Aggregation-induced Emission Enhancement Research Articles

A Multimode fluorescent sensor for sequential detection of Cu2+ and cysteine as well as pH sensor with real sample Applications: Extensive experimental and DFT studies

Highly responsive and optically selective (E)-1-((4-phenoxyphenyl) diazenyl)naphthalen-2-ol) sensor PDN with aggregation induced emission enhancement (AIEE) properties has been developed for the sequential detection of Cu2+ and L- Cysteine through fluorescence On-Off-On strategy. The selectivity of sensor depends on the presence of a diazo functional group and its appropriate cavity location in sensor molecule. Azo dye-based (E)-1-((4-phenoxyphenyl) diazenyl)naphthalen-2-ol) sensor PDN has been synthesized by utilizing a simple diazotization synthetic methodology that showed extraordinary AIEE behavior with bathochromic shift owing to the formation of J-aggregates. The morphology and size of aggregates were analyzed by SEM and DLS analysis, respectively. The calculated LOD of sensor PDN for Cu2+, and L-cysteine is 0.113 nM, and 84 nM, respectively. Fluorescence, UV–visible, 1H and 13C NMR titration were carried out to understand the interaction of sensor with Cu2+. The sensor was practically utilized in the sequential sensing of Cu2+ and Cys in real samples. Interestingly, sensor PDN was successfully employed for the sensing of a strong acid and base as well as the detection of Cu2+ ions in the solid state. Moreover, these experimental results were supported through DFT calculations.

Detection of C-reactive protein using a label-free NIR fluorescent aptasensor with a large Stokes shift based on an AIEE anthracene derivative

BackgroundC-reactive protein (CRP), one of the classic biomarkers of inflammation, is closely related to infectious inflammation, cardiovascular disease, cancer, and other diseases. Therefore, timely and accurate detection of CRP in human blood is crucial for the discovery, diagnosis, and treatment of the aforementioned diseases. Herein, a novel label-free NIR fluorescence aptasensor with a large Stokes shift based on an AIEE anthracene derivative B and a molybdenum disulfide (MoS2) platform was developed and used for the high sensitivity and specificity detection of CRP. ResultsCompound B could emit near-infrared (NIR) fluorescence with a large Stokes shift (190 nm). Notably, this compound could bind with the aptamer of CRP (CRP-Apt) through electrostatic attraction to form a B/CRP-Apt complex, generating an aggregation-induced emission enhancement effect and enhancing the fluorescent intensity of B. B/CRP-Apt could be adsorbed on the surface of MoS2 with the addition of MoS2 to its solution, and the fluorescence of Compound B was quenched. CRP was then added to the above solution. CRP-Apt had a substantially higher affinity for CRP than MoS2. Therefore, B/CRP-Apt detached from the surface of MoS2 and bound to CRP, thereby restoring the fluorescence of B. Experimental results showed a good linear relationship between the fluorescent recovery intensity of B and the concentration of CRP in the concentration range of 0.3–70 ng mL−1, with a limit of detection as low as 0.1 ng mL−1. Significance and NoveltyThe aptasensor integrates the advantages of high sensitivity of NIR fluorescence, high specificity of aptamers, good water-solubility and AIEE effect of Compound B. And it could be applied to the determination of CRP in human serum samples, while most of the reported methods can only determine CRP in spiked human serum samples.

Fluorescence Entrenched Probe for Onsite Detection of Amoxicillin Residue in Bovine Milk.

