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Perspectives in Chemistry: From Supramolecular Chemistry towards Adaptive Chemistry

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Supramolecular chemistry is actively exploring systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, on the basis of the molecular information stored in the covalent framework of the components and read out at the supramolecular level through specific non-covalent interactional algorithms, thus behaving as programmed chemical systems.

Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their components. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) covering both the molecular and supramolecular levels.

CDC introduces a paradigm shift with respect to constitutionally static chemistry. It takes advantage of dynamic diversity to allow variation and selection and operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.

CDC generates networks of dynamically interconverting constituents, constitutional dynamic networks, presenting agonistic and antagonistic relationships between their constituents which may respond to perturbations by physical stimuli or to chemical effectors.

The implementation of these concepts points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.

References Lehn, J.-M., Supramolecular Chemistry: Concepts and Perspectives, VCH Weinheim, 1995. Lehn, J.-M., Dynamic combinatorial chemistry and virtual combinatorial libraries, Chem. Eur. J., 1999, 5, 2455. Lehn, J.-M., Toward complex matter: Supramolecular chemistry and self-organization, Proc. Natl. Acad. Sci. USA , 2002, 99, 4763. Lehn, J.-M., From supramolecular chemistry towards constitutional dynamic chemistry and adaptive chemistry, Chem. Soc. Rev., 2007, 36, 151. Lehn, J.-M., Chapter 1, in Constitutional Dynamic Chemistry, ed. M. Barboiu, Topics Curr. Chem, 2012, 322, 1-32. Lehn, J.-M., Perspectives in Chemistry – Steps towards Complex Matter, Angew. Chem. Int. Ed., 2013, 52, 2836-2850. Lehn, J.-M., Perspectives in Chemistry – Aspects of Adaptive Chemistry and Materials, Angew. Chem. Int. Ed., 2015, 54, 3276-3289.

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