Covalent Organic Frameworks and Cage Compounds: Design and Applications of Polymeric and Discrete Organic Scaffolds

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 57(18), P. 4850 - 4878

Published: Dec. 5, 2017

Porous organic materials are an emerging class of functional nanostructures with unprecedented properties. Dynamic covalent assembly small building blocks under thermodynamic control is utilized for the intriguingly simple formation complex molecular architectures in one-pot procedures. In this Review, we aim to analyze basic design principles that govern either frameworks as crystalline porous polymers or cage compounds shape-persistent objects. Common synthetic procedures and characterization techniques will be discussed well more advanced strategies such postsynthetic modification self-sorting. When appropriate, comparisons drawn between polymeric discrete cages terms their underlying Furthermore, highlight potential these applications ranging from gas storage catalysis electronics.

Language: Английский

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Surface Coordination Chemistry of Atomically Dispersed Metal Catalysts

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(21), P. 11810 - 11899

Published: Aug. 13, 2020

Atomically dispersed metal catalysts (ADCs), as an emerging class of heterogeneous catalysts, have been widely investigated during the past two decades. The atomic dispersion nature catalytic centers makes them ideal system for bridging homogeneous and catalysts. recent rapid development new synthetic strategies has led to explosive growth ADCs with a wide spectrum atoms on supports different chemical compositions natures. availability diverse creates powerful materials platform investigating mechanisms complicated catalysis at levels. Considering most are coordinated by donors from supports, this review will demonstrate how surface coordination chemistry plays important role in determining performance ADCs. This start link between catalysis. After brief description advantages limitations common structure characterization methods ADCs, types be discussed. We mainly illustrate local vicinal species support systems act together center determine activity, selectivity, stability dynamic change highlighted. At end review, personal perspectives further field provided.

Language: Английский

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Porous Polymers as Multifunctional Material Platforms toward Task‐Specific Applications

Advanced Materials, Journal Year: 2018, Volume and Issue: 31(4)

Published: Oct. 22, 2018

Exploring advanced porous materials is of critical importance in the development science and technology. Porous polymers, being famous for their all-organic components, tailored pore structures, adjustable chemical have attracted an increasing level research interest a large number applications, including gas adsorption/storage, separation, catalysis, environmental remediation, energy, optoelectronics, health. Recent years witnessed tremendous breakthroughs these fields thanks to unique structures versatile skeletons polymers. Here, recent milestones diverse applications polymers are presented, with emphasis on structural requirements or parameters that dominate properties functionalities. The Review covers following applications: i) adsorption, ii) water treatment, iii) iv) heterogeneous v) electrochemical energy storage, vi) precursors carbons, vii) other (e.g., intelligent temperature control textiles, sensing, proton conduction, biomedicine, actuators). key each application discussed in-depth understanding structure-property relationships provided. Finally, perspective future directions challenges this field presented further studies.

Language: Английский

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Chiral 3D Covalent Organic Frameworks for High Performance Liquid Chromatographic Enantioseparation

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(3), P. 892 - 895

Published: Jan. 5, 2018

In spite of their great promise for enantioselective processes due to the rich host-guest chemistry, it remains a challenge construct covalent organic frameworks (COFs) with chiral three-dimensional (3D) structures. Here we report bottom-up synthesis first example 3D COFs by imine condensation an enantiopure 2-fold symmetric TADDOL-derived tetraaldehyde tetrahedral tetra(4-anilyl)methane. After postsynthetic oxidation linkages, framework is transformed into amide-linked COF retention crystallinity and permanent porosity as well enhanced chemical stability. The resultant isostructural feature 4-fold interpenetrated diamondoid open tubular channels decorated dihydroxy auxiliaries. Both can be used stationary phases high performance liquid chromatography enantioseparate racemic alcohols, oxidized shows superior separation compared pristine framework.

Language: Английский

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Chiral Covalent Organic Frameworks with High Chemical Stability for Heterogeneous Asymmetric Catalysis

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(25), P. 8693 - 8697

Published: June 9, 2017

Covalent organic frameworks (COFs) featuring chirality, stability, and function are of both fundamental practical interest, but yet challenging to achieve. Here we reported the metal-directed synthesis two chiral COFs (CCOFs) by imine-condensations enantiopure 1,2-diaminocyclohexane with C3-symmetric trisalicylaldehydes having one or zero 3-tert-butyl group. Powder X-ray diffraction modeling studies, together pore size distribution analysis demonstrate that Zn(salen)-based CCOFs possess a two-dimensional hexagonal grid network AA stacking. Dramatic enhancement in chemical stability toward acidic (1 M HCl) basic (9 NaOH) conditions was observed for COF incorporated tert-butyl groups on walls compared nonalkylated analog. The Zn(salen) modules allow installing multivariate metals into postsynthetic metal exchange. exchanged maintain high crystallinity porosity can serve as efficient recyclable heterogeneous catalysts asymmetric cyanation aldehydes, Diels–Alder reaction, alkene epoxidation, epoxide ring-opening, related sequential reactions up 97% ee.

Language: Английский

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