A novel fluorescent probe (E)-3-(4-hydroxyphenyl)-2-((pyrene-1-ylmethylene) amino)propanoic acid (PyT) was developed for the 'turn-on' detection of amoxicillin(AM), residues. The PyT molecule was developed by a simple condensation reaction between a biologically important tyrosine amino acid and pyrene carboxaldehyde. The small fluorophore molecule has spectacular photoluminescence properties such as large stock shift, high photostability, selectivity and sensitivity toward the analytes. The PyT upon dispersion in the liquid phase becomes highly luminescent possessing the restricted intramolecular rotation (RIR) and excited stated intramolecular proton transfer (ESIPT) properties which are the major criteria for aggregation induced emission enhancement (AIEE) mechanism prevailing the aggregation caused quenching (ACQ). PyT molecule shows a binding constant of 3.285 × 104 L mol-1for amoxicillin (AM). The limit of detection(LOD) values are found to be 1.67µM. Consuming bovine milk with antibiotic residues exceeding the maximum residue limit (MRL) can lead to food toxicity and life threatening diseases in humans. The milk sample with AM antibiotic residue in presence of PyT probe shows a distinct blue colour which infers the selectivity and sensitivity of the probe towards the analyte. The fluorescence probe adheres with merits like on site and visual examination by naked eye without aid of any instruments.

Excitation Dependent Multiemissive Behaviour of Triimidazole Carboxylic Acid anti‐Kasha Luminophore and its Mononuclear Metal Complexes

Materials based on small molecules characterized by multi‐component short and long‐lived emissive behaviour are extremely desirable for various applications. The derivative of cyclic triimidazole (TT) functionalized with a carboxylic group, namely TT‐COOH, is isolated, investigated and used as coordinative ligand to obtain a series of isomorphous mononuclear complexes of general formula [M(TT‐COO)2(H2O)2] (M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)). Crystals of TT‐COOH display aggregation induced enhanced emission (AIEE) comprising dual fluorescence and dual phosphorescence of molecular origin together with an aggregation induced long lived, low energy phosphorescence. Emissive features are retained in crystals of the Zn(II) and Cd(II) complexes, where the metal plays the role of an external heavy atom perturber, but strongly quenched in the others. The mechanisms involved in the photophysics of TT‐COOH and its metal complexes have been disclosed thanks to combined structural, spectroscopic and computational investigations which reveal the presence of anti‐Kasha emissions.

Amplification and Attenuation of Asymmetry via Kinetically Controlled Seed-Induced Supramolecular Polymerization.

The amplification of asymmetry in supramolecular polymers has recently garnered significant attention. While asymmetry amplification has predominantly been explored under thermodynamic conditions, the kinetic aspect of this process unveils intriguing observations, yet is scarcely reported in the literature. Herein, drawing inspiration from macromolecular systems, we propose a novel strategy for enhancing asymmetry in supramolecular polymers through a seed-induced supramolecular polymerization approach under kinetic conditions, employing a naphthalene diimide-derived monomer (ANSG) for template-induced supramolecular polymerization, utilizing adenosine triphosphate (ATP) and pyrophosphate (PPi) as templates. A chiral seed comprising [ANSG-ATP]S effectively amplifies the overall supramolecular asymmetry when exposed to a mixture of achiral templates (PPi) and monomers (ANSG), owing to its efficient seeding characteristics under kinetic conditions. As a result of efficient co-operativity, conversely, employing an achiral seed [ANSG-PPi]S in a mixture of chiral templates (ATP) and monomers (ANSG) results in the attenuation of asymmetry, highlighting the effective modulation achievable through the seeding approach, an unprecedented observation in the field. Exploiting the efficient aggregation-induced emission enhancement (AIEE) of the resultant supramolecular polymers further extends the amplification and attenuation of circularly polarized luminescence (CPL) as a potential function.

Rapid and accurate identification of multiple metal ions using a bispyrene‐based fluorescent sensor array with aggregation‐induced enhanced emission property

AbstractMultiple metal ions are traditionally detected using inductively coupled plasma mass spectrometry (ICP‐MS) and atomic fluorescence spectrometry. Although these methods are sensitive and accurate, they depend on complex instruments and require highly trained operators, making low costly rapid detection challenging. It is urgent to develop a convenient, rapid and sensitive method to detect multiple metal ions. Herein, we designed a bispyrene derivative (BP) with aggregation‐induced enhanced emission (AIEE) property to construct a high fluorescent sensor array to realize the effective identification of four metal ions (Fe3+, Cu2+, Co2+ and Cd2+). The differential coordination capability between metal ions and BP with the aid of acetate ions resulted the possibility of array‐based sensing. The four heavy metal ions could be immediately classified in the concentration of 100 nM. The limit of detection (LOD) of Fe3+, Cu2+, Co2+, and Cd2+ were as low as 16.2, 21.8, 51.4, and 25.9 nM, respectively. Furthermore, the sensor array was applied for identification multiple heavy metal ions in environmental samples and iron ion in rat serums with identified of 100%. The sample consumption as low as 2 µL for each detection and the results could be extracted by smartphones under ultraviolet lamps. It provided a rapid, sensitive, low‐cost, and on‐site multiple metal ions detection method.

