Picking the lock of coordination cage catalysis

Chemical Science, Год журнала: 2023, Номер 14(41), С. 11300 - 11331

Опубликована: Янв. 1, 2023

We provide an overview of coordination cage catalysis, highlighting how mechanistic understanding can help address the challenges in this area leading to new opportunities non-covalent reactivity.

Язык: Английский

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Counteranion-mediated efficient iodine capture in a hexacationic imidazolium organic cage enabled by multiple non-covalent interactions

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Сен. 28, 2023

Developing efficient adsorbents to capture radioactive iodine produced from nuclear wastes is highly desired. Here we report the facial synthesis of a hexacationic imidazolium organic cage and its adsorption properties. Crucial role counteranions has been disclosed for with this cage, where distinct behaviors were observed when different used. Mechanistic investigations, especially X-ray crystallographic analysis iodine-loaded sample, allowed direct visualization binding modes at molecular level. A network multiple non-covalent interactions including hydrogen bonds, halogen anion···π interactions, electrostatic interaction between polyiodides skeleton are found responsible high performance. Our results may provide an alternative strategy design adsorbents.

Язык: Английский

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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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Heteromeric Completive Self-Sorting in Coordination Cage Systems

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 6905 - 6911

Опубликована: Фев. 29, 2024

Heteroleptic coordination cages, nonstatistically assembled from a set of matching ligands, can be obtained by mixing individual components or via cage-to-cage transformations homoleptic precursors. Based on the latter approach, we here describe new level self-sorting in cage systems, namely, 'heteromeric completive self-sorting'. Here, two heteroleptic assemblies type Pd2A2B2 and Pd2A2C2, sharing one common ligand component A but differing other, are shown to coexist solution. This reached either statistical mixture based some ligands B C or, alternatively, following first step integrative giving distinct Pd2B2C2 intermediate. While subtle enthalpic factors dictate outcome self-sorting, found that it is controllable. From unique three demonstrate transition strict forming Pd2AB2C heteromeric give Pd2A2C2 variation ratio. Cage-to-cage were followed NMR MS experiments. Single crystal X-ray structures for cages obtained, impressively highlighting versatility form π-stacked trans-figure-of-eight arrangement occupy cis-edges only single edge Pd2AB2C. study paves way toward control populations systems chemistry context with emerging features such as chemical information processing, adaptive guest selectivity, stimuli-responsive catalytic action.

Язык: Английский

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Light-Powered Reversible Guest Release and Uptake from Zn₄L₄ Capsules

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 3828 - 3832

Опубликована: Фев. 8, 2023

A strategy for light-powered guest release from a tetrahedral capsule has been developed by incorporating azobenzene units at its vertices. new Zn

Язык: Английский

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Assembly of Six Types of Heteroleptic Pd₂L₄ Cages under Kinetic Control

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(51), С. 28061 - 28074

Опубликована: Дек. 14, 2023

Heteroleptic assemblies composed of several kinds building blocks have been seen in nature. It is still unclear how natural systems design and create such complicated selectively. Past efforts on multicomponent self-assembly artificial metal-organic cages mainly focused finding a suitable combination to lead single as the thermodynamically most stable product. Here, we present another approach selectively produce Pd(II)-based self-assemblies under kinetic control based selective ligand exchanges weak Pd-L coordination bonds retaining original orientation metal centers kinetically stabilized cyclic structure local reversibility given certain areas energy landscape presence assist molecule that facilitates error correction bonds. The enabled us build all six types Pd

Язык: Английский

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Structural Switching of a Distorted Trigonal Metal‐Organic Cage to a Tetragonal Cage and Singlet Oxygen Mediated Oxidations

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(28)

Опубликована: Май 11, 2023

Construction of metal-organic cages with unique architecture and guest binding abilities is highly desirable. Herein, we report the synthesis a distorted trigonal cage (1) from twisted tetratopic ligand (L) PdII acceptor. Surprisingly, 1 exhibited complete structural reorganization its building units in presence C70 C60 to form guest-encapsulated tetragonal cages, (C70 )2 @2 (C60 @2, respectively. These guest-bound were found be potential O2 generators, former effectively catalyzing two different varieties -mediated oxidation reactions.

Язык: Английский

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Tailor‐Made Pd_nL_2n Metal‐Organic Cages through Covalent Post‐Synthetic Modification

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(14)

Опубликована: Фев. 8, 2023

Post-synthetic modification (PSM) is an effective approach for the tailored functionalization of metal-organic architectures, but its generalizability remains challenging. Herein we report a general covalent PSM strategy to functionalize Pdn L2n cages (MOCs, n=2, 12) through efficient Diels-Alder cycloaddition between peripheral anthracene substituents and various functional motifs bearing maleimide group. As expected, solubility functionalized Pd12 L24 in common solvents can be greatly improved. Interestingly, concentration-dependent circular dichroism aggregation-induced emission are achieved with chiral binaphthol (BINOL)- tetraphenylethylene-modified , respectively. Furthermore, introduced two different groups (e.g., BINOL achiral pyrene) step-by-step route obtain chirality-induced circularly polarized luminescence. Moreover, similar results readily observed smaller Pd2 L4 system.

Язык: Английский

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Enhancing the Photosensitivity of Hypocrellin A by Perylene Diimide Metallacage-Based Host–Guest Complexation for Photodynamic Therapy

Nano-Micro Letters, Год журнала: 2024, Номер 16(1)

Опубликована: Июнь 25, 2024

The development of supramolecular hosts which can efficiently encapsulate photosensitizers to improve the photodynamic efficacy holds great promise for cancer therapy. Here, we report two perylene diimide-based metallacages that form stable host-guest complexes with planar conjugated molecules including polycyclic aromatic hydrocarbons and (hypocrellin A). Such complexation not only prevents aggregation in aqueous environments, but also offers fluorescence resonance energy transfer (FRET) from metallacage further singlet oxygen generation (Φ

Язык: Английский

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Triamine and Tetramine Edge-Length Matching Drives Heteroleptic Triangular and Tetragonal Prism Assembly

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5215 - 5223

Опубликована: Фев. 13, 2024

Heteroleptic metal–organic capsules, which incorporate more than one type of ligand, can provide enclosed, anisotropic interior cavities for binding low-symmetry molecules biological and industrial importance. However, the selective self-assembly a single mixed-ligand architecture, as opposed to numerous other possible outcomes, remains challenge. Here, we develop design strategy subcomponent heteroleptic architectures with internal void spaces. Zn6Tet3Tri2 triangular prismatic Zn8Tet2Tet′4 tetragonal were prepared through careful matching side lengths tritopic (Tri) or tetratopic (Tet, Tet′) panels.

Язык: Английский

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