The dream to prepare well-defined materials drives the methodological evolution for molecular synthesis, structural control and materials manufacturing. Among various methods, chemical approaches to design, synthesize, control and engineer small molecules, polymers and networks offer the fundamental strategies. Merging covalent bonds and non-covalent interactions into one method to establish a complex structural composition for specific functions, mimicking biological systems such as DNA, RNA and proteins, is at the centre of chemistry and materials science. Covalent organic frameworks (COFs) are a class of crystalline porous polymers that enable the integration of organic units into highly ordered structures via polymerization. This polymerization system is unique as it deploys covalent bonds to construct the primary order structures of polymeric backbones via polycondensation and leverages on non-covalent interactions to create the high order structures of polymeric networks via supramolecular polymerization in a one-pot reaction system. This Primer covers all aspects of the field of COFs from chemistry to physics, materials and applications, and outlines the design principle, experimental methods, characterization and applications, with an aim to show a concise yet full picture of the field. The key fundamental issues to be addressed are analysed with an outlook on the future major directions from different perspectives. Covalent organic frameworks (COFs) are a class of crystalline porous polymers consisting of highly ordered organic structures formed by polymerization. In this Primer, Tan et al. discuss the design principle, experimental methods, characterization and applications of COFs. 

https://mts.intechopen.com/storage/books/11903/authors_book/authors_book.pdf

Covalent organic frameworks

Covalent organic frameworks (COFs) are a class of organic crystalline porous materials discovered in the early 21st century that have become an attractive class of emerging materials due to their high crystallinity, intrinsic porosity, structural regularity, diverse functionality, design flexibility, and outstanding stability. However, many chemical and physical properties strongly depend on the presence of metal ions in materials for advanced applications, but metal-free COFs do not have these properties and are therefore excluded from such applications. Metalated COFs formed by combining COFs with metal ions, while retaining the advantages of COFs, have additional intriguing properties and applications, and have attracted considerable attention over the past decade. This review presents all aspects of metalated COFs, from synthetic strategies to various applications, in the hope of promoting the continued development of this young field.

Metalated covalent organic frameworks: from synthetic strategies to diverse applications.

The practical utilization of covalent organic frameworks (COFs) with manipulation at the atomic and molecular scale often demands their assembly on the nano-, meso-, and macroscale with precise control. Consequently, synthetic approaches that establish the ability to control the nucleation and growth of COF crystallites and their self-assembly to desired COF nanomorphologies have drawn substantial attention from researchers. On the basis of the dimensionality of the COF morphologies, we can categorize them into zero- (0-D), one- (1-D), two- (2-D), and three-dimensional (3-D) nanomorphologies. In this perspective, we summarize the reported synthetic strategies that enable precise control of the COF nanomorphologies' size, shape, and dimensionality and reveal the impact of the dimensionalities in their physicochemical properties and applications. The aim is to establish a synergistic optimization of the morphological dimensionality while keeping the micro- or mesoporosity, crystallinity, and chemical functionalities of the COFs in perspective. A detailed knowledge along the way should help us to enrich the performance of COFs in a variety of applications like catalysis, separation, sensing, drug delivery, energy storage, etc. We have discussed the interlinking between the COF nanomorphologies via the transmutation of the dimensionalities. Such dimensionality transmutation could lead to variation in their properties during the transition. Finally, the concept of constructing COF superstructures through the combination of two or more COF nanomorphologies has been explored, and it could bring up opportunities for developing next-generation innovative materials for multidisciplinary applications.

Landscaping Covalent Organic Framework Nanomorphologies.

ConspectusCovalent organic frameworks (COFs) are an emerging class of crystalline porous polymers and have received tremendous attention and research interest. COFs can be classified into two-dimensional (2D) and three-dimensional (3D) analogues. Resembling the architectures of porous graphene, 2D conjugated COFs have exhibited promising prospects in many fields, such as gas storage and separation, heterogeneous catalysis, sensing, photocatalysis, environmental remediation, drug delivery, energy storage and conversion, and so forth. However, efficient structural design for high-throughput production of crystalline 2D COFs remains challenging.In this Account, we summarize our recent contributions to the design, synthesis, and application exploration of 2D conjugated COFs. First, we raised an efficient "two-in-one" strategy for the facile synthesis of 2D imine COFs with good reproducibility and solvent adaptability. Thanks to this elaborate molecular design strategy, we could easily modulate the topology of COFs and fabricate COF films. In addition, we developed two approaches to stabilize the 2D conjugated COFs by using planar building blocks and donor-acceptor structures. We also proposed a skeleton engineering strategy to design COFs as electrode materials, through which redox-active orthoquinone moieties were stepwise-incorporated in the skeletons of isostructural 2D imine-linked COFs. This strategy enabled systematic investigations on a series of 2D conjugated COFs with analogous structures but different numbers of active sites for energy storage, which provides a good platform to unveil the underlying structure-property relationships. In addition, we recently developed a new kind of arylamine-linked 2D conjugated COFs. The electroactive diphenylamine linkages endowed these 2D conjugated COFs with extended conjugation and improved stability, which also conferred these COFs with excellent pseudocapacitive energy storage performance. Moreover, tailor-made sulfur-rich COFs were introduced that were synthesized by selective introduction of polysulfide or sulfonyl groups on the COF skeletons and were used for Li storage and proton conduction. At the end, the key challenges of 2D conjugated COFs toward practical applications and their future prospects are suggested. We hope that this Account will evoke new inspirations and innovative work in the field of 2D conjugated COFs in the near future, especially in some burgeoning and interdisciplinary research areas.

