing, high proton conductivity, and magnetic refrigeration, which provides a new clue for the development of fluorescent-responsive, magnetic-refrigerant, and proton-conductive RE-MOF materials.
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The unraveling of the stimuli-responsive mechanism is crucial to the design and precise synthesis of stimuli-responsive luminescent materials. We report herein the mechanochromic and selective vapochromic solid-state luminescence properties of a new bimetallic cuprous complex [{Cu(bpmtzH)}2(µ-dppm)2](ClO4)2 (1), and the corresponding response mechanisms are elucidated by investigating its two different solvated polymorphs 1·2CH2Cl2 (1-g) and 1·2CHCl3 (1-c). Green-emissive 1-g and cyan-emissive 1-c can be interconverted upon alternate exposure to CHCl3 and CH2Cl2 vapors, which is principally attributable to a combined alteration of both intermolecular NHbpmtzH···OClO3- hydrogen bonds and intramolecular "triazolyl/phenyl" π···π interactions induced by different solvents. Solid-state luminescence mechanochromism present in 1-g and 1-c is mainly ascribed to the grinding-induced breakage of the NHbpmtzH···OClO3- hydrogen bonds. It is suggested that intramolecular π···π-triazolyl/phenyl interactions are affected by different solvents but not by grinding. The results provide new insights into the design and precise synthesis of multi-stimuli-responsive luminescent materials by the comprehensive use of intermolecular hydrogen bonds and intramolecular π···π interactions.
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The development of a rapid and selective method for the identification of dipicolinic acid (DPA), a specific biomarker in Bacillus anthracis spores, is of great importance for the avoidance of anthrax infection. Herein, a chain-based EuIII metal-organic framework with the formula {[Eu3(BTDB)3(µ3-OH)3(H2O)]·solvents}n (JXUST-38, H2BTDB = (benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid) was obtained using 2-fluorobenzoic acid as the pH regulator. JXUST-38 exhibits good chemical and thermal stability and can specifically recognize DPA in N,N-dimethylformamide solution through luminescence enhancement and blue-shift effects with a detection limit of 0.05 µM. Furthermore, the significant luminescence enhancement and blue shift under UV lamps are obviously observable by the naked eye. The luminescence sensing mechanism is attributed to absorbance-induced enhancement between JXUST-38 and DPA. Test paper and mixed-matrix membrane based on JXUST-38 are designed for DPA detection. In addition, the feasibility of using JXUST-38 in biosensing is discussed in detail.
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A europium(III) metal-organic framework (MOF), namely, {[[(CH3)2NH2]3Eu2(DTTP-2OH)2(HCOO)(H2O)]·4H2O}n (Eu-MOF, H4DTTP-2OH = 2',5'-dihydroxy-[1,1':4',1â³-terphenyl]-3,3â³,5,5â³-tetracarboxylic acid) has been assembled through solvothermal method. The Eu-MOF is a three-dimensional (3D) (4,4,8)-connected topological framework with binuclear Eu(III) clusters as secondary building units, in which a richly ordered hydrogen bonding network formed among the free H2O molecules, dimethylamine cations, and phenolic hydroxyl groups provides a potential pathway for proton conduction. The proton conductivity reaches the category of superionic conductors (σ > 10-4 S cm-1) at room temperature with a maximum conductivity of 1.91 × 10-3 S cm-1 at 60 °C and 98% RH. Moreover, it also can be used as a fluorescence sensor in aqueous solution with detection limits of 0.14 µM for tetracycline, 0.13 µM for oxytetracycline and 0.11 µM for doxycycline. These results pave new methods for constructing MOFs with high proton conductivity and responsive fluorescence.
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In this work, we prepared a new orange-red phosphor Li2La1-xTiTaO7:xSm3+ (abbreviated as LLTT:Sm3+) for white light-emitting diodes (w-LEDs). Its crystal structure, microstructure, photoluminescence characteristics, luminescence lifetime and thermal quenching properties were studied in depth. The LLTT:Sm3+ phosphor shows four intense emission peaks at 563, 597, 643, and 706 nm when excited at 407 nm. Thermal quenching is caused by the dipole-quadrupole (d-q) interaction of Sm3+ ions, and the optimum doping concentration of Sm3+ is x = 0.05. Meanwhile, the LLTT:0.05Sm3+ phosphor has a high overall quantum yield (QY = 59.65%) and almost no thermal quenching. The emission intensity at 423 K is 101.5% of the initial value at 298 K, while the CIE chromaticity coordinates barely change as the temperature rises. The fabricated white LED device exhibits excellent CRI and CCT values of 90.4 and 5043 K, respectively. These findings demonstrate that the LLTT:Sm3+ phosphor has promise in w-LED applications.
