Chiral Metal–Organic Frameworks

Chemical Reviews, Год журнала: 2022, Номер 122(9), С. 9078 - 9144

Опубликована: Март 28, 2022

In the past two decades, metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) assembled from metal ions clusters and organic linkers via metal-ligand bonds have captivated significant scientific interest on account of their high crystallinity, exceptional porosity, tunable pore size, modularity, diverse functionality. The opportunity to achieve functional materials by design with promising properties, unattainable for solid-state in general, distinguishes MOFs other classes materials, particular, traditional such as activated carbon, silica, zeolites, thereby leading complementary properties. Scientists conducted intense research production chiral MOF (CMOF) specific applications including but not limited recognition, separation, catalysis since discovery first CMOF (i.e., d- l-POST-1). At present, CMOFs become interdisciplinary between chirality chemistry, material which involve many subjects physics, optics, medicine, pharmacology, biology, crystal engineering, environmental science, etc. this review, we will systematically summarize recent progress regarding strategies, synthetic approaches, cutting-edge applications. highlight successful implementation asymmetric catalysis, enantioselective sensing. We envision that review provide readers a good understanding chemistry and, more importantly, facilitate endeavors rational multifunctional industrial implementation.

Язык: Английский

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Tuning excited state electronic structure and charge transport in covalent organic frameworks for enhanced photocatalytic performance

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

Опубликована: Фев. 27, 2023

Covalent organic frameworks (COFs) represent an emerging class of photocatalysts. However, their complicated structures lead to indeterminacy about photocatalytic active sites and reaction mechanisms. Herein, we use reticular chemistry construct a family isoreticular crystalline hydrazide-based COF photocatalysts, with the optoelectronic properties local pore characteristics COFs modulated using different linkers. The excited state electronic distribution transport pathways in are probed host experimental methods theoretical calculations at molecular level. One our developed (denoted as COF-4) exhibits remarkable electron utilization efficiency charge transfer properties, achieving record-high uranium extraction performance ~6.84 mg/g/day natural seawater among all techniques reported so far. This study brings new understanding operation COF-based guiding design improved photocatalysts for many applications.

Язык: Английский

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Two-Dimensional Covalent Organic Frameworks with Cobalt(II)-Phthalocyanine Sites for Efficient Electrocatalytic Carbon Dioxide Reduction

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(18), С. 7104 - 7113

Опубликована: Май 3, 2021

The rapid development in synthesis methodology and applications for covalent organic frameworks (COFs) has been witnessed recent years. However, the of highly stable functional COFs still remains a great challenge. Herein two-dimensional polyimide-linked phthalocyanine (denoted as CoPc-PI-COF-1 CoPc-PI-COF-2) have devised prepared through solvothermal reaction tetraanhydrides 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with 1,4-phenylenediamine 4,4′-biphenyldiamine, respectively. resultant CoPc-PI-COFs four-connected sql net exhibit AA stacking configurations according to powder X-ray diffraction studies, showing permanent porosity, thermal stability above 300 °C, excellent resistance 12 M HCl aqueous solution 20 days. Current–voltage curves reveal conductivity CoPc-PI-COF-2 value 3.7 × 10–3 1.6 S m–1, Due same Co(II) electroactive sites together similar porosity CO2 adsorption capacity CoPc-PI-COFs, cathodes made up carbon black display CO2-to-CO Faradaic efficiency 87–97% at applied potentials between −0.60 −0.90 V (vs RHE) 0.5 KHCO3 solution. comparison CoPc-PI-COF-2&carbon electrode, counterpart provides larger current density (jCO) −21.2 mA cm–2 associated its higher conductivity. This cathode also high turnover number frequency, amounting 277 000 2.2 s–1 −0.70 during 40 h measurement. present result clearly discloses potential 2D porous crystalline solids electrocatalysis.

Язык: Английский

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Integration of metal-organic frameworks and covalent organic frameworks: Design, synthesis, and applications

Matter, Год журнала: 2021, Номер 4(7), С. 2230 - 2265

Опубликована: Июль 1, 2021

Язык: Английский

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Porous organic polymers for light-driven organic transformations

Chemical Society Reviews, Год журнала: 2022, Номер 51(7), С. 2444 - 2490

Опубликована: Янв. 1, 2022

As a new generation of porous materials, organic polymers (POPs), have recently emerged as powerful platform heterogeneous photocatalysis. POPs are constructed using extensive synthesis methodologies, with various functional units being connected via high-energy covalent bonds. This review systematically presents the recent advances in for visible-light driven transformations. Herein, we firstly summarize common construction strategies POP-based photocatalysts based on two major approaches: pre-design and post-modification; secondly, categorize methods reaction types constructing POPs. We then classify introduce specific reactions current light-driven POP-mediated Finally, outline state development problems faced transformations by POPs, present some perspectives to motivate reader explore solutions these confront challenges process.

