Luminescent lanthanide metallogels: situ fabrication, self-healing and rheological properties

Xue, Min; Chen, Ming; Chang, Wen-Hao; Chen, Ruiyang; Li, Pengna

doi:10.1007/s00396-020-04598-4

Cited by 6 publications

(9 citation statements)

References 41 publications

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“…Figure 1a shows the preparation procedure of the As-prepared hydrogel by photoinitiated micellar copolymerization and the Eu-hydrogel by further metal−ligand coordinate binding. A (pyridine-dicarbohydrazone)-based compound, namely, N,N′-((2,2′-((1Z,1′E)-pyridine-2,6-diylbis(ethan-1-yl-1-ylidene))bis(hydrazine-1-carbonyl))bis(4,1-phenylene))bis(2-methylacrylamide) (PDCH), serves as a hydrophobic cross-linker 1b, and its chemical structure is confirmed by 1 H NMR, 13 C NMR, FTIR, and HRMS (Figures S2 and S3). After the introduction of Eu 3+ , the (pyridine-dicarbohydrazone)-based cross-linker coordinated with Eu 3+ so as to achieve a transparent Eu-based metallohydrogel (Eu-hydrogel).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…9−12 Also, their visual color and/or fluorescence is tunable by controlling the coordination efficiency between ligands and metal ions. 6,8,13 However, most organic ligands are hydrophobic, which makes obstacles to incorporate these functional groups into hydrogel systems.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The most popular strategy to construct smart fluorescent hydrogels with multistimuli responsive behaviors and switchable fluorescence is to incorporate functional ligands into polymers. − In other words, depending on the stimuli-responsive ligands in the polymer matrix, it is possible to design smart fluorescent hydrogels with a wide range of responsivities toward various external stimuli. − Also, their visual color and/or fluorescence is tunable by controlling the coordination efficiency between ligands and metal ions. ,, However, most organic ligands are hydrophobic, which makes obstacles to incorporate these functional groups into hydrogel systems.…”

Section: Introductionmentioning

confidence: 99%

“…This mechanically strong (pyridine-dicarbohydrazone)-based polyacrylate hydrogel with multistimuli responsiveness is promising to be used in information transmission, smart windows, load-bearing devices, energy-absorbing materials, and soft wearable devices. sı Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsapm.1c00541.Stretching-induced mechanochromic property of Euhydrogel (30 × 10 × 1) (MP4) Stretching-induced mechanochromic property of Euhydrogel (50 × 10 × 1) (MP4)1 H NMR spectrum and13 C NMR spectrum of compound 1; 1 H NMR spectrum,13 C NMR spectrum, FTIR spectrum, and HRMS of cross-linker PDCH; photographs displaying the As-prepared hydrogel with a side length of 10 cm being stretched by hand palms; photographs of fluorescent patterning process of Euhydrogel using Zn 2+ ; photograph of the As-prepared hydrogel with big size (side length of 15 cm); the fluorescence emission spectra of the As-prepared hydrogel, the As-prepared hydrogel with H + and OH −recovered As-prepared hydrogel; the H + /OH − alternate titration cycles of the As-prepared hydrogel (PDF)…”

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confidence: 99%

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Pyridine-Dicarbohydrazone-Based Polyacrylate Hydrogels with Strong Mechanical Property, Tunable/Force-Induced Fluorescence, and Thermal/pH Stimuli Responsiveness

Yuan

Zhang

2021

ACS Appl. Polym. Mater.

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The smart fluorescent hydrogels exhibiting tunable fluorescence have been used as biosensors, probes, light-emitting devices, and information storage and confidentiality. However, they usually show single stimuli responsiveness and possess weak mechanical properties, which limit their applications. Herein, we report a pyridine-dicarbohydrazone-based polyacrylate hydrogel (the As-prepared hydrogel and Eu-hydrogel) showing strong mechanical property, tunable fluorescence ability, and thermal and pH stimuli responsiveness. The As-prepared hydrogel is prepared by light-induced micellar copolymerization, and Eu-hydrogel is obtained after the formation of Eu3+-(pyridine-dicarbohydrazone) coordination. The As-prepared hydrogel could be made in large size (side length of 15 cm), exhibiting a tensile strength of 1.55 MPa and a fracture tensile strain of 800%. The fluorescence intensity of Eu-hydrogel is tunable by [Eu3+] (approaching 655% of the minimum state at [Eu3+] = 0.1 mol). It is demonstrated that Eu-hydrogels display force-induced fluorochromic response during stretching. The transmittance temperature of the As-prepared hydrogel ranges from 36 to 42 °C. Reversible Eu3+-(pyridine-dicarbohydrazone) coordination enables Eu-hydrogels to have excellent fatigue resistance. The pH stimuli responsiveness of the As-prepared hydrogel and Eu-hydrogel is triggered by switchable covalent hydrozone bonds. In terms of the shape-memory ability, the As-prepared hydrogel could be reconstructed by Eu3+ and Eu-hydrogel could be deformed by H+. This mechanically strong (pyridine-dicarbohydrazone)-based polyacrylate hydrogel with multistimuli responsive behaviors is promising to be used in information transmission, smart windows, load-bearing devices, energy-absorbing materials, and soft wearable devices.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Pyridine-Dicarbohydrazone-Based Polyacrylate Hydrogels with Strong Mechanical Property, Tunable/Force-Induced Fluorescence, and Thermal/pH Stimuli Responsiveness

Yuan

Zhang

2021

ACS Appl. Polym. Mater.

