Self-Assembly of Topological Structures

In chemistry, self-assembly is defined as a phenomenon by which molecules order themselves into a particular arrangement without external intervention. The process occurs under the guidance of numerous weak non-covalent bonding interactions that represent the core of supramolecular chemistry. It is not surprising that chemists engaged in the synthesis of topologically non-trivial structures are interested in utilizing self-assembly to direct the templation of chemical components into intermediates prone to cyclization, followed by the formation of covalent bonds. 

Nevertheless, self-assembling processes by nature rely on weak interactions and the isolation of chemically stable knots and links requires a final knotting step in which covalent bonds are formed. While irreversible reactions such as Williamson ether reactions and ring closing methathesis are employed successfully to form knots and links, their template-directed syntheses have recently been enriched by the concept of dynamic covalent chemistry (DCC). DCC employs reversible covalent bond formation that allows equilibration of a system toward the most thermodynamically stable structures dictated by the sum of the non-covalent bonding interactions. 

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