Язык: Английский

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Three-Component Donor−π–Acceptor Covalent–Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8364 - 8374

Опубликована: Март 14, 2023

Two-dimensional covalent-organic frameworks (2D COFs) have recently emerged as great prospects for their applications new photocatalytic platforms in solar-to-hydrogen conversion; nevertheless, inefficient solar energy capture and fast charge recombination hinder the improvement of hydrogen production performance. Herein, two photoactive three-component donor-π-acceptor (TCDA) materials were constructed using a multicomponent synthesis strategy by introducing electron-deficient triazine electron-rich benzotrithiophene moieties into through sp2 carbon imine linkages, respectively. Compared with two-component COFs, novel TCDA-COFs are more convenient regulating inherent photophysical properties, thereby realizing outstanding activity evolution from water. Remarkably, first carbon-linked TCDA-COF displays an impressive rate 70.8 ± 1.9 mmol g-1 h-1 excellent reusability presence 1 wt % Pt under visible-light illumination (420-780 nm). Utilizing combination diversified spectroscopy theoretical prediction, we show that full π-conjugated linkage not only effectively broadens harvesting COFs but also enhances transfer separation efficiency.

Язык: Английский

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Metalated covalent organic frameworks: from synthetic strategies to diverse applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(15), С. 6307 - 6416

Опубликована: Янв. 1, 2022

This review highlights the recent advances of metalated covalent organic frameworks, including synthetic strategies and applications, discusses current challenges future directions.

Язык: Английский

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Multicharged cyclodextrin supramolecular assemblies

Chemical Society Reviews, Год журнала: 2022, Номер 51(11), С. 4786 - 4827

Опубликована: Янв. 1, 2022

Multicharged cyclodextrin (CD) supramolecular assemblies, including those based on positively/negatively charged modified mono-6-deoxy-CDs, per-6-deoxy-CDs, and random 2,3,6-deoxy-CDs, as well parent CDs binding guests, have been extensively applied in chemistry, materials science, medicine, biological catalysis, other fields. In this review, we primarily focus summarizing the recent advances encapsulating especially construction process of assemblies their applications. Compared with uncharged CDs, multicharged display remarkably high antiviral antibacterial activity efficient protein fibrosis inhibition. Meanwhile, can interact oppositely dyes, drugs, polymers, biomacromolecules to achieve effective encapsulation aggregation. Consequently, CD show great advantages improving drug-delivery efficiency, luminescence properties materials, molecular recognition imaging, toughness hydrogels, addition enabling multistimuli-responsive assemblies. These features are anticipated not only promote development CD-based chemistry but also contribute rapid exploitation these diverse interdisciplinary

Язык: Английский

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Crystalline C—C and C═C Bond-Linked Chiral Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2020, Номер 143(1), С. 369 - 381

Опубликована: Дек. 24, 2020

While crystalline covalent organic frameworks (COFs) linked by C–C bonds are highly desired in synthetic chemistry, it remains a formidable challenge to synthesize. Efforts generate single COFs via de novo synthesis usually afford amorphous structures rather than phases. We demonstrate here that bond-based can be prepared direct reduction of C═C bond-linked crystal-to-crystal transformation. By Knoevenagel polycondensation chiral tetrabenzaldehyde dibinaphthyl-22-crown-6 with 1,4-phenylenediacetonitrile or 4,4′-biphenyldiacetonitrile, two olefin-linked 2D layered tetragonal structure prepared. Reduction olefin linkages the as-prepared CCOFs produces bond frameworks, which retains high crystallinity and porosity as well chemical stability both strong acids bases. The quantitative is confirmed Fourier transform infrared cross-polarization magic angle spinning 13C NMR spectroscopy. Compared pristine structures, reduced display blue-shifted emission enhanced quantum yields fluorescence lifetimes, while parent exhibit higher enantioselectivity analogs when used fluorescent sensors detect amino alcohols supramolecular interactions built-in crown ether moieties. This work provides an attractive strategy for making chemically stable functionalized new otherwise hard produce.

Язык: Английский

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Highly Stable Zr(IV)-Based Metal–Organic Frameworks for Chiral Separation in Reversed-Phase Liquid Chromatography

Journal of the American Chemical Society, Год журнала: 2020, Номер 143(1), С. 390 - 398

Опубликована: Дек. 24, 2020

Separation of racemic mixtures is great importance and interest in chemistry pharmacology. Porous materials including metal–organic frameworks (MOFs) have been widely explored as chiral stationary phases (CSPs) resolution. However, it remains a challenge to develop new CSPs for reversed-phase high-performance liquid chromatography (RP-HPLC), which the most popular chromatographic mode accounts over 90% all separations. Here we demonstrated first time that highly stable Zr-based MOFs can be efficient RP-HPLC. By elaborately designing synthesizing three tetracarboxylate ligands enantiopure 1,1′-biphenyl-20-crown-6, prepared porous Zr(IV)-MOFs with framework formula [Zr6O4(OH)8(H2O)4(L)2]. They share same flu topological structure but channels different sizes display excellent tolerance water, acid, base. Chiral crown ether moieties are periodically aligned within channels, allowing stereoselective recognition guest molecules via supramolecular interactions. Under acidic aqueous eluent conditions, Zr-MOF-packed HPLC columns provide high resolution, selectivity, durability separation variety model racemates, unprotected protected amino acids N-containing drugs, comparable or even superior several commercial separation. DFT calculations suggest Zr-MOF provides confined microenvironment ethers dictates selectivity.

Язык: Английский

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