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Waterproof architectures through subcomponent self-assembly.

Published version
Peer-reviewed

Type

Article

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Authors

Percástegui, Edmundo G  ORCID logo  https://orcid.org/0000-0003-4346-2443
Mosquera, Jesús 
Plajer, Alex J 

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.

Description

Keywords

0303 Macromolecular and Materials Chemistry, 0306 Physical Chemistry (incl. Structural)

Journal Title

Chem Sci

Conference Name

Journal ISSN

2041-6520
2041-6539

Volume Title

10

Publisher

Royal Society of Chemistry (RSC)
Sponsorship
European Commission (642192)
Engineering and Physical Sciences Research Council (EP/P027067/1)
European Research Council (695009)