Unveiling the Local Structure of Palladium Loaded into Imine‐Linked Layered Covalent Organic Frameworks for Cross‐Coupling Catalysis

Layered covalent organic frameworks (2D‐COFs), composed of reversible imine linkages and accessible pores, offer versatility for chemical modifications towards the development of catalytic materials. Nitrogen‐enriched COFs are good candidates for binding Pd species. Understanding the local structure of reacting Pd sites bonded to the COF pores is key to rationalize interactions between active sites and porous surfaces. By combining advanced synchrotron characterization methods with periodic computational DFT modeling, the precise atomic structure of catalytic Pd sites attached to local defects is resolved within an archetypical imine‐linked 2D‐COF. This material was synthesized using an in situ method as a gel, under which imine hydrolysis and metalation reactions are coupled. Local defects formed in situ within imine‐linked 2D‐COF materials are highly reactive towards Pd metalation, resulting in active materials for Suzuki–Miyaura cross‐coupling reactions.     

Recent Advances in Covalent Organic Frameworks for Catalysis

Covalent organic frameworks (COFs) as an emerging type of crystalline porous materials, have obtained considerable attention recently. They have exhibited diverse structure and attractive performance in various catalytic reactions. It is highly expected to have a systematic and comprehensive review summing up COFs‐derived catalysts in homogeneous and heterogeneous catalysis, which is favorable to the judicious design of an efficient catalyst for targeted reaction. Herein, we focus on summarizing recent and significant developments in COFs materials, with an emphasis on both the synthetic strategies and targeted functionalization, and categorize it in accordance with the different types of catalytic reactions. Their potential catalysis applications are reviewed thoroughly. Moreover, a personal view about the future development of COFs catalysts with respect to the large‐scale production is also discussed.     

Homochiral Covalent Organic Frameworks for Asymmetric Catalysis

Owing to their permanent porosity, highly ordered and extended structure, good chemical stability, and tunability, covalent organic frameworks (COFs) have emerged as a new type of organic materials that can offer various applications in different fields. Benefiting from the huge database of organic reactions, the required functionality of COFs can be readily achieved by modification of the corresponding organic functional groups on either polymerizable monomers or established COF frameworks. This striking feature allows homochiral covalent organic frameworks (HCCOFs) to be reasonably designed and synthesized, as well as their use as a unique platform to fabricate asymmetric catalysts. This contribution provides an overview of new progress in HCCOF-based asymmetric catalysis, including design, synthesis, and their application in asymmetric organic synthesis. Moreover, major challenges and developing trends in this field are also discussed. It is anticipated that this review article will provide some new insights into HCCOFs for heterogeneous asymmetric catalysis and help to encourage further contributions in this young but promising field.     

共价有机框架材料催化剂

共价有机框架材料（covalent organic frameworks, COF）是功能材料领域研究的热点之一。COF具有孔道结构高度有序、孔径可调、比表面积较大、合成方法多样和易于功能化修饰等优点,是一类新兴的多相催化剂。目前,COF催化剂主要设计思路是：基于“自下而上”策略将非金属催化活性中心嵌入材料骨架来构筑本征型COF催化剂,或者以COF为载体,通过后修饰方式负载金属颗粒或离子构建多相催化剂。鉴于COF以上优势,预计COF催化剂在多相催化和手性催化领域中的应用也将取得更大的进展。本文综述了COF催化剂的合成和功能化策略,并展望了COF在多相催化领域中的应用前景。     

Design of Photoactive Covalent Organic Frameworks as Heterogeneous Catalyst for Preparation of Thiophosphinates from Phosphine Oxides and Thiols

Two new covalent organic frameworks (COFs) were synthesized from 4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetrayl)tetraaniline and 2,5-dimethoxyterephthalaldehyde (Py-DMTA-COF) or 2′,5′-dimethoxy-[1,1′:4′,1′′-terphenyl]-4,4′′-dicarbaldehyde (Py-DMTPDA-COF) under solvothermal conditions. These two COFs were further facilely developed as efficient photocatalytic platforms for the synthesis of thiophosphinates. Py-DMTA-COF exhibited better photocatalytic activity, broad substrate applicability, and excellent recycling capacity for the preparation of thiophosphinates from P(O)H compounds and thiols compared to Py-DMTPDA-COF. This methodology was further extended to the seamless gram-scale production of target phosphorothioate derivatives. The results demonstrate that COFs can provide a robust platform for developing metal-free, base-free, highly efficient, and reusable heterogeneous photocatalysts for organic transformations.     

