Kinetically controlled phenomena in dynamic combinatorial libraries

Abstract

Dynamic combinatorial libraries (DCLs) are collections of structurally related compounds that can interconvert through reversible chemical reaction(s). Such reversibility endows DCLs with adaptability to external stimuli, as rapid interconversion allows quick expression of those DCL components which best respond to the disturbing stimulus. This Tutorial Review focuses on the kinetically controlled phenomena that occur within DCLs. Specifically, it will describe dynamic chiral resolution of DCLs, their self-sorting under the influence of irreversible chemical and physical stimuli, and the autocatalytic behaviours within DCLs which can result in self-replicating systems. A brief discussion of precipitation-induced phenomena will follow and the review will conclude with the presentation of covalent organic frameworks (COFs)-porous materials whose synthesis critically depends on the fine tuning of the crystal growth and error correction rates within large DCLs.

Rewiring Chemical Networks Based on Dynamic Dithioacetal and Disulfide Bonds

“…The study of reaction kinetics on dynamic chemical systems is gaining increasing attention . Differences in reactivity between isolated and networked reversible reactions have been previously described by the group of Lehn for imine formation and exchange, showing that competition between different amino compounds may lead to out‐of‐equilibrium states in which a slow formation step leads towards the equilibrium with a nonlinear kinetics.…”

“…The study of reaction kinetics on dynamic chemical systems is gaining increasing attention. [25] Differences in reactivity between isolated and networked reversible reactions have been previously described by the group of Lehn for iminef ormation and exchange, [2a] showingt hat competition between different amino compounds may lead to out-of-equilibrium states in which as low formation step leads towardst he equilibrium with an onlinear kinetics. In other example, some simultaneous communicating reactions have been shown to have av ery slow velocity,i mpeding the exact determination as to whether the equilibrium point has been reached or not.…”

Imine‐based dynamic polymer networks as photoprogrammable amine sensing devices

“…Integrating dynamic covalent bonds in everyday materials can unlock unique properties, as we recently demonstrated by manufacturing an adaptive material by simple mixing of a commodity polysiloxane with a photoswitchable dialdehyde crosslinker . This system autonomously self‐repairs, which is based on continuous exchange reactions between imine moieties in the material.…”

“…[18][19][20] Among the variety of dynamic covalent reactions, reversible imine formation is unique, as it takes place at ambient conditions while relying on highly abundant amine derivatives. [21][22][23] Integrating dynamic covalent bonds in everyday materials can unlock unique properties, [24][25][26][27][28] as we recently demonstrated by manufacturing an adaptive material by simple mixing of a commodity polysiloxane with a photoswitchable dialdehyde crosslinker. 29 This system autonomously self-repairs, which is based on continuous exchange reactions between imine moieties in the material.…”

Adsorption‐Driven Self‐Sorting of Dynamic Imine Libraries

“…[3] We and others have explored this behavior to achieve self-sorting, [3,4] dynamic kinetic resolution, [5] and self-replication. [3] We and others have explored this behavior to achieve self-sorting, [3,4] dynamic kinetic resolution, [5] and self-replication.…”