Molecular recognition plays an essential role in the self-assembly and self-organisation of biological and chemical systems alike—allowing individual components to form complex interconnected networks. Within these systems, the nature of the recognition and reactive processes determines their functional and structural properties, and even small changes in their identity or orientation can exert a dramatic effect on the observed properties. The rapidly developing field of systems chemistry aims to move away from the established paradigm in which molecules are studied in isolation, towards the study of networks of molecules that interact and react with each other. Taking inspiration from complex natural systems, where recognition processes never operate in isolation, systems chemistry aims to study chemical networks with the view to examining the system-level properties that arise from the interactions and reactions between the components within these systems. The work presented in this thesis aims to advance the nascent field of systems chemistry by bringing together small organic molecules that can react and interact together to form interconnected networks, exhibiting complex behaviour, such as self-replication, as a result. Three simple building blocks are used to construct a network of two structurally similar replicators and their kinetic behaviour is probed through a comprehensive kinetic analysis. The selectivity for one of the recognition-mediated reactive processes over another is examined within the network in isolation as well as in a scenario where the network is embedded within a pool of exchanging components. The interconnected, two-replicator network is examined under far-from-equilibrium reaction-diffusion conditions, showing that chemical replicating networks can exhibit signs of selective replication—a complex phenomenon normally associated with biological systems. Finally, a design of a well-characterised replicator is exploited for the construction of a network integrating self-replication with a another recognition-directed process, leading to the formation of a mechanically-interlocked architecture—a [2]rotaxane.

Cette thèse décrit la Chimie Covalente Dynamique (CCD) des échanges imine/imine, Knoevenagel/imine et Knoevenagel/Knoevenagel. La L-proline est un excellent organocatalyseur pour la formation de Bibliothèques Covalentes Dynamiques (BCDs). Cependant, l’interconversion entre des dérivées Knoevenagel de l’acide diméthylbarbiturique et des imines se déroule rapidement sans catalyseur. Une nouvelle classe de CCD basée sur des échanges par substitutions nucléophiles (SN2/SN2’) entre des sels d’ammonium quaternaires et des amines tertiaires est développée, impliquant la catalyse par l’iodure. Les réactions d’échange entre des sels de pyridinium et un dérivé de pyridine génèrent des liquides ioniques dynamiques. Enfin, la sélection cinétique et thermodynamique de la formation d’imines dans la CCD est réalisée en solution aqueuse e ten solvant organique. / This thesis describes the dynamic covalent chemistry (DCC) of imine/imine, Knoevenagel/imine, and Knoevenagel/Knoevenagel exchange. L-proline is shown to be an excellent organocatalyst to accelerate the formation of dynamic covalent libraries (DCLs). The interconversion between Knoevenagel derivatives of dimethylbarbituric acid and imines is found to occur rapidly in the absence of catalyst. A new class of DCC based on nucleophilic substitution (SN2/SN2’) component exchange between quaternary ammonium salts and tertiary amines is developed, by the use of iodide as a catalyst. The exchange reactions between pyridinium salts and a pyridine derivative generate dynamic ionic liquids. Finally, kinetic and thermodynamic selection of imine formation in a DCC is perfomed in aqueous solution and organic solvent.