The synthesis of highly crystalline covalent organic frameworks via the monomer crystal induction for the photocatalytic asymmetric α-alkylation of aldehydes

Covalent organic frameworks (COFs) are ordered porous organic frameworks, which found wide applications in gas sorption and separation, catalysis, sensoring, and many others owing to their permanent porosity and designable structural motifs. To take full advantage of the well-defined porous structure, COFs need to be synthesized with high crystallinity. However, the synthesis of COFs with high crystalline is a general challenge, which requires dedicated linker design and reaction condition optimization. To achieve this, we developed a monomer crystal-induced strategy to construct crystalline COFs. The synthesized COFs have higher crystallinity, surface area, and thermal stability than those prepared without monomer crystal induction. Furthermore, the high crystalline COFs exhibit excellent performance in the photocatalytic asymmetric alkylation of aldehydes. The monomer crystal-induced method not only represents a new route for the synthesis of crystalline COFs but also sheds light on the mechanism of the formation of COFs.     

Construction of Covalent‐Organic Frameworks (COFs) from Amorphous Covalent Organic Polymers via Linkage Replacement

Covalent‐organic frameworks (COFs) as porous crystalline materials show promising potential applications. However, developing facile strategies for the construction of COFs directly from amorphous covalent organic polymers (COPs) is still a great challenge. To this end, we report a novel approach for easy preparation of COFs from amorphous COPs through the linkage replacement under different types of reactions. Four COFs with high crystallinity and porosity were constructed via the linkage substitution of polyimide‐linked COPs to imine‐linked COFs as well as imine‐linked COPs to polyimide‐linked COFs. The realization of the linkage substitution would significantly expand the research scope of COFs.     

An overview on covalent organic frameworks: synthetic reactions and miscellaneous applications

Covalent organic frameworks (COFs) are an emerging class of porous crystalline materials which are completely constructed from organic building blocks through robust covalent bonds. High surface areas, compositional and structural tunability, low density, and superior stability have rendered COF candidates in a variety of applications, such as adsorption and separation, catalysis, electronics, chemical sensing, optics, and so forth. To better understand the structures and properties of COFs as well as the design principles, it is of great significance to learn about the linkages formed during synthetic reactions that contribute to the high crystallinity and stability of COFs. In this review, we will first discuss various linkages that have been utilized for COF construction up to date, followed by an outline of their miscellaneous applications, providing a comprehensive and detailed overview in this file.     

Ionic Covalent Organic Framework: What Does the Unique Ionic Site Bring to Us?

Ionic covalent organic frameworks featuring both crystallinity and charged sites have arose tremendous attention from scientific community. The adjustable textural structures, well-defined channels and abundant charged sites of ionic COFs facilitate great potential in diverse aspects, such as separation, ion conduction, sensing, catalysis and energy storage. In this review, we first introduced the design and construction of ionic covalent organic frameworks(COFs), and classified them according to the types of charged sites. We focused on the various applications of ionic COFs in diverse fields. The structure-function relationship was also explored in detail. Finally, the opportunities and challenges of ionic COFs were summarized to provide guidance for better design and application of ionic COFs.     

Crystallinity and stability of covalent organic frameworks

Covalent organic frameworks(COFs) are a class of organic porous polymers with high crystallinity, and their structures can be precisely tailored via topology design. Owing to the characteristics of permanent pores, periodic structures and rich building blocks, COFs have triggered tremendous attention in the past fifteen years and are extensively investigated in various fields.Crystallinity and stability are two crucial features for practical applications. In general, these two features are contradictory for COFs formed via dynamic covalent chemistry(DCC). High thermodynamic reversibility is usually required to attain exceptional crystallinity of COFs, often resulting in limited stability. The first two reported COFs are based on the boroxine and boronate ester linkages, which are unstable in water and even in humid conditions. Therefore, many researchers doubt the stability of COFs for real applications. Actually, in these years, various novel linkages have been developed for the construction of COFs,and numerous newly synthesized COFs are robust towards strong acid/base and even some of them can resist the attack of strong oxidizing and reducing agents. In this review, we focus on the linkage chemistry of the COFs in terms of crystallinity and stability, further extending it to the investigation in the mechanisms of the crystal growth and the overall regulation of the contradiction between stability and crystallinity. The strategies for improving the crystallinity, including selecting building units,introducing non-covalent interactions and slowing nucleation and growth rate, are described in the third section, while the methodologies for increasing the stability from the viewpoints of chemical modification and non-covalent interactions are summarized in the fourth section. Finally, the challenges and perspectives are presented.     

