Luminescent lanthanide (Eu(<scp>iii</scp>)) cross-linked supramolecular metallo co-polymeric hydrogels: the effect of ligand symmetry

Bradberry, Samuel J.; Dee, Garret; Kotova, Oxana; McCoy, Colin; Gunnlaugsson, Thorfinnur

doi:10.1039/c8cc08888h

Cited by 31 publications

(13 citation statements)

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“…Accurate design of luminescent materials that are sensitive to external stimuli, such as light, temperature, pH, metal ions, chemical action, and mechanical stress, is critical to the development of next-generation smart optical materials. − Over the past few decades, luminescent supramolecular hydrogels have shown extraordinary potential and established a multibillion dollar industry until today for their versatile functions and unique biocompatibility. − Various functional supramolecular hydrogels have been constructed through internal network cross-linking triggered by non-covalent interactions, such as π–π interactions, hydrogen bond, metal-coordination, and electrostatic interactions. − Particularly, a metal/ligand complex has unique kinetic properties and sensitive stimulus responsiveness arising from the coordination bonds, which provides a worthy strategy for the construction of luminescent stimulus-responsive supramolecular hydrogels …”

Section: Introductionmentioning

confidence: 99%

Coordination-Assembly of Lanthanide Supramolecular Hydrogels with Luminescent Multi-stimulus Response

Wang

Liu

et al. 2021

Inorg. Chem.

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Luminescent supramolecular hydrogels have shown extensive potential for a variety of applications due to their unique optical properties and biocompatibility. Coordination self-assembly provides a promising strategy for the preparation of supramolecular hydrogels. In this contribution, a series of luminescent lanthanide (Ln) supramolecular hydrogels HG-Ln 2n L 3n 1/2 are synthesized by coordination self-assembly of Ln ions and V shaped bis-tetradentate ligands (H 4 L 1 and H 4 L 2 ) with different bent angles (∠B). Two rigid conjugated ligands H 4 L 1 and H 4 L 2 with bent angles (∠B ≈ 150°) featuring a 2,6-pyridine bitetrazolate chelating moiety were designed and synthesized, which generated hydrogels via the deprotonation self-assembly with lanthanide ions. Characteristic Eu 3+ and Yb 3+ emissions were realized in the corresponding hydrogels, with intriguing multi-stimulus response behaviors. The luminescence of the HG-Eu 2n L 3n 1 hydrogel can be enhanced or quenched when stimulated by diverse metal ions, attributed to the replacement of the coordinated lanthanide ions and changes in the intersystem crossing efficiency of the ligand. Furthermore, pH-responsive emission of the HG-Eu 2n L 3n 1 hydrogel has also been observed. Our work provides potential strategies for the design of next-generation smart responsive hydrogel materials with variable structures.

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Section: Introductionmentioning

confidence: 99%

Coordination-Assembly of Lanthanide Supramolecular Hydrogels with Luminescent Multi-stimulus Response

Wang

Liu

et al. 2021

Inorg. Chem.

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“…One strategy is to design small chelating ligands that can form a lanthanide-metal network based on coordination, leading to metallogels with tunable luminescence and stimuli-responsive properties but low modulus and no/limited plasticity and processability. , Alternatively, the chelating groups can be grafted onto polymer chains that forms supramolecular hydrogels upon mixing with Eu(III); nonetheless, the obtained hydrogels still have very poor mechanical strength . Incorporating lanthanide coordination into covalent cross-linking network leads to much stronger hydrogels, on the other hand, at the expense of self-healability and reprocessibility. , So far, designing lanthanide coordination hydrogels with integrated properties, such as self-healability, stimuli-response, high modulus, and plasticity, remains a great challenge. − , Here, we seek to overcome this limitation by introducing the strategy of polyelectrolyte complex coacervation.…”

Section: Introductionmentioning

confidence: 99%

“…9 Incorporating lanthanide coordination into covalent cross-linking network leads to much stronger hydrogels, on the other hand, at the expense of selfhealability and reprocessibility. 10,11 So far, designing lanthanide coordination hydrogels with integrated properties, such as selfhealability, stimuli-response, high modulus, and plasticity, remains a great challenge. [7][8][9]12 Here, we seek to overcome this limitation by introducing the strategy of polyelectrolyte complex coacervation.…”