Fluorescent Ionic Liquid Aggregates: A Self-Assembled Approach for Pesticide Detection and Catalysis.

The unregulated use of pesticides, industrial discharge of heavy metals, waste, and agricultural runoff may contaminate surface water and groundwater, consequently threatening ecosystems and human health. Thus, the sensitive detection and degradation of pesticides are essential for safety. In this context, herein, we have developed benzimidazolium-based fluorescent surfactant assemblies TA-1/SDS and TA-2/SDBS, which exhibit aggregation-induced emission enhancement in an aqueous medium. The aggregates (TA-1/SDS and TA-2/SDBS) displayed a turn-on emission response upon interaction with carbendazim and azamethiphos with limits of detection 7.5 and 7.8 nM, respectively. The FE-SEM and AFM studies revealed that TA-1/SDS and TA-2/SDBS undergo self-assembly with the addition of AZA and CBZ, resulting in the formation of dendritic structures. In addition to the quantification of AZA and CBZ, TA-1/SDS and TA-2/SDBS have also been evaluated to degrade both pesticides and validated using 31P NMR spectroscopy and LC-MS spectrometry.

Solvent-induced modulation of sensitivity and selectivity in the self-assembly of tetracationic cyclophanes with cholesterol sulphate, sodium dodecyl sulfate, and sodium dodecyl benzene sulfonate: Observations of significant shifts

Cyclophane CP-1 demonstrates markedly distinct sensitivities toward Cholesterol sulfate (CH-S), Sodium Dodecyl Sulfate (SDS), and Sodium Dodecyl Benzene Sulfonate (SDBS) when the solvent is shifted minimally from a 95 % to a 98 % HEPES-DMSO mixture. In a 98:2 HEPES-DMSO mixture, CP-1 engages in highly selective self-assembly with CH-S, which is characterized by aggregation-induced emission enhancement (AIEE) in contrast to other steroidal sulfates such as pregnenolone sulfate (PRG-S), dehydroisoandrosterone sulfate (DIAND-S), taurocholic acid (TACH-S), and the surfactants SDS and SDBS. This assembly results in an approximate 40-fold increase in fluorescence intensity with three equivalents of CH-S and allows for the detection of concentrations as low as 200 nM under physiological conditions. Dynamic light scattering (DLS) studies illustrate the aggregation of CP-1 and CH-S, with the zeta potential of each shifting from negative values to nearly zero in a 1:2 CP-1:CH-S mixture, indicating self-assembly. This aggregation behavior is reversible, as demonstrated by a corresponding decrease and then increase in fluorescence intensity with temperature variations from 25 °C to 70 °C and back to 25 °C. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) analyses show that CP-1 forms aggregates ranging from 100 to 180 nm, which increase to 150–250 nm upon interaction with CH-S. In a 95:5 HEPES-DMSO mixture, CP-1 exhibits a stronger AIEE response with SDS and SDBS compared to CH-S. Cyclophane CP-2, when dissolved in binary DMSO-water mixtures with water content exceeding 80 %, shows similar AIEE phenomena and undergoes selective fluorescence quenching with SDS and only a 50 % increase in fluorescence intensity with CH-S, irrespective of the HEPES concentration (95 % or 98 %).