Covalent organic frameworks for applications in lithium batteries

With the stone energy increasingly dried up and the environment polluted severely, developing renewable clean energy is already in extreme urgency. Exploiting new energy storage and transformation systems has progressively become the focal point in the energy research field. Covalent organic frameworks (COFs) have attracted extensive attention as a new kind of crosslinked polymers owing to the high crystallinity, excellent porosity, and favorable stability. The last decade has witnessed the great progress in crystalline COFs for the application in various arenas. The tailor-made functional skeleton together with well-defined periodical alignment has endowed COFs with enormous potential in lithium batteries. In this review, we initially illustrated the design principle of COFs for the application in lithium batteries. Furthermore, we made a comprehensive summary of the fast-developing COFs field in terms of lithium batteries, including lithium ion and lithium sulfur batteries. Finally, we discussed the remaining challenges and perspectives in this area and also proposed several possible future directions of development for lithium batteries. It is expected that this short review would contribute to the development of COFs materials in energy-related applications.     

Covalent Organic Frameworks for Chemical and Biological Sensing

Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with polygonal porosity and highly ordered structures. The most prominent feature of the COFs is their excellent crystallinity and highly ordered modifiable one-dimensional pores. Since the first report of them in 2005, COFs with various structures were successfully synthesized and their applications in a wide range of fields including gas storage, pollution removal, catalysis, and optoelectronics explored. In the meantime, COFs also exhibited good performance in chemical and biological sensing, because their highly ordered modifiable pores allowed the selective adsorption of the analytes, and the interaction between the analytes and the COFs’ skeletons may lead to a detectable change in the optical or electrical properties of the COFs. In this review, we firstly demonstrate the basic principles of COFs-based chemical and biological sensing, then briefly summarize the applications of COFs in sensing some substances of practical value, including some gases, ions, organic compounds, and biomolecules. Finally, we discuss the trends and the challenges of COFs-based chemical and biological sensing.     

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.     

Progress and Perspectives on Covalent-Organic Frameworks (COFs) and Composites for Various Energy Applications

Covalent-organic frameworks (COFs), being a new member of the crystalline porous materials family, have emerged as important materials for energy storage/conversion/generation devices. They possess high surface areas, ordered micro/mesopores, designable structures and an ability to precisely control electro-active groups in their pores, which broaden their application window. Thanks to their low weight density, long range crystallinity, reticular nature and tunable synthesis approach towards two and three dimensional (2D and 3D) networks, they have been found suitable for a range of challenging electrochemical applications. Our review focuses on the progress made on the design, synthesis and structure of COFs and their composites for various energy applications, such as metal-ion batteries, supercapacitors, water-splitting and solar cells. Additionally, attempts have been made to correlate the structural and mechanistic characteristics of COFs with their applications.     

Intermediate Formation of Macrocycles for Efficient Crystallization of 2D Covalent Organic Frameworks with Enhanced Photocatalytic Hydrogen Evolution

Covalent organic frameworks (COFs) have gained significant attention as key photocatalysts for efficient solar light conversion into hydrogen production. Unfortunately, the harsh synthetic conditions and intricate growth process required to obtain highly crystalline COFs greatly hinder their practical application. Herein, we report a simple strategy for the efficient crystallization of 2D COFs based on the intermediate formation of hexagonal macrocycles. Mechanistic investigation suggests that the use of 2,4,6-triformyl resorcinol (TFR) as the asymmetrical aldehyde build block allows the equilibration between irreversible enol-to-keto tautomerization and dynamic imine bonds to produce the hexagonal β-ketoenamine-linked macrocycles, the formation of which could provide COFs with high crystallinity in half hour. We show that COF-935 with 3 wt % Pt as cocatalyst exhibit a high hydrogen evolution rate of 67.55 mmol g⁻¹ h⁻¹ for water splitting when exposed to visible light. More importantly, COF-935 exhibits an average hydrogen evolution rate of 19.80 mmol g⁻¹ h⁻¹ even at a low loading of only 0.1 wt % Pt, which is a significant breakthrough in this field. This strategy would provide valuable insights into the design of highly crystalline COFs as efficient organic semiconductor photocatalysts.     

