Applications of Dynamic Covalent Chemistry Concept toward Tailored Covalent Organic Framework Nanomaterials: A Review

Abstract

Covalent organic frameworks (COFs) are a rapidly developing class of materials that have been of immense research interest during the last 10 years. Numerous reviews have been devoted to summarizing the synthesis and applications of COFs. However, the underlying dynamic covalent chemistry (DCC), which is the foundation of COF synthesis, has never been systematically reviewed in this context. Dynamic covalent chemistry is the practice of using thermodynamic equilibriums to molecular assemblies. This Critical Review will cover the state-of-the-art use of DCC to both synthesize COFs and expand the applications of COFs. Five synthetic strategies for COF synthesis are rationalized, namely, modulation, mixed linker/linkage, substoichiometric reaction, framework isomerism, and linker exchange, which highlight the dynamic covalent chemistry to regulate the growth and to modify the properties of COFs. Furthermore, the challenges in these approaches and potential future perspectives in the field of COF chemistry are also provided.

Solving the COF trilemma: towards crystalline, stable and functional covalent organic frameworks

“…The design of nets is normally straightforward, but there are exceptions where competing interactions hinder the formation of the desired net. 164,165 This was initially demonstrated with the unexpected formation of a bex net instead of the desired tbo net, driven by p-p interactions. 23 In this case, a 2D framework was obtained instead of a 3D framework from nominally a tetraamine and a trialdehyde building block.…”

Probe metal binding mode of imine covalent organic frameworks: cycloiridation for (photo)catalytic hydrogen evolution from formate

“…The designable ordered porous structure of covalent organic frameworks (COFs) has attracted broad research interest in the past decades. [1][2][3][4] Although COFs are completely composed of light elements (typically H, B, C, N, O, Si), their advanced applications, particularly catalysis, [5][6][7][8] have stressed the role of metal species anchored onto the network. [8][9][10] To accommodate the target metal, a building unit with a suitable metal binding site is required to be incorporated into the framework, which usually meets complicated organic synthesis.…”

Electrochemical Recognition of Aromatic Species with Ferrocenylated 1,3,5‐Triazine‐ or 1,3,5‐Triphenylbenzene‐Containing Highly Organized Molecules

“…Self-assembly and dynamic covalent chemistry concepts have emerged as useful tools toward the selective and efficient formation of highly organized molecules in a specific manner. [1][2][3] The importance of as-fabricated compounds results not only from their interesting properties and structures, but also from the number of potential applications in many important fields, such as catalysis [4][5][6] or medicine. [7][8][9] Cage or cage-like compounds, which are commonly synthesized by utilizing dynamic covalent chemistry concepts starting from various building blocks, act as the prominent class of highly organized organic compounds for various applications.…”

“…Self‐assembly and dynamic covalent chemistry concepts have emerged as useful tools toward the selective and efficient formation of highly organized molecules in a specific manner [1–3] . The importance of as‐fabricated compounds results not only from their interesting properties and structures, but also from the number of potential applications in many important fields, such as catalysis [4–6] or medicine [7–9] .…”