Triphenylamine-Based Solid-State Emissive Fluorene Derivative with Aggregation-Induced Emission Enhancement Characteristics

Aggregation-induced emission (AIE) has garnered considerable attention in recent years. Understanding the mechanisms underlying AIE phenomena is crucial. Here, we present the design and synthesis of a novel fluorene derivative (4) based on triphenylamine, which exhibits typical AIE properties. The structure of it was totally characterized using FT-IR, MALDI-TOF mass analysis, elemental analysis, 1H, and 13C NMR spectroscopy. It displayed strong solid-state emission with diverse fluorescence characteristics. The AIE property of the compound was systematically studied using photoluminescence spectroscopy, revealing a distinct yellow light-emitting phenomenon. The solid-state luminescence showed a red shift of 148 nm compared to its luminescence in dilute dimethylformamide (DMF) solutions. Moreover, photophysical characteristics, including absorption and emission spectra, as well as fluorescence lifetime, were examined using UV–vis absorption and fluorescence emission spectroscopy. Compound (4) exhibited superior photosensitization abilities in both solid and solution states, with a notably enhanced effect observed in the solid state compared to the solution state.

An Acid-Responsive Fluorescent Molecule for Erasable Anti-Counterfeiting.

A tetraphenylethylene (TPE) derivative, TPEPhDAT, modified by diaminotriazine (DAT), was prepared by successive Suzuki-Miyaura coupling and ring-closing reactions. This compound exhibits aggregation-induced emission enhancement (AIEE) properties in the DMSO/MeOH system, with a fluorescence emission intensity in the aggregated state that is 5-fold higher than that of its counterpart in a dilute solution. Moreover, the DAT structure of the molecule is a good acceptor of protons; thus, the TPEPhDAT molecule exhibits acid-responsive fluorescence. TPEPhDAT was protonated by trifluoroacetic acid (TFA), leading to fluorescence quenching, which was reversibly restored by treatment with ammonia (on-off switch). Time-dependent density functional theory (TDDFT) computational studies have shown that protonation enhances the electron-withdrawing capacity of the triazine nucleus and reduces the bandgap. The protonated TPEPhDAT conformation became more distorted, and the fluorescence lifetime was attenuated, which may have produced a twisted intramolecular charge transfer (TICT) effect, leading to fluorescence redshift and quenching. MeOH can easily remove the protonated TPEPhDAT, and this acid-induced discoloration and erasable property can be applied in anti-counterfeiting.

Rational design of narrowband deep blue MR-TADF dendrimers for high performance solution-processed all fluorescence white OLEDs

Developing solution-processable deep-blue multiple resonances thermally activated delayed fluorescence (MR-TADF) is a formidable challenge. Here, we using a convergent synthesis process successfully developed a series of MR-TADF dendrimers based on C=O/N resonant core (QAO). The alkyl chain alternate-linked functional dendrons not only ensure the narrow-band deep-blue emission but also enable the dendrimers with aggregation-induced emission enhancement (AIEE) properties, which efficiently mitigate the aggregation-induced exciton quenching (ACQ) and obnoxious spectral redshift broadening effect. Notably, the solution-processed deep blue MR-TADF OLEDs achieved a maximum external quantum efficiency (EQE) of 13.5 % and CIE of (0.15, 0.12) with an electroluminescence peak below 450 nm. Further using such dendrimer as a sensitizer for white OLEDs resulted in an optimized high EQE of 18.9 % and a high color-rendering index (CIR) of 81.1 for two and three optical components of white emissions, which are among the highest values of previously reported solution-processed all-fluorescence white OLEDs. This is the first attempt to construct white OLED based on an MR-TADF emitter and the satisfactory results indicate that the flexible dendron engineering strategy can effectively develop high-performance narrow band deep-blue MR-TADF for wide-color gamut display and high CIR white OLEDs.

Aggregation-Induced Enhanced Red Emission Graphene Quantum Dots for Integrated Fabrication of Luminescent Solar Concentrators.

