Issue 4, 2020

Self-sorting of two imine-based metal complexes: balancing kinetics and thermodynamics in constitutional dynamic networks

Abstract

A major hurdle in the development of complex constitutional dynamic networks (CDNs) is the lack of strategies to simultaneously control the output of two (or more) interconnected dynamic processes over several species, namely reversible covalent imine bond formation and dynamic metal–ligand coordination. We have studied in detail the self-sorting process of 11 constitutional dynamic libraries containing two different amines, aldehydes and metal salts into two imine-based metal complexes, having no overlap in terms of their compositions. This study allowed us to determine the factors influencing the fidelity of this process (concentration, electronic and steric parameters of the organic components, and nature of the metal cations). In all 11 systems, the outcome of the process was primarily determined by the ability of the octahedral metal ion to select its pair of components from the initial pool of components, with the composition of the weaker tetrahedral complex being imposed by the components rejected by the octahedral metal ions. Different octahedral metal ions required different levels of precision in the “assembling instructions” provided by the organic components of the CDN to guide it towards a sorted output. The concentration of the reaction mixture, and the electronic and steric properties of the initial components of the library were all found to influence the lifetime of unwanted metastable intermediates formed during the assembling of the two complexes.

Graphical abstract: Self-sorting of two imine-based metal complexes: balancing kinetics and thermodynamics in constitutional dynamic networks

Supplementary files

Article information

Article type
Edge Article
Submitted
04 Oct 2019
Accepted
04 Dec 2019
First published
17 Dec 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 1114-1121

Self-sorting of two imine-based metal complexes: balancing kinetics and thermodynamics in constitutional dynamic networks

J. Ayme and J. Lehn, Chem. Sci., 2020, 11, 1114 DOI: 10.1039/C9SC04988F

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