Issue 7, 2019

Waterproof architectures through subcomponent self-assembly

Abstract

Metal–organic containers are readily prepared through self-assembly, but achieving solubility and stability in water remains challenging due to ligand insolubility and the reversible nature of the self-assembly process. Here we have developed conditions for preparing a broad range of architectures that are both soluble and kinetically stable in water through metal(II)-templated (MII = CoII, NiII, ZnII, CdII) subcomponent self-assembly. Although these structures are composed of hydrophobic and poorly-soluble subcomponents, sulfate counterions render them water-soluble, and they remain intact indefinitely in aqueous solution. Two strategies are presented. Firstly, stability increased with metal–ligand bond strength, maximising when NiII was used as a template. Architectures that disassembled when CoII, ZnII and CdII templates were employed could be directly prepared from NiSO4 in water. Secondly, a higher density of connections between metals and ligands within a structure, considering both ligand topicity and degree of metal chelation, led to increased stability. When tritopic amines were used to build highly chelating ligands around ZnII and CdII templates, cryptate-like water-soluble structures were formed using these labile ions. Our synthetic platform provides a unified understanding of the elements of aqueous stability, allowing predictions of the stability of metal–organic cages that have not yet been prepared.

Graphical abstract: Waterproof architectures through subcomponent self-assembly

Supplementary files

Article information

Article type
Edge Article
Submitted
14 nov 2018
Accepted
12 dec 2018
First published
12 dec 2018
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., 2019,10, 2006-2018

Waterproof architectures through subcomponent self-assembly

E. G. Percástegui, J. Mosquera, T. K. Ronson, A. J. Plajer, M. Kieffer and J. R. Nitschke, Chem. Sci., 2019, 10, 2006 DOI: 10.1039/C8SC05085F

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