Graphene quantum dots (GQDs) commonly suffer from the fluorescence problem of aggregation-caused quenching under high-concentration loading or in the solid state, which seriously hinders the application. Here we report a type of GQDs with red aggregation-induced enhanced emission (AIEE). It is confirmed that the aggregation state of the AIEE GQDs is a J-aggregate. The GQDs/poly(methyl methacrylate) film presented a photoluminescence quantum yield as high as 60.81%, and the record-high performance of luminescent solar concentrators (LSCs) was achieved. The power conversion efficiency (ηPCE) is up to 8.35% and the external optical efficiency (ηext) is ∼8.99% for the GQD-based LSCs (45 mW/cm2). Even under one sun illumination (100 mW/cm2), the corresponding ηPCE and ηext values are 3.12% and 4.52%, respectively. The internal photon efficiency (ηint) of an LSC device is about 5.02%. The synthesis of AIEE GQDs bridges the research gap in the emission mechanism of AIEE in GQDs.

Hierarchical Self-Assembly and Aggregation-Induced Emission Enhancement in Tetrabenzofluorene-Based Red Emitting Molecules.

The newly synthesized chiral active [5]helicene-like tetrabenzofluorene (TBF) based highly red-emitting molecules exhibit flower-like self-assembly. These molecules display photophysical and structural properties such as intramolecular charge transfer, dual state emission, large fluorescence quantum yield, and solvatochromism. In TBFID, the indandione functional group attached on both sides as the terminal group offers an A-D-A push-pull effect and acts as a strong acceptor to cause more redshift in solution as well as in solid state as compared to TBFPA (TBF with benzaldehyde functional group in terminal position). The self-assembly studies of TBFID demonstrate the aggregation-induced emission enhancement (AIEE) attributed to the restriction of intramolecular rotation at the aggregated state. Furthermore, TBFID shows high quantum yield and intense red emission, making the molecule fit for organic light-emitting diodes (OLED) and bioimaging applications.

Effect of multi-donor and extended π-conjugation in ferrocene appended indanedione chromophores for aggregation induced emission enhancement (AIEE) and nonlinear optics†

A new (D-D’π-A) type ferrocene and methoxyphenyl (D-D′) conjugated indanedione (A) based linear and π-extended multi-donor-π-acceptor chromophores 1–4 were synthesized and characterized. The chromophores 2–4 were further investigated by single-crystal analysis through X-ray diffraction, revealing centrosymmetric space groups with non-covalent interactions (inter, intramolecular hydrogen bonding, and C–H…π interactions) and these molecular packing interactions favor SHG efficiencies. Electrochemical studies show the one-electron charge transfer (Fe2+⇌Fe3+) and observed greater redox potential of chromophore 4 than the parent ferrocene due to the substitution effect. The solvatochromic studies in emission spectra resulted in redshift (56–109 nm) for the chromophores 1–4 by increasing the solvent polarities, which indicates higher excited state stabilization relative to the ground state, results effective intramolecular charge transfer process within the chromophores. The occurrence of ferrocene moieties lowers the fluorescence intensities of the chromophores 1–4, which was overcome through aggregation induced emission enhancement (AIEE) studies at 60 % (THF/H2O). The AIEE state also shows 23 times higher quantum yield than the THF solution for chromophore 4. In addition, a thin film using polymethyl methacrylate as a binder shows a significant blue shift with higher emission intensity than those obtained in the solution due to the intermolecular interactions and enhancement of viscosity. The SHG efficiency studied using the Kurtz and Perry powder technique results in a higher value for chromophore 4 (2 times higher than the reference KDP) attribute to the multi donors, acceptor, and extended π conjugation reducing the anti-parallel alignment in the solid state. The computational calculations were done to validate the experimental results using B3LYP/6-31+G** level of theory.

Base‐Promoted Regioselective Synthesis of α‐Amino BODIPYs through Cross‐Dehydrogenative Coupling with Anilines

AbstractThe construction of C−N bond at the α‐position of BODIPYs (boron dipyrromethene) not only enables flexible reactivity but also leads to strong electron‐donating properties. In this study, a base‐promoted oxidative cross‐dehydrogenative coupling was developed to synthesize α‐amino BODIPYs with air as a green oxidant. By this strategy, a series of weak nitrogen nucleophiles, such as heteroaryl and aryl anilines, were installed to the α‐position. Remarkably, pyrrole, pyrazole and indole were also employed to realize the synthesis of α‐heteroaryl BODIPYs through direct functionalization. Further aggregation‐induced emission enhancement (AIE) properties and lipid droplet‐targeting bioimaging experiments of representative dyes demonstrated their potential applications as organic probes.

