Revolutionizing the structural design and determination of covalent–organic frameworks: principles, methods, and techniques

Chemical Society Reviews, Год журнала: 2023, Номер 53(1), С. 502 - 544

Опубликована: Дек. 15, 2023

Covalent organic frameworks (COFs) represent an important class of crystalline porous materials with designable structures and functions. The interconnected monomers, featuring pre-designed symmetries connectivities, dictate the COFs, endowing them high thermal chemical stability, large surface area, tunable micropores. Furthermore, by utilizing pre-functionalization or post-synthetic functionalization strategies, COFs can acquire multifunctionalities, leading to their versatile applications in gas separation/storage, catalysis, optoelectronic devices. Our review provides a comprehensive account latest advancements principles, methods, techniques for structural design determination COFs. These cutting-edge approaches enable rational precise elucidation COF structures, addressing fundamental physicochemical challenges associated host-guest interactions, topological transformations, network interpenetration, defect-mediated catalysis.

Язык: Английский

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Unravelling nonclassical beam damage mechanisms in metal-organic frameworks by low-dose electron microscopy

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 2, 2025

Язык: Английский

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Three-Dimensional Crystalline Organic Framework Stabilized by Molecular Mortise-and-Tenon Jointing

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12547 - 12555

Опубликована: Апрель 24, 2024

Three-dimensional (3D) crystalline organic frameworks with complex topologies, high surface area, and low densities afford a variety of application prospects. However, the design construction these have been largely limited to systems containing polyhedron-shaped building blocks or those relying on component interpenetration. Here, we report synthesis 3D framework based molecular mortise-and-tenon jointing. This new material takes advantage tetra(4-pyridylphenyl)ethylene chlorinated bis(benzodioxaborole)benzene as is driven by dative B-N bonds. A single-crystal X-ray diffraction analysis reveals presence two-dimensional (2D) layers helical channels that are formed presumably during boron-nitrogen coordination process. The protrusion dichlorobenzene units from upper lower surfaces 2D facilitates key connections. These connections enable interlocking adjacent stabilization an overall framework. resulting endowed porosity attractive mechanical properties, rendering it potentially suitable for removal impurities acetylene.

Язык: Английский

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Constructing Covalent Organic Polymers through Dative B─N Bonds: Synthesis, Single Crystal Structures, and Physical Properties

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Март 10, 2024

Abstract Growing single crystals of covalent organic polymers (COPs) for single‐crystal X‐ray diffraction analysis is very important and highly desirable because such strategy provides a deep understanding crystallization kinetics the structure‐property relationship COPs. Based on that dynamic bonds can allow self‐correction structures during crystal growth, two COPs ( CityU‐15 CityU‐16 ) based dative boron‐nitrogen (B─N) have been successfully obtained. Detailly, tetra(4‐pyridyl)tetrathiafulvalene (TTF(py) 4 tetra(4‐pyridyl)porphine (TPYP) are employed as N‐donor ligands to react with 1,4‐bis(benzodioxaborole) benzene prepare COPs, named , respectively. exhibits enhanced stability compared size reach up 0.7 cm. shows good recyclability reveals noticeable photosensitivity upon iodine doping. After treatment iodine, both display obvious color changes. Specially, device I 2 ‐treated excellent low‐voltage operation low energy consumption 3.3 fJ, facilitating development artificial vision. This work highlights successful introduction functional groups into B‐N‐containing opening new avenues expanding their applications.

Язык: Английский

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A recyclable polyurethane with characteristic thermal stiffening behavior via B-N coordination with reversible B-O bonds

Science China Materials, Год журнала: 2024, Номер 67(10), С. 3339 - 3346

Опубликована: Авг. 5, 2024

Язык: Английский

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Adaptive and Robust Vitrimers Fabricated by Synergy of Traditional and Supramolecular Polymers

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 8, 2024

Abstract Vitrimers offer a unique combination of mechanical performance, reprocessability, and recyclability that makes them highly promising for wide range applications. However, achieving dynamic behavior in vitrimeric materials at their intended usage temperatures, thus combining reprocessability with adaptivity through associative covalent bonds, represents an attractive but formidable objective. Herein, we couple boron‐nitrogen (B−N) dative bonds B−O to generate new class vitrimers, vitrimers (BNVs), endow features temperatures. Compared boron‐ester (BEVs) without B−N the BNVs showcase enhanced performance. The excellent properties come from synergistic effect supramolecular polymer networks. Moreover, benefiting exchange above topological freezing temperature ( T v ), resultant also possess processability. This study leveraged structural characteristics boron‐based vitrimer achieve material reinforcement toughness enhancement, simultaneously providing novel design concepts construction materials.

