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Issue 22, 2017
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Rapid self-healing and anion selectivity in metallosupramolecular gels assisted by fluorine–fluorine interactions

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Abstract

Simple ML2 [M = Fe(II), Co(II), Ni(II)] complexes obtained from a perfluoroalkylamide derivative of 4-aminophenyl-2,2′,6,2′-terpyridine spontaneously, yet anion selectively, self-assemble into gels, which manifest an unprecedented rapid gel strength recovery, viz. self-healing, and thermal rearrangement in aqueous dimethyl sulfoxide. The key factor for gelation and rheological properties emerges from the fluorine–fluorine interactions between the perfluorinated chains, as the corresponding hydrocarbon derivative did not form metallogels. The perfluoro-terpyridine ligand alone formed single crystals, while its Fe(II), Co(II) or Ni(II) complexes underwent rapid gelation leading to highly entangled fibrillar networks visualized by electron microscopy. The thermodynamic parameters of gelation based on variable temperature NMR 1H and 19F resonances showed that gelation was enthalpically favourable and entropically disfavourable. The step strain rheological experiments revealed that the gels undergo rapid self-healing and the morphological features, thermal stability and mechanical properties were found to depend on the nature of the metal ion.

Graphical abstract: Rapid self-healing and anion selectivity in metallosupramolecular gels assisted by fluorine–fluorine interactions

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Publication details

The article was received on 18 Mar 2017, accepted on 08 May 2017 and first published on 08 May 2017


Article type: Paper
DOI: 10.1039/C7DT00983F
Citation: Dalton Trans., 2017,46, 7309-7316
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    Rapid self-healing and anion selectivity in metallosupramolecular gels assisted by fluorine–fluorine interactions

    L. Arnedo-Sánchez, Nonappa, S. Bhowmik, S. Hietala, R. Puttreddy, M. Lahtinen, L. De Cola and K. Rissanen, Dalton Trans., 2017, 46, 7309
    DOI: 10.1039/C7DT00983F

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