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Thermal quenching (TQ) is still a critical challenge for lanthanide (Ln3+)-doped luminescent materials. Herein, we report the novel negative thermal expansion nonhygroscopic phosphor ZrSc(WO4)2PO4:Yb3+/Er3+. Upon excitation with a 980 nm laser, a simultaneous thermal enhancement is realized on upconversion (UC) and downshifting (DS) emissions from room temperature to 573 K. In situ temperature-dependent X-ray diffraction and photoluminescence dynamics are used to reveal the luminescence mechanism in detail. The coexistence of the high energy transfer efficiency and the promoted radiative transition probability can be responsible for the thermally enhanced luminescence. On the basis of the luminescence intensity ratio of thermally coupled energy levels 2H11/2 and 4S3/2 at different temperatures, the relative and absolute sensitivities of the targeted samples reach 1.10% K-1 and 1.21% K-1, respectively, and the low-temperature uncertainty is approximately 0.1-0.4 K on the whole temperature with a high repeatability (98%). Our findings highlight a general approach for designing a hygro-stable, thermostable, and highly efficient Ln3+-doped phosphor with UC and DS luminescence.
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Multifunctional materials with working temperatures near room temperature are crucial for practical applications. Until now, it is still a great challenge to obtain such materials. In this paper, a complex of (C5 NH13 Cl)2 MnBr4 (1) with a structural phase transition near room temperature is reported. The phase transition induces switchable magnetic properties, dielectric anomalies and luminescent response over the same range of temperatures. It is the first time the synergetic effect of magnetism, dielectricity and luminescence near room temperature have been observed in the same molecular complex.
Assuntos
Luminescência , Magnetismo , Temperatura , Transição de FaseRESUMO
An aqueous stable europium-based metal-organic framework with properties of ratiometric fluorescence sensing, namely, {[(CH3)2NH2][Eu(TCPB)(H2O)2]·DMF}n (Eu-MOF; H4TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)-benzene), was synthesized under solvothermal conditions and structurally characterized. Crystal structure analysis shows that Eu-MOF is a three-dimensional porous crystal, in which the EuIII ion is an eight-coordinate square inverse prism with eight oxygen atoms. Fluorescence measurements show that Eu-MOF exhibits characteristic emission of the EuIII ion and ligand. Eu-MOF displays good selectivity and sensitivity as a ratiometric fluorescence sensor for phosphate anions with a low detection limit in Tris-HCl buffer solution. Furthermore, Eu-MOF also has a good ability to identify salicylaldehyde through fluorescence quenching with a detection limit of 0.095 ppm. Therefore, it is an excellent fluorescent sensing material for phosphate and organic salicylaldehyde.
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A novel three-dimensional Eu3+-based metal-organic framework with the formula {[(CH3)2NH2][Eu(BTDI)]·H2O·DMF}n (JXUST-25) was prepared by solvothermal method based on Eu3+ and 5,5'-(benzothiadiazole-4,7-diyl)diisophthalic acid (H4BTDI) with benzothiadiazole (BTD) luminescent groups. Due to the presence of Eu3+ and organic fluorescence ligand, JXUST-25 displays turn-on and blue-shift fluorescence toward Cr3+, Al3+ and Ga3+ with limits of detection (LOD) of 0.073, 0.006 and 0.030 ppm, respectively. Interestingly, the alkaline environment can change the fluorescence of JXUST-25 toward Cr3+/Al3+/Ga3+ and the addition of HCl solution realizes the reversible change of the fluorescence of JXUST-25 toward Cr3+/Al3+/Ga3+. It is noteworthy that the fluorescent test paper and light-emitting diode lamp based on JXUST-25 can effectively detect Cr3+, Al3+ and Ga3+ by the visual changes. In addition, the turn-on and blue-shift fluorescence between JXUST-25 and M3+ ions may be caused by the host-guest interaction and the absorbance caused enhancement mechanism.