Aggregation-Induced Emission Enhancement and Solid-State Photoswitching of Crystalline Carbazole N-Salicylidene Anilines.

The development of fluorescent stimuli-responsive organic materials has attracted substantial interest due to their increasing optoelectronic applications. This study systematically introduces fluorine atoms on one end of carbazole-based N-salicylidene anilines 5a-5f to elucidate the impact in their solution and solid-state photophysics. The addition of fluorine atoms at one end of the molecule induced significant changes, for example, a reduction in the quantum yield (QY) fluorescence emission in solution, going from QY near unity in compound 5a (QY ∼ 100%) to a negligible emission in 5f (QY < 1%). Similarly, compound 5a showed a very strong aggregation-induced enhancement emission behavior, whereas compounds with a higher fluorine content were almost quenched. Furthermore, the crystalline solid-state photoisomerization in N-salicylidene anilines is not trivial, and only compounds with three (5e) and five fluorine atoms (5f) exhibited reversible solid-state photoisomerization under 405 nm light source irradiation. We propose that the presence of the arene-perfluoroarene interaction in the crystalline array facilitates the latter behavior. Our findings present a comprehensive study of crystal engineering for the obtention of photoswitchable crystalline materials and adjustable photophysics response, paving the way for its implementation in other systems.

Aggregation induced emission enhancement of [Ag3Cu8] clusters protected by alkyne and phosphane ligands

In this work, three isostructural clusters of [Ag3Cu8(R-Ph-CC)6(N-triphos)2(Ph2PO2)3](NO3)2 (R = 4-H (1), 4-CH3 (2), 4-F (3)) were successfully synthesized and structurally determined by single crystal X-ray diffraction. At room temperature, they show weak photoluminescence in CH2Cl2 solution at ∼715 nm but with a 20-fold increase of quantum yields in their aggregation. Crystallographic and Hirshfeld surface analysis reveals a plentiful of intermolecular interactions (C−H…N, C−H…O, C−H…π, π…π) exist in their solid states, which can inhibit the intra-/inter-molecular motions (vibration and rotation) and thus generate the aggregation induced emission enhancement phenomenon. Moreover, their solid luminescent intensities at 100 K are much higher than those at room temperature. Comparisons of their luminescence show that the substituents on the para-positions of phenylethynes not only have a charge effect on emission, but also have steric effect on the molecular stacking and supramolecular interactions in the aggregated and crystalline states, and then on the aggregation-induced emission. The density functional theory (DFT) calculations show that the possible luminescence mechanism of these clusters is ligand-to-metal−metal charge transfer (LMMCT).

A new luminescent nickel nanocluster with solvent and ion induced emission enhancement toward heavy metal analysis

Expanding the family of fluorescent metal clusters beyond gold, silver, and copper has always been an issue for researchers to solve. In this study, a novel type of cysteine-capped nickel nanoclusters (Cys-Ni NCs) with bright turquoise emission was developed. The as-synthesized Ni NCs showed aggregation-induced emission enhancement (AIEE) properties across Cd2+ and various polar organic solvents. Concurrently, solvents with different viscosities were used to explore the principle of solvent-induced AIEE of Cys-Ni NCs, revealing a positive correlation between fluorescence intensity and solution viscosity. In addition, the concentration of Cd2+ that induced the AIEE effect was reduced by nearly two orders of magnitude in highly viscous solvents, indicating the possibility of Cys-Ni NCs as a promising nanomaterial platform for Cd2+ sensing analysis. Moreover, we propose a novel fluorescent sensing method for rapid detection of Cu2+ based on the carboxyl group of Cys-Ni NCs coupling with Cu2+. Further, validation of Cu2+ detecting methodologies in environmental water samples with the accuracy up to 93.94% underscores their potential as robust and efficient sensing platforms. This study expands the repertoire of fluorescent metal nanoclusters for highly sensitive and selective sensing of hazardous ions and paves the way for further exploration and wide applications in Cu2+ detection in biological and medicine fields.

