Design and assembly of porous organic cages

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(17), P. 2261 - 2282

Published: Jan. 1, 2024

This comprehensive review provides various perspectives on porous organic cages, encompassing their synthesis methods, structural attributes, material properties, computational methodologies, and diverse applications.

Language: Английский

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Unraveling Early-Stage Dynamics of Cage-to-Covalent Organic Framework Transformation at Liquid–Liquid Interface

Langmuir, Journal Year: 2024, Volume and Issue: 40(31), P. 16419 - 16429

Published: July 23, 2024

Postsynthetic linker exchange (PLE) has emerged as an emerging synthetic strategy for constructing high-quality covalent organic frameworks (COFs) from preassembled entities such linear polymers, amorphous networks, COFs, and porous cages by using the principles of dynamic chemistry. The PLE recently been extended at liquid-liquid interface to fabricate highly crystalline two-dimensional (2D)-COF membranes a faster time scale (24 h). Examining early stages interfacial dynamics becomes essential understanding expedited COF growth process. In this regard, pendant drop tensiometry employed probe initial reaction imine cage-to-COF transformation through tension (IFT) measurements. contrasting trends in IFT profiles between PLE-mediated (from cage) direct synthesis parent monomers) are qualitative agreement with kinetics bulk-scale polymerizations. Further, distinct early-stage behaviors diverse routes have experimentally demonstrated tensiometry, optical microscopy, electron powder X-ray diffraction (PXRD) analysis. pivotal role situ generated intermediates (ImIs) phenomenon spontaneous emulsification toward accelerated process was delineated. current study on deploying tensiometric technique examine polymerization opens up gripping avenue mechanistic exploration PLE-based synthesis. generality developed methodology new transformation.

Language: Английский

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Effect of π-Linkages in Covalent Organic Framework-Catalyzed Light-Harvesting Thioesterification Reaction

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 24, 2025

Covalent organic frameworks (COFs) serve as an outstanding platform for heterogeneous photocatalysis. We synthesized two analogous pyrene-based two-dimensional COFs with π-conjugated networks, one linked by C═N bonds and the other C═C bonds, through Schiff base Knoevenagel condensation reactions, respectively. investigated impact of these linkages on photocatalytic activity COFs, using visible-light-mediated thioesterification a model reaction. It was found that olefin-linkage COF outperformed imine-linkage photocatalyst. The developed protocol demonstrated broad substrate scope, including 35 diverse carboxylic acids, 14 drug molecules, several disulfide coupling partners, achieving up to 95% yield thioesters. practical utility this strategy is further its successful application in gram-scale reactions. photocatalyst robust successfully reused multiple cycles without any loss catalytic activity. backbone facilitated enhanced electron transfer upon light irradiation, enabling cross-coupling acid reductive cycle.

Language: Английский

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Tandem Solid‐Solution Post‐Synthetic Modification of Porous Molecular Crystals for In‐situ Generation of Fluorophores

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(46)

Published: Aug. 10, 2024

Abstract Conventional synthetic methods of organic luminescent molecules often involve labor‐intensive solution‐phase synthesis, which violate the principles atom‐economic transformation. Post‐synthetic modification (PSM) offers a promising alternative, allowing direct transformation from one fluorophore to another. Although PSM is commonly implemented in extended frameworks, its application porous molecular crystals remains challenging. Herein, we focus on utilizing crystals, specifically tetraphenylethylene‐cored as versatile platforms for tandem reactions customize fluorophores. The tailored skeleton design ensures both formation structures and occurrence solid‐solution phase while maintaining solid state reactants products each step. inherent non‐covalent bonding nature frameworks facilitates processing characterization, offering unparalleled advantages networks. accompanying solid‐state fluorescence transition green blue then (or yellow) enables real‐time monitoring provides intuitive mechanistic insights. This phenomenon exploited facile construction dynamic information encryption system using fluorescent quick response codes.

Language: Английский

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Tandem Solid‐Solution Post‐Synthetic Modification of Porous Molecular Crystals for In‐situ Generation of Fluorophores

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 10, 2024

Conventional synthetic methods of organic luminescent molecules often involve labor-intensive solution-phase synthesis, which violate the principles atom-economic transformation. Post-synthetic modification (PSM) offers a promising alternative, allowing direct transformation from one fluorophore to another. Although PSM is commonly implemented in extended frameworks, its application porous molecular crystals remains challenging. Herein, we focus on utilizing crystals, specifically tetraphenylethylene-cored as versatile platforms for tandem reactions customize fluorophores. The tailored skeleton design ensures both formation structures and occurrence solid-solution phase while maintaining solid state reactants products each step. inherent non-covalent bonding nature frameworks facilitates processing characterization, offering unparalleled advantages networks. accompanying solid-state fluorescence transition green blue then (or yellow) enables real-time monitoring provides intuitive mechanistic insights. This phenomenon exploited facile construction dynamic information encryption system using fluorescent quick response codes.

Language: Английский

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