Section: ■ Introductionmentioning

confidence: 99%

Processable and Luminescent Supramolecular Hydrogels from Complex Coacervation of Polycations with Lanthanide Coordination Polyanions

Wang

Sun

et al. 2019

Macromolecules

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Luminescent supramolecular gels based on dynamic lanthanide coordination can be of profound interest in optical and sensing applications. However, most of the current lanthanide-based gels suffer from their poor mechanical strength and processability for practical uses. Here, we develop an effective strategy to fabricate a multifunctional robust luminescent hydrogel via the ionic coacervation of an anionic lanthanide coordination polymer with a cationic polyelectrolyte. The resultant hydrogels turn out to be moldable, self-healable, recyclable, and may be regarded as a new kind of "luminescent plastic". Owing to the unique force-induced plastic deformation, long fibers can be directly drawn from the hydrogel reservoir at room temperature. Moreover, the dynamic nature of such a physical polymer network leads to multiple responses to various stimuli, such as temperature, salt, and sonication. The studies described herein not only enable the easy processability of luminescent hydrogels, but also provide a new strategy to prepare stimuli-responsive and self-healing lanthanide-based hydrogels as sustainable and smart materials.

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“…Amide-based LMWGs contain an amide N−H donor and C=O acceptor resulting in a strong N−H···O=C interaction, which self-assemble to a 3-D network via cooperative and unidirectional hydrogen bonding involving amide units [43]. These 3-D networks are capable of immobilizing solvent molecules to form organo/hydrogels [34,44,45,46,47,48,49]. Recently, we reported the structural modification of trimesic amide-based gelator N 1 ,N 3 ,N 5 -tri(pyridin-3-yl)benzene-1,3,5-tricarboxamide [50] to corresponding tris- N -oxide compound ( L-3Nox ) [38].…”

Section: Introductionmentioning

confidence: 99%

Tuning Gel State Properties of Supramolecular Gels by Functional Group Modification

2019

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The factors affecting the self-assembly process in low molecular weight gelators (LMWGs) were investigated by tuning the gelation properties of a well-known gelator N-(4-pyridyl)isonicotinamide (4PINA). The N―H∙∙∙N interactions responsible for gel formation in 4PINA were disrupted by altering the functional groups of 4PINA, which was achieved by modifying pyridyl moieties of the gelator to pyridyl N-oxides. We synthesized two mono-N-oxides (INO and PNO) and a di-N-oxide (diNO) and the gelation studies revealed selective gelation of diNO in water, but the two mono-N-oxides formed crystals. The mechanical strength and thermal stabilities of the gelators were evaluated by rheology and transition temperature (Tgel) experiments, respectively, and the analysis of the gel strength indicated that diNO formed weak gels compared to 4PINA. The SEM image of diNO xerogels showed fibrous microcrystalline networks compared to the efficient fibrous morphology in 4PINA. Single-crystal X-ray analysis of diNO gelator revealed that a hydrogen-bonded dimer interacts with adjacent dimers via C―H∙∙∙O interactions. The non-gelator with similar dimers interacted via C―H∙∙∙N interaction, which indicates the importance of specific non-bonding interactions in the formation of the gel network. The solvated forms of mono-N-oxides support the fact that these compounds prefer crystalline state rather than gelation due to the increased hydrophilic interactions. The reduced gelation ability (minimum gel concentration (MGC)) and thermal strength of diNO may be attributed to the weak intermolecular C―H∙∙∙O interaction compared to the strong and unidirectional N―H∙∙∙N interactions in 4PINA.

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Luminescent lanthanide (Eu(iii)) cross-linked supramolecular metallo co-polymeric hydrogels: the effect of ligand symmetry

Abstract: Two lanthanide luminescent naphthyl-dipicolinic amide (dpa) methacrylate monomers for the synthesis of grafted supramolecular co-polymer gels (hydrogels), and their use as additional crosslinks in robust covalently cross-linked HEMA hydrogels is presented.

Cited by 31 publications

References 50 publications

Coordination-Assembly of Lanthanide Supramolecular Hydrogels with Luminescent Multi-stimulus Response

Coordination-Assembly of Lanthanide Supramolecular Hydrogels with Luminescent Multi-stimulus Response

Processable and Luminescent Supramolecular Hydrogels from Complex Coacervation of Polycations with Lanthanide Coordination Polyanions

Tuning Gel State Properties of Supramolecular Gels by Functional Group Modification

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