Chiral covalent organic frameworks: design, synthesis and property

Covalent organic frameworks (COFs) are constructed using reticular chemistry with the building blocks being connected via covalent bonds and have emerged as a new series of porous materials for multitudinous applications. Most COFs reported to date are achiral, and only a small fraction of COFs with chiral nature are reported. This review covers the recent advances in the field of chiral COFs (CCOFs), including their design principles and synthetic strategies, structural studies, and potential applications in asymmetric catalysis, enantioselective separation, and chiral recognition. Finally, we illustrate the remaining challenges and future opportunities in this field.

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Recent Progress in the Synthesis and Characterization of Diarylethene-based MOFs

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314087762 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C1223-C1223

Author(s):

Jason Benedict ◽

Ian Walton ◽

Dan Patel ◽

Jordan Cox

Keyword(s):

Chemical Properties ◽

Building Blocks ◽

Synthesis And Characterization ◽

Next Generation ◽

Design Synthesis ◽

Thermally Induced ◽

Potential Applications ◽

External Stimuli ◽

Physical And Chemical

Metal-organic Frameworks (MOFs) remain an extremely active area of research given the wide variety of potential applications and the enormous diversity of structures that can be created from their constituent building blocks. While MOFs are typically employed as passive materials, next-generation materials will exhibit structural and/or electronic changes in response to applied external stimuli including light, charge, and pH. Herein we present recent results in which advanced photochromic diarylethenes are combined with MOFs through covalent and non-covalent methods to create photo-responsive permanently porous crystalline materials. This presentation will describe the design, synthesis, and characterization of next-generation photo-switchable diarylethene based ligands which are subsequently used to photo-responsive MOFs. These UBMOF crystals are, by design, isostructural with previously reported non-photoresponsive frameworks which enables a systematic comparison of their physical and chemical properties. While the photoswitching of the isolated ligand in solution is fully reversible, the cycloreversion reaction is suppressed in the UBMOF single crystalline phase. Spectroscopic evidence for thermally induced cycloreversion will be presented, as well as a detailed analysis addressing the limits of X-ray diffraction techniques applied to these systems.

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Chiral covalent organic frameworks: design, synthesis and property

Chemical Society Reviews ◽

10.1039/d0cs00009d ◽

2020 ◽

Vol 49 (17) ◽

pp. 6248-6272 ◽

Cited By ~ 4

Author(s):

Xing Han ◽

Chen Yuan ◽

Bang Hou ◽

Lujia Liu ◽

Haiyang Li ◽

...

Keyword(s):

Heterogeneous Catalysis ◽

Structural Features ◽

Enantioselective Separation ◽

Covalent Organic Frameworks ◽

Design Synthesis

Owing to the unique structural features and facile tunability of the subcomponents and channels, chiral COFs show great potential in heterogeneous catalysis, enantioselective separation, and recognition.

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Sequential Single-Crystal-to-Single-Crystal Vapochromic inclusion in non-porous coordination polymer: Unravelling dynamic rearrangement for selective pyridine sensing

Inorganic Chemistry Frontiers ◽

10.1039/d1qi00059d ◽

2021 ◽

Author(s):

Estefania Fernandez-Bartolomé ◽

Esther Resines-Urien ◽

Maria Murillo-Vidal ◽

Lucia Piñeiro-Lopez ◽

Jose Sanchez Costa

Keyword(s):

Coordination Polymer ◽

Single Crystal ◽

Porous Materials ◽

Metal Organic Frameworks ◽

Covalent Organic Frameworks ◽

Potential Applications ◽

Metal Organic ◽

Porous Coordination Polymer

Alternative porous materials beyond zeolites, such as metal-organic frameworks (MOF) or covalent organic frameworks (COF), have provided a variety of materials with potential applications ranging from sensing to catalysis. However,...