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.     

Challenges and perspectives of covalent organic frameworks for advanced alkali-metal ion batteries

Covalent organic frameworks(COFs) are a class of porous crystalline polymers that have been widely investigated in various fields, including energy storage, photo/electrocatalysis, drug delivery. The covalent-bond interconnection allows COFs extraordinary chemical and thermal stability, and the porous structure ensures a high ion-diffusion coefficient. These merits compensate for the drawbacks of organic electrodes that are easy to dissolve and have low charge conductivity, and promote the development of novel electrode materials with excellent performance, environmental friendliness, and low price. However, the application of COFs also encountered many problems, such as poor electronic conductivity due to the large band gap. Moreover,in some three-dimensional(3D) COFs and stacked two-dimensional(2D) COFs, the huge crystal structure, aligned ultralong channels, and numerous crystal defects usually impede ion transport, and the large molecular weights of COFs generally decrease the specific capacities. These issues are urgently needed to be solved. Here in this review, we summarize the latest progress, core challenges and coping strategies concerning with the use of COFs in alkali-metal ion batteries, discuss the impact of material structure on energy storage, and propose strategies for the construction of high-performance COF-based electrodes.     

Chiral covalent organic frameworks for asymmetric catalysis and chiral separation

Covalent organic frameworks (COFs), covalently assembled from the condensation reactions of organic building blocks, are a fascinating class of functional porous materials with two- or three-dimensional crystalline organic structures. Generally, it is preferable to use symmetric and rigid building blocks to construct highly crystalline COFs with desired topology. On the other hand, the incorporation of chiral functional moieties in the building blocks would open up new applications such as asymmetric catalysis and chiral separation. This mini review highlights the principle strategies in the design and synthesis of chiral COFs. The interesting and potential applications of these chiral COFs for asymmetric catalysis and chiral separation are also summarized. This mini review aims to provide an up-to-date advancement of chiral COFs for asymmetric catalysis and chiral separation.     

Covalent Organic Frameworks with trans-Dimensionally Vinylene-linked π-Conjugated Motifs

Vinylene-linked covalent organic frameworks(COFs) are a class of promising porous organic materials that feature fully π-conjugated structures, high crystallinity, permanent porosity, ultrahigh chemical stability, and extraordinary optoelectronic properties. Over the past 5 years, this kind of material has been witnessed rapid development either in chemical synthesis or in potential applications. In this review, we summarize the chemistry to synthesize vinylene-linked COFs, especially the synthetic strategies involving activation of aryl methyl groups for condensation reaction. We then scrutinize the state-of-the-art development in properties and functions of this kind of COFs. Our own opinions on the further development of the vinylene-linked COFs are also presented for discussion.     

卟啉共价有机框架化合物的研究进展

共价有机框架化合物(COFs)是一类新兴的具有多孔结构的晶态有机聚合物,在储存与分离、催化、能量转化等领域具有广泛应用。本文介绍了一类基于卟啉单元的COFs,从框架构筑及应用开发两方面综述了这类材料的研究进展。     

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.     

Two-dimensional porphyrin- and phthalocyanine-based covalent organic frameworks

Covalent organic frameworks (COFs) represent an emerging class of porous crystalline materials and have recently shown interesting applications from catalysis to optoelectronic devices. In this review, by covering most of the reported work, we summarized the research progress of two-dimensional (2D) porphyrin- and phthalocyanine-based COFs, with highlighting the synthesis of these 2D COFs via various dynamic covalent reactions and emphasizing their potential applications in different areas.     