Язык: Английский

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Crystalline Porous Organic Frameworks Based on Multiple Dynamic Linkages

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(28)

Опубликована: Апрель 24, 2024

Abstract A novel class of crystalline porous materials has been developed utilizing multilevel dynamic linkages, including covalent B−O, dative B←N and hydrogen bonds. Typically, boronic acids undergo in situ condensation to afford B 3 O ‐based units, which further extend molecular complexes or chains via The obtained superstructures are subsequently interconnected bonds π–π interactions, producing organic frameworks (CPOFs). CPOFs display excellent solution processability, allowing dissolution subsequent crystallization their original structures, independent recrystallization conditions, possibly due the diverse bond energies involved interactions. Significantly, can be synthesized on a gram‐scale using cost‐effective monomers. In addition, numerous acidic sites endow with high NH capacity, surpassing most commercial materials.

Язык: Английский

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Self-Healing B ← N-Based Hydrogen-Bonded Organic Framework for Exclusive Recognition and Separation of Toluene from Methyl-Cyclohexane

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19425 - 19433

Опубликована: Июль 1, 2024

The effective separation of aromatic and aliphatic hydrocarbons remains a notable challenge in the petrochemical industry. Herein, we report self-healing three-dimensional B ← N-based hydrogen-bonded organic framework (HOF), BN-HOF-1, constructed from discrete N inclusive dimers through weak C–H···F C–H···N hydrogen-bonding interactions. To make use specific recognition for toluene molecules reversible ad/desorption nature this novel HOF, BN-HOF-1 can exclusively recognize separate mixtures toluene-methylcyclohexane, thus generating 99.6% pure its after gentle heating, recorded value among any reported materials purification. After were released framework, it becomes condensed BN-HOF-1a, which be further reused highly selective purification binary mixtures, structural recovery back to BN-HOF-1. Single-crystal X-ray diffraction molecular modeling studies reveal that high is attributed complementary electrostatic potential between host guest toluene, while HOF intermolecular

Язык: Английский

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A Covalent Organic Nanoribbon: Preparation, Single‐Crystal Structure with Chinese Luban Lock Configuration, and Photocatalytic Behavior

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июнь 27, 2024

Abstract The multiple mortise‐and‐tenon joint parts are the core factors to provide structural stability and diversity of Chinese Luban locks; however, constructing such structures is very challenging. Herein, single crystals a covalent organic nanoribbon (named CityU‐27 ) prepared through assembly hexahydroxytriphenylene (HHTP), 4,4′‐vinylenedipyridine (BYE), phenylboronic acid (BA) together dative boron←nitrogen (B←N) bonds. single‐crystal X‐ray diffraction analysis indicates that has structure, where each forms tight π–π interactions with four neighboring others generate lock‐like configuration. been demonstrated be an efficient photocatalyst in one‐pot tandem reaction hydrogen evolution (HER) semi‐hydrogenation alkynes series produce olefins without any additional photosensitizers co‐catalysts (metal‐free).

Язык: Английский

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High-Molecular-Weight Poly[2]catenanes Prepared by Hydroxyl-Alkyne Click Chemistry

Macromolecules, Год журнала: 2024, Номер 57(8), С. 3824 - 3830

Опубликована: Апрель 10, 2024

Due to the combination of flexibility and mobility, polycatenanes have potential in constructing various functional materials. To date, most previous works reported poly[2]catenanes with a degree polymerization (DP) around 20. However, it remains significant challenge synthesize higher DP value. Hydroxyl–yne click polymerization, bearing merits obtaining polymers high values, short reaction time, mild condition, is promising be employed preparing values. Herein, strategy using hydroxyl–yne chemistry fabricate was proposed. With two hydroxyl groups on both rings, [2]catenane monomer M1 prepared. Meanwhile, hexaethylene glycol alkyne functionalized as M2. bicyclo[2.2.2]-1,4-diazaoctane (DABCO) catalyzing, M2 reacted via at room temperature. The resultant poly[2]catenane reached up 36. In addition, tetraphenylethylene (TPE) modified propiolic acid obtain M3. Then, poly([2]catenane-alt-TPE) aggregation-induced emission (AIE) properties obtained between M3 well.

Язык: Английский

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