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“…The rich topology of the assembled structures fully demonstrates the charm of the directed assembly 15 , which can form lanthanide metal complexes with the desired functions and thus obtain various materials with the desired properties 16 . In recent years, the most studied organic aromatic carboxylic acid ligands 17 have been used to construct crystal structures because these ligands are usually rigid, thermally stable, and high in dimensionality. There are also various coordination geometric configurations, such as tetragonal antiprism with cap, triangular dodecahedron, doublecap trigonal prism, triangular trigonal prism, etc.…”

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Construction, Thermochemistry, and Fluorescence Properties of Novel Lanthanide Complexes Synthesized from Halogenated Aromatic Carboxylic Acids and Nitrogen-Containing Ligands

Wang¹,

Xu²,

Ren³

et al. 2022

Acta Physico Chimica Sinica

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In this study, new lanthanide complexes were synthesized via the volatilization method in solution at room temperature. The general molecular formulas for the lanthanide complexes are as follows: [Ln(2,4-DFBA)3(phen)]2 (Ln = Sm 1, Eu 2, and Er 3; 2,4-DFBA = 2,4-difluorobenzoate; and phen = 1,10-phenanthroline), as well as [Ln(2-Cl-6-FBA)2(terpy)(NO3)(H2O)]2 (Ln = Tb 4 and Dy 5; 2-Cl-6-FBA = 2chloro-6-fluorobenzoate; and terpy = 2,2':6'2''-tripyridine). Based on single-crystal Xray analysis, the five complexes exhibited a monoclinic crystal structure belonging to the space group P21/n. Even though complexes 1, 2 (I), and 3 (II) share a general molecular formula, their coordination modes were different. For example, complexes 1 and 2 formed a muffin-like structure with nine coordinated atoms, while complex 3 formed a double hat triangular geometry with eight coordinated atoms. The twodimensional (2D) polyhedral structures of complexes 1 and 2 were formed via weak π-π stacking interactions, whereas complex 3 exhibited a 2D faceted supramolecular structure through C-H•••F hydrogen bonds. Complexes 4 and 5 were isostructural, with the presence of nitrate ions in their structure. This occurred through the C-H•••F hydrogen bonds and π-π stacking of the molecules to form a faceted supramolecular crystal structure. A series of characterizations, such as elemental analysis, infrared and Raman spectroscopy, as well as powder X-ray diffraction, were performed on the five complexes. Thermogravimetry-derivative thermogravimetry-differential scanning calorimetry were performed between 299.25 and 1073.15 K to investigate the mechanism for the thermal decomposition of complexes 1-5. The analysis of the escaping gas stacking maps of the five complexes using thermogravimetric and 3D infrared coupling techniques further confirmed the correctness of the thermal decomposition mechanism of each complex. The results obtained revealed that similar structured complexes follow a similar thermal decomposition mechanism, and the end solid products for all complexes were their corresponding metal oxides. During the irradiation of the Xe lamp, the solid fluorescence of complexes 1, 2, 4, and 5 were measured. The characteristic transition peaks were located at 4 G5/2 → 6 H5/2, 4 G5/2 → 6 H7/2, and 4 G5/2 → 6 H9/2 (1); 5 D0 → 7 F0, 5 D0 → 7 F1, 5 D0 → 7 F2, 5 D0 → 7 F3, and 5 D0 → 7 F4 (2); 5 D4 → 7 F6, 5 D4 → 7 F5, 5 D4 → 7 F4, and 5 D4 → 7 F3 (4); and 4 F9/2 → 6 H15/2, 4 F9/2 → 6 H13/2 (5). The peaks observed indicated the characteristic transitions of Ln(III). The lanthanide complexes exhibited characteristic fluorescence due to this fact, which also explained their characteristic color. Furthermore, the fluorescence lifetimes of complexes 2 and 4 were measured, and their fluorescence decay curves indicated fluorescence lifetimes of 1.288 and 0.648 ms, respectively.

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Recent Advances in Stimuli‐Responsive Luminescent Supramolecular Lanthanide‐Based Metallogels

Roy,

Kundu,

Biswas

et al. 2024

ChemistrySelect

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The use of lanthanide‐based metallogels presents a promising approach for the engineering of stimuli‐responsive gel materials. Stimuli‐responsive luminescent materials based on lanthanides have promising applications in bio‐applications and optical encoding. Synthetic supramolecular metallogels typically become kinetically trapped and usually do not exhibit time‐variable changes in their material properties. However, such supramolecular metallogels can switch between gel to sol when subjected to different external physical and chemical stimuli. This is because weak noncovalent interactions hold together the gel structure and are also influenced by the coordination dynamics of the metal‐ligand bond. This review summarizes recent research progress on stimuli‐responsive supramolecular lanthanide‐based luminescent metallogels. Chemical, physical, and multiple stimuli‐responsiveness of the metallogels are discussed elaborately based on the external stimulus sources. Finally, the latest challenges and opportunities for developing novel metallogels that respond to stimuli are discussed.

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Luminescent lanthanide metallogels: situ fabrication, self-healing and rheological properties

Cited by 6 publications

References 41 publications

Pyridine-Dicarbohydrazone-Based Polyacrylate Hydrogels with Strong Mechanical Property, Tunable/Force-Induced Fluorescence, and Thermal/pH Stimuli Responsiveness

Pyridine-Dicarbohydrazone-Based Polyacrylate Hydrogels with Strong Mechanical Property, Tunable/Force-Induced Fluorescence, and Thermal/pH Stimuli Responsiveness

Construction, Thermochemistry, and Fluorescence Properties of Novel Lanthanide Complexes Synthesized from Halogenated Aromatic Carboxylic Acids and Nitrogen-Containing Ligands

Recent Advances in Stimuli‐Responsive Luminescent Supramolecular Lanthanide‐Based Metallogels

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