Covalent Organic Frameworks for Photocatalytic Organic Transformation

Photocatalytic organic transformation is an efficient, energysaving and environmentally friendly strategy for organic synthesis. The key to developing a green and economical route for photocatalytic organic synthesis lies in the construction of optimal photocatalysts. Covalent organic frameworks(COFs), a kind of porous crystalline materials with characteristics of high surface area, excellent porosity, and superior thermo-chemical stability, have driven people to explore their potential as photocatalysts in photocatalytic organic transformations by virtue of their structural versatility and designability. Furthermore, the insolubility of COFs makes it possible to recycle the catalysts by simple technical means. In recent years, researchers have made great efforts to develop both the design strategies of COFs as heterogeneous photocatalysts and the reaction types of photocatalytic organic transformations. In this review, we focus on the design of COF-based photocatalytic materials and analyze the influence factors of photocatalytic performance. Moreover, we summarize the application of COFbased photocatalysts in photocatalytic organic conversion. Finally, the perspectives on new opportunities and challenges in the field are discussed.     

共价有机框架材料在多相催化领域的研究进展（英文）

共价有机框架(COFs)材料是近年来在拓扑学基础上发展起来的一类新型有机多孔聚合物,是有机单体通过可逆共价键连接而形成的晶型多孔材料,具有拓扑结构"可设计"、比表面积大、结构规整、孔道均一、孔径可调节以及易于修饰和功能化等优点.与金属有机框架材料(MOFs)相比,由于COFs是以共价键连接形成空间网络结构,具有较好的热稳定性和化学稳定性,又被称为"有机分子筛".COFs的构筑单体为有机小分子,有机小分子来源广泛而且种类繁多,使得构筑单体多样化,便于通过构筑单体来调控目标材料的结构和功能.自2005年首次报道以来,COFs以其独特的结构和优越的性能,吸引了广大科研工作者的极大兴趣,对其结构设计、可控合成、结构解析以及功能探索成为了研究热点,在气体吸附与分离、光电材料等领域展现出了广阔的应用前景.特别是在催化领域,由于COFs材料的多孔性、敞开的孔道结构、良好的稳定性以及易于修饰的特点,采用COFs作为催化剂以及催化剂载体受到了人们普遍的关注.作为催化剂,COFs可分为本征型催化剂和负载型催化剂.本征型催化剂的设计方法是基于"自下而上"策略将催化活性中心嵌入材料骨架之中;负载型催化剂的设计方法是以COFs为载体,通过后修饰方式负载金属颗粒或离子来构建多相催化剂.本征型COFs催化剂是在分子水平上引入催化活性中心,具有活性位点均匀分散、数量可控的特点,而且COFs规整均一的孔道结构有利于底物的传质,也为择形催化提供了可能;负载型催化剂通过后修饰方式引入催化活性中心,由于COFs以共价键连接,催化剂稳定性较高.COFs载体具有较大的比表面积,使得催化活性位点分散性好,也有利于底物与催化活性位点的结合.本文综述了COFs作为多相催化剂在催化领域的发展状况,按照COFs引入催化活性位点的类别,如单催化位点、双催化位点以及负载的金属纳米粒子进行了细致的阐述,重点讨论了COFs催化剂的设计理念、制备方式、功能化策略、材料的稳定性、催化活性以及选择性等内容.此外,对COFs作为光催化剂以及电催化剂方面的研究也进行了详细的介绍.最后,我们讨论了COFs在未来催化领域所面临的问题及挑战,并展望了COFs在超分子催化以及酶催化等方面的应用前景.     

Covalent organic frameworks

Covalent organic frameworks (COFs) are a class of crystalline porous polymers that allow the atomically precise integration of organic units to create predesigned skeletons and nanopores. They have recently emerged as a new molecular platform for designing promising organic materials for gas storage, catalysis, and optoelectronic applications. The reversibility of dynamic covalent reactions, diversity of building blocks, and geometry retention are three key factors involved in the reticular design and synthesis of COFs. This tutorial review describes the basic design concepts, the recent synthetic advancements and structural studies, and the frontiers of functional exploration.