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Optoelectronic processes in covalent organic frameworks

Chemical Society Reviews ◽

10.1039/d0cs00793e ◽

2021 ◽

Author(s):

Niklas Keller ◽

Thomas Bein

Keyword(s):

Electron Transfer ◽

Porous Materials ◽

Building Blocks ◽

Covalent Organic Frameworks ◽

Molecular Building Blocks ◽

Donor Acceptor

Covalent organic frameworks (COFs) are crystalline porous materials constructed from molecular building blocks using diverse linkage chemistries. The image illustrates electron transfer in a COF-based donor–acceptor system. Image by Nanosystems Initiative Munich.

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Enantiospecificity in achiral zeolites for asymmetric catalysis

Physical Chemistry Chemical Physics ◽

10.1039/d0cp00262c ◽

2020 ◽

Vol 22 (34) ◽

pp. 18757-18764

Author(s):

Tianxiang Chen ◽

Ching Kit Tommy Wun ◽

Sarah J. Day ◽

Chiu C. Tang ◽

Tsz Woon Benedict Lo

Keyword(s):

Porous Materials ◽

Asymmetric Catalysis ◽

Potential Applications

We highlight the recent study in using chiral and achiral porous materials for the potential applications in asymmetric catalysis.

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Organocatalytic atroposelective synthesis of axially chiral styrenes

Nature Communications ◽

10.1038/ncomms15238 ◽

2017 ◽

Vol 8 (1) ◽

Cited By ~ 40

Author(s):

Sheng-Cai Zheng ◽

San Wu ◽

Qinghai Zhou ◽

Lung Wa Chung ◽

Liu Ye ◽

...

Keyword(s):

Asymmetric Catalysis ◽

Addition Reaction ◽

Building Blocks ◽

Biologically Active Compounds ◽

Biologically Active ◽

Active Compounds ◽

Chiral Compounds ◽

Axially Chiral ◽

Potential Applications ◽

Styrene Derivatives

Abstract Axially chiral compounds are widespread in biologically active compounds and are useful chiral ligands or organocatalysts in asymmetric catalysis. It is well-known that styrenes are one of the most abundant and principal feedstocks and thus represent excellent prospective building blocks for chemical synthesis. Driven by the development of atroposelective synthesis of axially chiral styrene derivatives, we discovered herein the asymmetric organocatalytic approach via direct Michael addition reaction of substituted diones/ketone esters/malononitrile to alkynals. The axially chiral styrene compounds were produced with good chemical yields, enantioselectivities and almost complete E/Z-selectivities through a secondary amine-catalysed iminium activation strategy under mild conditions. Such structural motifs are important precursors for further transformations into biologically active compounds and synthetic useful intermediates and may have potential applications in asymmetric synthesis as olefin ligands or organocatalysts.

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Covalent Organic Frameworks: New Materials Platform for Photocatalytic Degradation of Aqueous Pollutants

Materials ◽

10.3390/ma14195600 ◽

2021 ◽

Vol 14 (19) ◽

pp. 5600

Author(s):

Yuhang Qian ◽

Dongge Ma

Keyword(s):

Near Infrared ◽

Gas Adsorption ◽

Degradation Mechanism ◽

Co2 Reduction ◽

Polymeric Materials ◽

Structural Type ◽

Research Area ◽

Covalent Organic Frameworks ◽

Covalent Bonds ◽

Potential Applications

Covalent organic frameworks (COFs) are highly porous and crystalline polymeric materials, constructed by covalent bonds and extending in two or threedimensions. After the discovery of the first COF materials in 2005 by Yaghi et al., COFs have experienced exciting progress and exhibitedtheirpromising potential applications invarious fields, such as gas adsorption and separation, energy storage, optoelectronics, sensing and catalysis. Because of their tunablestructures, abundant, regular and customizable pores in addition to large specific surface area, COFs can harvest ultraviolet, visible and near-infrared photons, adsorb a large amount of substrates in internal structures and initiate surface redox reactions to act as effective organic photocatalysts for water splitting, CO2 reduction, organic transformations and pollutant degradation. In this review, we will discuss COF photocatalysts for the degradation of aqueous pollutants. The state-of-the-art paragon examples in this research area will be discussed according to the different structural type of COF photocatalysts. The degradation mechanism will be emphasized. Furthermore, the future development direction, challenges required to be overcome and the perspective in this field will be summarized in the conclusion.

