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Issue 7, 2019
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Waterproof architectures through subcomponent self-assembly

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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

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Publication details

The article was received on 14 Nov 2018, accepted on 12 Dec 2018 and first published on 12 Dec 2018


Article type: Edge Article
DOI: 10.1039/C8SC05085F
Citation: Chem. Sci., 2019,10, 2006-2018
  • Open access: Creative Commons BY-NC license
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    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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