Ligand-selective turn-off sensing, harvesting and post-adsorptive use of Dy(III) and Yb(III) by intrinsically fluorescent flower-shaped Gum Acacia-grafted hydrogels

Rare earth metals (REMs), such as Dysprosium (Dy) and Ytterbium (Yb), have experienced unprecedented demand in recent times due to their applications in high-end technologies. REMs are found only in select geographic locations placing tremendous economic constraints on their use. In this work, we have developed Gum Acacia-grafted hydrogels (GmAc-FluoroTerPs) that are capable of selective detection and capture of Dy and Yb. The intrinsically blue fluorescent polymer hydrogel GmAc-FluoroTerP has been optimized for Dy(III) and Yb(III) specific quenching, enabling limit of detection of the REMs at 0.13 nM and 60.8 pM, respectively. A comprehensive structural characterization of the fluorescent hydrogel has been performed via NMR, FTIR, XPS, EPR, TGA, XRD, TEM, SEM, EDX, TCSPC, and DLS. In addition to an in situ generated fluorophore, GmAc-FluoroTerP displays a distinctive aggregation induced emission enhancement in mixed solvents. The complexation of Dy(III)/Yb(III) with GmAc-FluoroTerP hydrogel has been characterized by XPS, TCSPC, and logic gate analyses, and the adsorptive capacity for Dy(III) and Yb(III) are found to be best reported till date as 125.57 mg g−1 and 102.27 mg g−1, respectively. Desorption at acidic pH allows recovery of the REMs. We also report semiconducting behaviour of the native fluorescent hydrogel, that is enhanced upon adsorptive capture of Dy(III) and Yb(III), with calculated band gaps at 1.37, 0.77, and 0.49 eV, respectively. The convergent sensing, capture, and reuse of Dy(III) and Yb(III) presented in this work promises a hitherto unreported template for application on other REMs.

Hydrates of N-(Anthracen-9-ylmethyl)-3-(1H-imidazolium-1-yl)propan-1-ammonium Zinc(II) or Cobalt(II) 2,6-pyridinedicarboxylate: Inter-conversions, assembling and utilities

Different hydrates [(H3anthraimmida)M(26pdc)2]⋅nH2O⋅mCH3OH {(M = Co; n, m = 4, 0 or n, m = 4.5: 0 or n, m = 2, 2 and M = Zn; n, m = 4, 0 or n, m = 1, 1.5) N-(anthracen-9-ylmethyl)-3-(1H-imidazolium-1-yl)propan-1-amommonium cation (H3anthraimmida), 2,6-pyridinedicarboxylates (26pdc)} of N-(anthracen-9-ylmethyl)-3-(1H-imidazolium-1-yl)propan-1-ammonium zinc(II) or cobalt(II) 2,6-pyridinedicarboxylate were crystallized from solutions of same reacting components but each at different concentration. Among these hydrates, the ones having methanol also as solvent of crystallization were metastable, easily transformed to corresponding tetrahydrate. The crystals of the metastable hydrate of zinc complex (monoclinic) transformed to tetrahydrate (triclinic) by halving of unit cell dimension of the metastable form. This transformation was observed under an optical microscope in real time. The transformation of the metastable hydrate of the cobalt complex also resulted the corresponding tetrahydrate. In this case, the unit-cell of the metastable form was doubled than the unit-cell dimension of the corresponding tetrahydrate. The crystals of the metastable form of the zinc complex (monoclinic) transformed to the tetrahydrate (triclinic) though a top-down approach, whereas the crystals of the metastable hydrate of the cobalt complex underwent a bottom-up approach. Diffused light scattering studies have revealed that the average particle sizes of the metastable hydrate of the zinc or cobalt complex dissolved in methanol, were decreased or increased upon addition of water to the solution. The zinc complexes in methanol showed aggregation induced emission enhancement at 415 nm upon addition of water.