3D Microporous Base‐Functionalized Covalent Organic Frameworks for Size‐Selective Catalysis

The design and synthesis of 3D covalent organic frameworks (COFs) have been considered a challenge, and the demonstrated applications of 3D COFs have so far been limited to gas adsorption. Herein we describe the design and synthesis of two new 3D microporous base‐functionalized COFs, termed BF‐COF‐1 and BF‐COF‐2, by the use of a tetrahedral alkyl amine, 1,3,5,7‐tetraaminoadamantane (TAA), combined with 1,3,5‐triformylbenzene (TFB) or triformylphloroglucinol (TFP). As catalysts, both BF‐COFs showed remarkable conversion (96 % for BF‐COF‐1 and 98 % for BF‐COF‐2), high size selectivity, and good recyclability in base‐catalyzed Knoevenagel condensation reactions. This study suggests that porous functionalized 3D COFs could be a promising new class of shape‐selective catalysts.     

Metal–Covalent Organic Frameworks (MCOFs): A Bridge Between Metal–Organic Frameworks and Covalent Organic Frameworks

Many sophisticated chemical and physical properties of porous materials strongly rely on the presence of the metal ions within the structures. Whereas homogeneous distribution of metals is conveniently realized in metal–organic frameworks (MOFs), the limited stability potentially restricts their practical implementation. From that perspective, the development of metal–covalent organic frameworks (MCOFs) may address these shortcomings by incorporating active metal species atop highly stable COF backbones. This Minireview highlights examples of MCOFs that tackle important issues from their design, synthesis, characterization to cutting‐edge applications.     

CO2 Capture by Hydroxylated Azine-Based Covalent Organic Frameworks

Covalent organic frameworks (COFs) RIO-13, RIO-12, RIO-11, and RIO-11m were investigated towards their CO₂ capture properties by thermogravimetric analysis at 1 atm and 40 °C. These microporous COFs bear in common the azine backbone composed of hydroxy-benzene moieties but differ in the relative number of hydroxyl groups present in each material. Thus, their sorption capacities were studied as a function of their textural and chemical properties. Their maximum CO₂ uptake values showed a strong correlation with an increasing specific surface area, but that property alone could not fully explain the CO₂ uptake data. Hence, the specific CO₂ uptake, combined with DFT calculations, indicated that the relative number of hydroxyl groups in the COF backbone acts as an adsorption threshold, as the hydroxyl groups were indeed identified as relevant adsorption sites in all the studied COFs. Additionally, the best performing COF was thoroughly investigated, experimentally and theoretically, for its CO₂ capture properties in a variety of CO₂ concentrations and temperatures, and showed excellent isothermal recyclability up to 3 cycles.     

咔唑基共价有机框架用于光催化析氢

光催化析氢反应是获得高纯氢气的一种具有广阔应用前景的技术. 目前, 开发经济高效、 经久耐用的催化剂仍然是一个巨大的挑战. 我们以3,3'',6,6''-四醛-9,9''-双咔唑和3,7-二氨基二苯并[b,d]噻吩-5,5-二氧化物为基本构建单元, 通过经典的席夫碱反应, 合成了供体-受体型咔唑基共价有机框架(CZ-COF), 对其结构进行了表征, 并探究了其光催化析氢性能. CZ-COF展现了优异的光催化活性, 平均产氢速率为31 μmol·h^-1.     