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Three-Dimensional Triptycene-Based Covalent Organic Frameworks with ceq or acs Topology

10.26434/chemrxiv.13311602.v1 ◽

2020 ◽

Author(s):

Hui Li ◽

Fengqian Chen ◽

Xinyu Guan ◽

JIali Li ◽

Cuiyan Li ◽

...

Keyword(s):

Three Dimensional ◽

Building Blocks ◽

Triangular Prism ◽

Covalent Organic Frameworks ◽

Related Field ◽

Design And Synthesis ◽

Connected Node ◽

Potential Applications ◽

Complex Building ◽

Adsorption Of Co

<a>The growth of three-dimensional covalent organic frameworks (3D COFs) with new topologies is still considered as a great challenge due to limited availability of high-connectivity building units. Here we report the design and synthesis of novel 3D triptycene-based COFs, </a><a></a><a>termed</a> JUC-568 and JUC-569, following the deliberate symmetry-guided design principle. By combining a triangular prism (6-connected) node with a planar triangle (3-connected) or another triangular prism node, the targeted COFs adopt unreported ceq or non-interpenetrated acs topology, respectively. <a>Both materials</a> show permanent porosity and impressive performance <a>in the adsorption of CO2</a> (~ 98 cm3/g at 273 K and 1 bar), CH4 (~ 48 cm3/g at 273 K and 1 bar), and especially H2 (up to 274 cm3/g or 2.45 wt% at 77 K and 1 bar), which is <a>highest </a>among <a>porous organic materials</a> reported to date. This research thus provides a promising strategy for diversifying 3D COFs based on complex building blocks and promotes their <a></a><a>potential applications</a> <a>in</a><a></a><a> energy storage and environment-related field</a>s.

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Three-Dimensional Triptycene-Based Covalent Organic Frameworks with ceq or acs Topology

10.26434/chemrxiv.13311602 ◽

2020 ◽

Author(s):

Hui Li ◽

Fengqian Chen ◽

Xinyu Guan ◽

JIali Li ◽

Cuiyan Li ◽

...

Keyword(s):

Three Dimensional ◽

Building Blocks ◽

Triangular Prism ◽

Covalent Organic Frameworks ◽

Related Field ◽

Design And Synthesis ◽

Connected Node ◽

Potential Applications ◽

Complex Building ◽

Adsorption Of Co

<a>The growth of three-dimensional covalent organic frameworks (3D COFs) with new topologies is still considered as a great challenge due to limited availability of high-connectivity building units. Here we report the design and synthesis of novel 3D triptycene-based COFs, </a><a></a><a>termed</a> JUC-568 and JUC-569, following the deliberate symmetry-guided design principle. By combining a triangular prism (6-connected) node with a planar triangle (3-connected) or another triangular prism node, the targeted COFs adopt unreported ceq or non-interpenetrated acs topology, respectively. <a>Both materials</a> show permanent porosity and impressive performance <a>in the adsorption of CO2</a> (~ 98 cm3/g at 273 K and 1 bar), CH4 (~ 48 cm3/g at 273 K and 1 bar), and especially H2 (up to 274 cm3/g or 2.45 wt% at 77 K and 1 bar), which is <a>highest </a>among <a>porous organic materials</a> reported to date. This research thus provides a promising strategy for diversifying 3D COFs based on complex building blocks and promotes their <a></a><a>potential applications</a> <a>in</a><a></a><a> energy storage and environment-related field</a>s.

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