Coordination-Directed Self-Assembly of Functional Polynuclear Lanthanide Supramolecular Architectures

Chemical Reviews, Год журнала: 2022, Номер 122(6), С. 6374 - 6458

Опубликована: Фев. 8, 2022

Lanthanide supramolecular chemistry is a fast growing and intriguing research field due to the unique photophysical, magnetic, coordination properties of lanthanide ions (LnIII). Compared with intensively investigated mononuclear Ln-complexes, polymetallic assemblies offer more structural superiority functional advantages. In recent decades, significant progress has been made in polynuclear supramolecules, varying from evolution luminescent magnetic materials. This review summarizes design principles ligand-induced coordination-driven self-assembly Ln-structures intends guidance for construction elegant Ln-based architectures optimization their performances. Design concerning water solubility chirality lanthanide-organic that are vital extending applications emphasized. The strategies improving up-conversion, host–guest chemistry, sensing, catalysis have summarized. Magnetic materials based on assembled given an individual section classified features. Challenges remaining perspective directions this also briefly discussed.

Язык: Английский

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Guest-Driven Self-Assembly and Chiral Induction of Photofunctional Lanthanide Tetrahedral Cages

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(9), С. 4244 - 4253

Опубликована: Фев. 23, 2022

Chiral luminescent lanthanide–organic cages have many potential applications in enantioselective recognition, sensing, and asymmetric catalysis. However, due to the paucity of structures their limited cavities, host–guest chemistry with has remained elusive so far. Herein, we report a guest-driven self-assembly chiral induction approach for construction otherwise inaccessible Ln4L4-type (Ln = lanthanide ions, i.e., EuIII, TbIII; L ligand) tetrahedral hosts. Single crystal analyses on series complexes reveal remarkable guest-adaptive cavity breathing cages, reflecting advantage variation tolerance coordination geometry f-elements. Meanwhile, noncovalent confinement pyrene within cage not only leads diminishment its excimer emission but also facilitates guest host energy transfer, opening up new sensitization window luminescence cage. Moreover, stereoselective either Λ4- or Δ4- type Eu4L4 been realized via R/S-BINOL R/S-SPOL templates, as confirmed by NMR, circular dichroism (CD), circularly polarized (CPL) high dissymmetry factors (glum) ±0.125.

Язык: Английский

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Strategies to address key challenges of metallacycle/metallacage-based supramolecular coordination complexes in biomedical applications

Chemical Society Reviews, Год журнала: 2024, Номер 53(6), С. 3167 - 3204

Опубликована: Янв. 1, 2024

We report strategies employed by metallacycle/metallacage-based supramolecular coordination complexes to enhance water solubility and biostability reduce potential toxicity side effects for biomedical applications.

Язык: Английский

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Hexameric Lanthanide–Organic Capsules with Tertiary Structure and Emergent Functions

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(16), С. 6202 - 6210

Опубликована: Апрель 19, 2021

Biological macromolecules always function through a collective behavior of the aggregated constituents, which usually are self-assembled together via noncovalent interactions. Likewise, artificial supramolecular assemblies, whose properties and functions mainly derived from their primary secondary structures, may also aggregate into high-order architectures with emergent not available on individual components. Here we report first example an insulin-like hexamerization lanthanide triple helicates toward 4 nm diameter hexameric capsule consecutive metal-directed anion-directed assembly processes. Hierarchical chiral-sorting self-assembly endows hexamers aggregation-induced stability emission enhancement. Furthermore, guest-encapsulation enantioselectivity terpene drugs have been realized in late-formed central cavity hexamers. This study only provides feasible strategy for constructing sophisticated multifunctional lanthanide–organic materials but sheds some light processes nature.

Язык: Английский

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Metallacycles, metallacages, and their aggregate/optical behavior

Aggregate, Год журнала: 2021, Номер 2(5)

Опубликована: Июнь 24, 2021

Abstract Since the first metallacycle was prepared by Verkade in 1983, various metallacycles and metallacages with controllable nanoscale shapes sizes have been created modular design synthesis, showing unique properties that enable applications catalysis, sensors, biomedicine. Everything from their photophysical to antitumor activities catalysis found be influenced suprastructures. Thus, it is necessary helpful develop a systematic understanding of relationships among micro/nanostructures, resultant photophysical/chemical properties, corresponding applications. In this review, we summarized latest progress area approximately past 5 years.

Язык: Английский

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A Redox-Active Supramolecular Fe₄L₆ Cage Based on Organic Vertices with Acid–Base-Dependent Charge Tunability for Dehydrogenation Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(19), С. 8778 - 8788

Опубликована: Май 4, 2022

Supramolecular cage chemistry is of lasting interest because, as artificial blueprints natural enzymes, the self-assembled structures not only provide substrate-hosting biomimetic environments but also can integrate active sites in confined nanospaces for function synergism. Herein, we demonstrate a vertex-directed organic-clip chelation assembly strategy to construct metal–organic Fe4L68+ (MOC-63) incorporating 12 imidazole proton donor–acceptor motifs and four redox-active Fe centers an octahedral coordination nanospace. Different from regular supramolecular cages assembled with metal vertices, MOC-63 comprises six ditopic ligands vertices tris-chelating Fe(N∩N)3 moieties faces, thus improving its acid, base, redox robustness by virtue cage-stabilized dynamics solution. Improved dehydrogenation catalysis 1,2,3,4-tetrahydroquinoline derivatives accomplished owing effect that synergizes multiple radical species expedite intermediate conversion multistep reactions cage-confined The acid–base buffering play vital role modulating total charge state resist pH variation tune solubility among varied solvents, thereby enhancing reaction acceleration acidic conditions rendering facile recycling catalytic process.

Язык: Английский

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Hierarchically Porous Organic Cages

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(22), С. 12490 - 12497

Опубликована: Март 11, 2021

Abstract Imparting mesopores to organic cages of an intrinsic microporous nature build up hierarchically porous cage soft materials is a grand challenge and will reshape the property application scope traditional molecules. Herein, we discovered how engineer into via their host–guest interactions with long chain ionic surfactants. Equally important, head surfactants equips supramolecularly assembled structures charge‐selective uptake release function in solution. Interestingly, such can serve as nanoreactor once trapping enzymes within cavity, which show 5‐fold enhanced activity enzymatic catalysis when compared free enzymes.

Язык: Английский

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One‐Pot and Shape‐Controlled Synthesis of Organic Cages

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(33), С. 17904 - 17909

Опубликована: Май 26, 2021

Abstract Organic cages are fascinating because of their well‐defined 3D cavities, excellent stability, and accessible post‐modification. However, the synthesis is normally realized by fragment coupling approach in low yields. Herein, we report one‐pot, gram‐scale shape‐controlled two covalent organic (box‐shaped [4]cage triangular prism‐shaped [2]cage) yields 46 % 52 %, involving direct condensation 1,3,5‐tris(2,4‐dimethoxyphenyl)benzene monomer with paraformaldehyde isobutyraldehyde, respectively. The can convert into high‐yielding per‐hydroxylated analogues. [2]cage be utilized as gas chromatographic stationary phase for high‐resolution separation benzene/cyclohexane toluene/methylcyclohexane. By changing central moiety and/or aldehyde, this synthetic method would have potential to a general strategy access diverse tunable shape, size, electronic properties.

Язык: Английский

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Functionalization of luminescent lanthanide complexes for biomedical applications

Coordination Chemistry Reviews, Год журнала: 2022, Номер 474, С. 214866 - 214866

Опубликована: Окт. 8, 2022

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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