Constitutional Dynamic Selection at Low Reynolds Number in a Triple Dynamic System: Covalent Dynamic Adaptation Driven by Double Supramolecular Self-Assembly

A triple dynamic complex system has been designed, implementing a dynamic covalent process coupled to two supramolecular self-assembly steps. To this end, two dynamic covalent libraries (DCLs), DCL-1 and DCL-2, have been established on the basis of dynamic covalent CC/CN organo-metathesis between...

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Veröffentlicht in:Journal of the American Chemical Society 2021-09, Vol.143 (35), p.14136-14146
Hauptverfasser: Gu, Ruirui, Lehn, Jean-Marie
Format: Artikel
Sprache:eng
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Zusammenfassung:A triple dynamic complex system has been designed, implementing a dynamic covalent process coupled to two supramolecular self-assembly steps. To this end, two dynamic covalent libraries (DCLs), DCL-1 and DCL-2, have been established on the basis of dynamic covalent CC/CN organo-metathesis between two Knoevenagel derivatives and two imines. Each DCL contains a barbituric acid-based Knoevenagel constituent that may undergo a sequential double self-organization process involving first the formation of hydrogen-bonded hexameric supramolecular macrocycles that subsequently undergo stacking to generate a supramolecular polymer SP yielding a viscous gel state. Both DCLs display selective self-organization-driven amplification of the constituent that leads to the SP. Dissociation of the SP on heating causes reversible randomization of the constituent distributions of the DCLs as a function of temperature. Furthermore, diverse distribution patterns of DCL-2 were induced by modulation of temperature and solvent composition. The present dynamic systems display remarkable self-organization-driven constitutional adaption and tunable composition by coupling between dynamic covalent component selection and two-stage supramolecular organization. In more general terms, they reveal dynamic adaptation by component selection in low Reynolds number conditions of living systems where frictional effects dominate inertial behavior.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.1c04446