Encapsulation engineering of porous crystalline frameworks for delayed luminescence and circularly polarized luminescence

Chemical Society Reviews, Год журнала: 2024, Номер 53(13), С. 6694 - 6734

Опубликована: Янв. 1, 2024

Delayed luminescence (DF), including phosphorescence and thermally activated delayed fluorescence (TADF), circularly polarized (CPL) exhibit common broad application prospects in optoelectronic displays, biological imaging, encryption. Thus, the combination of is attracting increasing attention. The encapsulation guest emitters various host matrices to form host-guest systems has been demonstrated be an appealing strategy further enhance and/or modulate their luminescence. Compared with conventional liquid crystals, polymers, supramolecular matrices, porous crystalline frameworks (PCFs) metal-organic (MOFs), covalent-organic (COFs), zeolites hydrogen-bonded organic (HOFs) can not only overcome shortcomings such as flexibility disorder but also achieve ordered guests long-term stability chiral structures, providing new promising platforms for development DF CPL. In this review, we provide a comprehensive critical summary recent progress photochemistry

Язык: Английский

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Multistate Circularly Polarized Luminescence Switching through Stimuli‐Induced Co‐Conformation Regulations of Pyrene‐Functionalized Topologically Chiral [2]Catenane

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(44)

Опубликована: Авг. 24, 2022

Aiming at the construction of novel circularly polarized luminescence (CPL) switches with multiple switchable emission states and high dissymmetry factors (glum ), topologically chiral [2]catenanes were employed as key platform to construct a multistate CPL switching system. Taking advantage precise co-conformation regulations resultant pyrene-functionalized under different external stimuli, reversible transformations between three performances, i.e. initial "closed" form |glum | value 0.012, "open" an almost complete turn-off emission, "protonated" boosted 0.022, successfully realized. This study demonstrates successful not only first topological chirality-based switch, but also bidirectional thus providing promising for materials.

Язык: Английский

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Hexaphenylbenzene‐Based Deep Blue‐Emissive Metallacages as Donors for Light‐Harvesting Systems

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(34)

Опубликована: Июнь 10, 2022

Abstract We herein report the preparation of a series hexaphenylbenzene (HPB)‐based deep blue‐emissive metallacages via multicomponent coordination‐driven self‐assembly. These feature prismatic structures with HPB derivatives as faces and tetracarboxylic ligands pillars, evidenced by NMR, mass spectrometry X‐ray diffraction analysis. Light‐harvesting systems were further constructed employing donor naphthalimide derivative (NAP) acceptor, owing to their good spectral overlap. The judiciously chosen metallacage serves antenna, providing suitable energy excite non‐emissive NAP, thus resulting in bright emission for NAP solid state. This study provides type HPB‐based emissive explores applications donors light up fluorophores state, which will advance development useful luminescent materials.

Язык: Английский

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Design of lanthanide based metal–organic polyhedral cages for application in catalysis, sensing, separation and magnetism

Coordination Chemistry Reviews, Год журнала: 2022, Номер 472, С. 214786 - 214786

Опубликована: Сен. 6, 2022

Lanthanide organic polyhedral cage complexes are a class of supramolecular compounds that present exciting opportunities in applications ranging from sensing to catalysis and magnetism. Metal polyhedra incorporating transition metal vertices bridged by ligands have been extensively studied. By contrast analogous lanthanide complexes, which additional benefits beyond those their counterparts, remain an underrepresented supramolecule. One unique property cages is the luminescence properties bestowed ions offer interesting imaging applications, whilst large ionic radii trivalent enables formation novel structures with incorporate ancillary not possible for structures. This review summarizes key developments synthesis characterization cages, allowing general structural trends emerge highlights already demonstrated these complexes.

Язык: Английский

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Emissive Metallacage‐Cored Polyurethanes with Self‐Healing and Shape Memory Properties

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(39)

Опубликована: Авг. 5, 2022

The structures of the crosslinks in supramolecular polymer networks play an important role on their properties and functions. Herein, emissive metallacages are used as to prepare metallacage-cored polyurethanes. mechanical including storage modulus, toughness, Young's modulus breaking strength polymers greatly enhanced with increase crosslinking densities. Moreover, such not only exhibit good fluorescence solid state, but also show self-healing shape memory owing dynamic reversible non-covalent bonds structures. This study offers a convenient strategy metallacage-crosslinked networks, explores applications materials, which will promote smart materials.

