Carbon–Carbon Linked Organic Frameworks: An Explicit Summary and Analysis

• Published in: Macromolecular rapid communications. Vol. 44; no. 8; pp. e2200950 - n/a
• Main Authors: Nath, Satyapriya, Puthukkudi, Adithyan, Mohapatra, Jeebanjyoti, Bommakanti, Suresh, Chandrasekhar, Naisa, Biswal, Bishnu P.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.04.2023
• Subjects: Aldehydes; Carbon; Catalysis; Chemical reactions; Chemical synthesis; Condensates; covalent organic frameworks; Electrons; Energy storage; framework solids; functional materials; Magnetism; Optoelectronics; porous organic polymers; Reaction mechanisms; sustainable chemistry; Topology; covalent organic frameworks; sustainable chemistry; framework solids; functional materials; porous organic polymers
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.202200950

Organic frameworks with carbon–carbon (CC) linkage are an important class of materials owing to their outstanding chemical stability and extended π‐electron delocalization resulting in unique optoelectronic properties. In the first part of this review article, the design principles for the bottom‐up synthesis of 2D and 3D sp/sp2 CC linked organic frameworks are summarized. Representative reaction methodologies, such as Knoevenagel condensation, Aldol condensation, Horner–Wadsworth–Emmons reaction, Wittig reaction, and coupling reactions (Ullmann, Suzuki, Heck, Yamamoto, etc.) are included. This is discussed in the context of their reaction mechanism, reaction dynamics, and whether and why resulting in an amorphous or crystalline product. This is followed by a discussion of different state‐of‐the art bottom‐up synthesis methodologies, like solvothermal, interfacial, and solid‐state synthesis. In the second part, the structure–property relationships in CC linked organic frameworks with representative examples of organocatalysis, photo(electro)catalysis, energy storage and conversion, magnetism, and molecular storage and separation are analyzed. The importance of linkage type, building blocks, topology, and crystallinity of the framework material in connection with the structure–property relationship is highlighted. Finally, brief concluding remarks are presented based on the key development of bottom‐up synthetic methods and provide perspectives for future development in this field. This review emphasizes the design principles, synthesis‐reaction dynamics, and structure–property relationships of sp/sp2 CC‐linked crystalline, and amorphous organic frameworks. The framework structures, built‐in functions, and properties are covered. A fine correlation between the choice of monomers and intrinsic properties is presented in a harmonic manner.