共价有机框架(COFs)材料的结构控制及其在环境化学中的应用

近年来,共价有机框架(COFs)材料因其稳定的结构、高比表面积、大孔隙率、可修饰结构和易于功能化而受到了科学家们的广泛关注。通过控制COFs材料的孔径、形状和链接方式以及后合成修饰,功能性COFs材料在气体储存分离、传感器和药物传输等领域发挥了越来越重要的作用。尤其在环境化学领域,COFs材料的研究和应用已成为一热门课题。本文综述了COFs材料的结构控制、分类以及在环境污染物检测和去除中的应用,包括对重金属离子、放射性核素、有机污染物和气体污染物的吸附和催化等。通过改变构筑单体的大小和形状、引入特殊官能团和活性位点等方法,可以增强污染物与COFs材料的相互作用(氢键相互作用、π-π相互作用和范德华力等),使COFs材料在环境领域应用中有优异的表现。本文最后展望了COFs材料在环境领域的应用前景和今后的研究方向,希望能为该领域的研究提供参考。     

Covalent Organic Frameworks (COFs) for Cancer Therapeutics

As newly emerged crystalline porous materials, covalent organic frameworks (COFs) possess fascinating structures and some specific features such as modularity, crystallinity, porosity, stability, versatility, and biocompatibility. Besides adsorption/separation, sensing, catalysis, and energy applications, COFs have recently shown a promise in biomedical applications. This contribution provides an overview of the recent developments of COF-based medicines in cancer therapeutics, including drug delivery, photodynamic therapy (PDT), photothermal therapy (PTT), and combined therapy. Furthermore, the major challenges and developing trends in this field are also discussed. These recent developments are summarized and discussed to help encourage further contributions in this emerging and promising field.     

共价有机骨架材料在分离科学中的研究进展

共价有机骨架(COFs)材料是一类由有机单体通过共价键连接而成的新型多功能结晶有机聚合物,具有比表面积大、热和化学稳定性好、结构和功能可控等优点,在气体存储、药物传递、传感和催化等方面有着广泛的应用。多样的结构和丰富的官能团也使COFs在分离科学中具有巨大的应用潜力。COFs及其复合材料作为吸附剂已被用于固相萃取、磁固相萃取、固相微萃取,以及气相色谱、高效液相色谱和毛细管电色谱的新型固定相。该文综述了近3年来COFs在分离科学中的最新进展,着重介绍了COFs在水介质、食品基质、生物样本等复杂基质中样品前处理和有机分子(包括手性和异构化合物)分离等方面的研究进展,为进一步研究COFs的应用提供参考。     

Ionothermal Synthesis of Imide-Linked Covalent Organic Frameworks

Covalent organic frameworks (COFs) are an extensively studied class of porous materials, which distinguish themselves from other porous polymers in their crystallinity and high degree of modularity, enabling a wide range of applications. COFs are most commonly synthesized solvothermally, which is often a time-consuming process and restricted to well-soluble precursor molecules. Synthesis of polyimide-linked COFs (PI-COFs) is further complicated by the poor reversibility of the ring-closing reaction under solvothermal conditions. Herein, we report the ionothermal synthesis of crystalline and porous PI-COFs in zinc chloride and eutectic salt mixtures. This synthesis does not require soluble precursors and the reaction time is significantly reduced as compared to standard solvothermal synthesis methods. In addition to applying the synthesis to previously reported imide COFs, a new perylene-based COF was also synthesized, which could not be obtained by the classical solvothermal route. In situ high-temperature XRPD analysis hints to the formation of precursor–salt adducts as crystalline intermediates, which then react with each other to form the COF.     