Язык: Английский

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Circularly polarized luminescence of lanthanide complexes: From isolated individuals, discrete oligomers, to hierarchical assemblies

InfoMat, Год журнала: 2022, Номер 5(3)

Опубликована: Дек. 26, 2022

Abstract Circularly polarized luminescence (CPL) is the emission featured spatial orientation equivalent to circular dichroism. Owning unique magnetic dipole‐allowed but electric‐dipole‐forbidden 4 f → transitions, chiral lanthanide complexes have been recognized as ideal candidates achieve unprecedented dissymmetry factor ( g lum ). Their inherent transition can be partly allowed, through rational design of coordination ligands lower surrounding symmetry, further endowing them with relatively high quantum yields (QYs). Moreover, blossom supramolecular chemistry in allows for construction discrete oligomers and hierarchical assemblies, rendering enhanced chiroptical activities. Here, we deploy this review by summarizing recent advances properties complexes, spanning multiple scales from isolated mononuclear individuals, polynuclear oligomers, infinite assemblies. We first introduce basic concept several important parameters assessment CPL activity. Then, coordinated different types antennas, along chirality transfer induction achiral were discussed. Next, systematical discussion on assemblies was presented. Meanwhile, state‐of‐the‐art applications CPL‐active revisited. end up conclusion prospects, involving ligands, directed hierarchically precise self‐assembly, extending complexes. image

Язык: Английский

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Construction and Hierarchical Self-Assembly of Multifunctional Coordination Cages with Triangular Metal–Metal-Bonded Units

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(13), С. 7446 - 7453

Опубликована: Март 22, 2023

Herein, a series of face-capped (Tr2M3)4L4 (Tr = cycloheptatrienyl cationic ring; M metal; L organosulfur ligand) tetrahedral cages 1-3 functionalized with 12 appended crown ether moieties were designed and synthesized. The reversible binding ammonium cations peripheral to adjust internal guest-binding was realized. Combination bisammonium linker cage 3 led the formation supramolecular gel SPN1 via host-guest interactions between salts. obtained exhibited multiple-stimuli responsiveness, injectability, excellent self-healing properties could be further developed SPN1-based drug delivery system. In addition, storage modulus 20 times higher than that model without Pd-Pd bonded blocks, had better compared latter, demonstrating importance such in improving mechanical strength losing dynamic material. cytotoxicity vitro drug-loaded (doxorubicin or methotrexate) significantly improved free drugs.

Язык: Английский

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Subtle Stereochemical Effects Influence Binding and Purification Abilities of an Fe^II₄L₄ Cage

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(9), С. 5570 - 5577

Опубликована: Фев. 27, 2023

A tetrahedral FeII4L4 cage assembled from the coordination of triangular chiral, face-capping ligands to iron(II). This exists as two diastereomers in solution, which differ stereochemistry their metal vertices, but share same point chirality ligand. The equilibrium between these was subtly perturbed by guest binding. perturbation correlated with size and shape fit within host; insight interplay provided atomistic well-tempered metadynamics simulations. understanding thus gained stereochemical impact on binding enabled design a straightforward process for resolution enantiomers racemic guest.

Язык: Английский

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Construction of Covalent Organic Cages with Aggregation‐Induced Emission Characteristics from Metallacages for Mimicking Light‐Harvesting Antenna

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июль 15, 2023

A series of covalent organic cages built from fluorophores capable aggregation-induced emission (AIE) were elegantly prepared through the reduction preorganized M2 (LA )3 (LB )2 -type metallacages, simultaneously taking advantage synthetic accessibility and well-defined shapes sizes good chemical stability as well bright AIE fluorophores. Moreover, could be further post-synthetically modified into an amide-functionalized cage with a higher quantum yield. Furthermore, these presented proved to energy donors used construct light-harvesting systems employing Nile Red acceptor. These displayed efficient transfer relatively high antenna effect, which enabled their use photocatalysts for dehalogenation reaction. This research provides new avenue development luminescent photocatalysis.

Язык: Английский

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Emergent induced circularly polarized luminescence in host–guest crystalline porous assemblies

Coordination Chemistry Reviews, Год журнала: 2024, Номер 514, С. 215859 - 215859

Опубликована: Май 9, 2024

Язык: Английский

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