2D Conjugated Covalent Organic Frameworks: Defined Synthesis and Tailor-Made Functions.

When new covalent organic frameworks (COFs) are designed, the main efforts are typically focused on selecting specific building blocks with certain geometries and properties to control the structure and function of the final COFs. The nature of the linkage (imine, boroxine, vinyl, etc.) between these building blocks naturally also defines their properties. However, besides the linkage type, the orientation, i.e., the constitutional isomerism of these linkages, has rarely been considered so far as an essential aspect. In this work, three pairs of constitutionally isomeric imine-linked donor-acceptor (D-A) COFs are synthesized, which are different in the orientation of the imine bonds (D-C=N-A (DCNA) and D-N=C-A (DNCA)). The constitutional isomers show substantial differences in their photophysical properties and consequently in their photocatalytic performance. Indeed, all DCNA COFs show enhanced photocatalytic H2 evolution performance than the corresponding DNCA COFs. Besides the imine COFs shown here, it can be concluded that the proposed concept of constitutional isomerism of linkages in COFs is quite universal and should be considered when designing and tuning the properties of COFs. 

/pdf/constitutional-isomerism-of-the-linkages-in-donor-acceptor-skrnl8c0.pdf

Constitutional isomerism of the linkages in donor–acceptor covalent organic frameworks and its impact on photocatalysis

In principle, polymerization tends to produce amorphous or poorly crystalline materials. Efficiently producing high-quality single crystals by polymerization in solvent remains as an unsolved issue in chemistry, especially for covalent organic frameworks (COFs) with highly complex structures. To produce μm-sized single crystals, the growth time is prolonged to >15 days, far away from the requirements in practical applications. Here, we find supercritical CO2 (sc-CO2) accelerates single-crystal polymerization by 10,000,000 folds, and produces two-dimensional (2D) COF single crystals with size up to 0.2 mm within 2~5 min. Although it is the fastest single-crystal polymerization, the growth in sc-CO2 leads to not only the largest crystal size of 2D COFs, but also higher quality with improved photoconductivity performance. This work overcomes traditional concept on low efficiency of single-crystal polymerization, and holds great promise for future applications owing to its efficiency, industrial compatibility, environmental friendliness and universality for different crystalline structures and linkage bonds. Rapid growth of highly crystalline Covalent organic framework (COF) materials remains challenging. Here, the authors accelerate single-crystal polymerization using supercritical CO2 and realize the fabrication of two-dimensional COF single crystals within several minutes.

/pdf/ultra-fast-single-crystal-polymerization-of-large-sized-s7b6z7jdvy.pdf

Ultra-fast single-crystal polymerization of large-sized covalent organic frameworks.

The invention belongs to the technical field of covalent organic frame materials, and particularly relates to a method for preparing a covalent organic frame material in supercritical fluid The supercritical fluid is used as a main solvent The method comprises the following steps: adding reaction monomers (and a catalyst) as well as a small amount of an organic solvent in a reaction device, thenadding liquid and/or gas substances which can reach supercritical state in the reaction device, heating the reaction device, enabling the substances capable of reaching the supercritical state in thereaction device to become the supercritical fluid, maintaining the reaction conditions for a certain time and then cooling the reaction device, opening the reaction device, then taking out a productand washing the product with the organic solvent, and drying the product to obtain the covalent organic frame material The method is simple and convenient to operate, a preparation process is environmentally friendly, and the method can be used for producing covalent organic frame materials on a large scale The crystallinity of the prepared covalent organic frame material is good

Method for preparing covalent organic frame material in supercritical fluid

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Ultra-fast single-crystal polymerization of large-sized covalent organic frameworks.

Method for preparing covalent organic frame material in supercritical fluid