Self-assembly is a key process in biology, chemistry, and materials science, underlying DNA replication, quaternary structure formation in proteins, the complexation of primary alkylammonium salts by crown ethers, liquid crystalline behavior, to mention but a few examples. When it comes to multicomponent self-assembly and the template-directed synthesis of mechanically interlocked molecules (MIMs), dynamic covalent chemistry (DCC) provides an efficient route to supramolecular and molecular entities of considerable complexity. DCC, a process whereby covalent bonds are formed reversibly under thermodynamic control and so possesses the elements of "error-checking" and "proofreading", has yielded oligorotaxanes near quantitatively in a cooperative fashion. An alternative synthetic approach, based on irreversible kinetic covalent chemistry (KCC), is more likely to require arduous purification procedures in order to remove unwanted by-products.
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