Regenerable Covalent Organic Frameworks for Photo-enhanced Uranium Adsorption from Seawater

Uranium is a key resource for the development of the nuclear industry, and extracting uranium from the natural seawater is one of the most promising ways to address the shortage of uranium resources. Herein, a semiconducting covalent organic framework (named NDA-TN-AO) with excellent photocatalytic and photoelectric activities was synthesized. The excellent photocatalytic effect endowed NDA-TN-AO with a high anti-biofouling activity by generating biotoxic reactive oxygen species and promoting photoelectrons to reduce the adsorbed U^VI to insoluble U^IV, thereby increasing the uranium extraction capacity. Owing to the photoinduced effect, the adsorption capacity of NDA-TN-AO to uranium in seawater reaches 6.07 mg g⁻¹, which is 1.33 times of that in dark. The NDA-TN-AO with enhanced adsorption capacity is a promising material for extracting uranium from the natural seawater.     

Sophisticated Design of Covalent Organic Frameworks with Controllable Bimetallic Docking for a Cascade Reaction

Precise control of the number and position of the catalytic metal ions in heterogeneous catalysts remains a big challenge. Here we synthesized a series of two‐dimensional (2D) covalent organic frameworks (COFs) containing two different types of nitrogen ligands, namely imine and bipyridine, with controllable contents. For the first time, the selective coordination of the two nitrogen ligands of the 2D COFs to two different metal complexes, chloro(1,5‐cyclooctadiene)rhodium(I) (Rh(COD)Cl) and palladium(II) acetate (Pd(OAc)₂), has been realized using a programmed synthetic procedure. The bimetallically docked COFs showed excellent catalytic activity in a one‐pot addition–oxidation cascade reaction. The high surface area, controllable metal‐loading content, and predesigned active sites make them ideal candidates for their use as heterogeneous catalysts in a wide range of chemical reactions.     

Microtubular Self‐Assembly of Covalent Organic Frameworks

Despite significant progress in the synthesis of covalent organic frameworks (COFs), reports on the precise construction of template‐free nano‐ and microstructures of such materials have been rare. In the quest for dye‐containing porous materials, a novel conjugated framework DPP‐TAPP‐COF with an enhanced absorption capability up to λ=800 nm has been synthesized by utilizing reversible imine condensations between 5,10,15,20‐tetrakis(4‐aminophenyl)porphyrin ( TAPP ) and a diketopyrrolopyrrole ( DPP ) dialdehyde derivative. Surprisingly, the obtained COF exhibited spontaneous aggregation into hollow microtubular assemblies with outer and inner tube diameters of around 300 and 90 nm, respectively. A detailed mechanistic investigation revealed the time‐dependent transformation of initial sheet‐like agglomerates into the tubular microstructures.     

Sulfonated 2D Covalent Organic Frameworks for Efficient Proton Conduction

Open 1D channels found in covalent organic frameworks are unique and promising to serve as pathways for proton conduction; how to develop high-rate yet stable transporting systems remains a substantial challenge. Herein, this work reports a strategy for exploring proton-conducting frameworks by engineering pore walls and installing proton-containing polymers into the pores. Amide-linked and sulfonated frameworks were synthesized from imine-linked precursors via sequentially engineering to oxidize into amide linkages and to further anchor sulfonic acid groups onto the pore walls, enabling the creation of sulfonated frameworks with high crystallinity and channel ordering. Integrating sulfonated polyether ether ketone chains into the open channels enables proton hopping to across the channels, greatly increases proton conductivity and enables a stable continuous run. These results suggest a way to explore proton-conducting COFs via systematic engineering of the wall and space of the open nanochannels.     

共价有机框架材料的发展与应用:气体存储、催化与化学传感

共价有机框架材料（Covalent Organic Frameworks,COFs）是由有机结构单元通过共价键连接的具有周期性结构的多孔化合物。作为一类新型的结晶性有机多孔材料,由于其密度低、比表面积大、孔隙率高、结晶度好、稳定性高及结构单元可设计等特点受到科学界的广泛关注,在气体吸附与分离、光电、催化、药物传递、储能及化学传感与色谱分离等领域表现出良好的应用前景。本文对COFs材料的发展与应用研究进展进行了简要的综述,对COFs应用中尚待解决的问题进行了总结并对未来的发展方向进行了展望。     

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

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