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Issue 7, 2016
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Structural switching in self-assembled metal–ligand helicate complexes via ligand-centered reactions

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Abstract

Ligand centered reactions are capable of conferring structural switching between a metastable, self-assembled Fe–iminopyridine aggregate and a stable M2L3 helicate. The reactivity is directed and accelerated by the stability of the final product structure. Under aerobic conditions, both substitution and oxidation occurs at the ligand, exploiting atmospheric oxygen as the oxidant. In the absence of air, reaction occurs more slowly, forming the less stable substitution product. Control ligands show a preference for simple substitution, but the self-assembly directs both substitution and oxidation. The metastable nature of the initial aggregate species is essential for the reaction: while the aggregate is “primed” for reaction, other analogous helicate structures are “locked” by self-assembly, preventing reactivity.

Graphical abstract: Structural switching in self-assembled metal–ligand helicate complexes via ligand-centered reactions

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Publication details

The article was received on 05 Mar 2016, accepted on 22 Mar 2016 and first published on 29 Mar 2016


Article type: Edge Article
DOI: 10.1039/C6SC01038E
Chem. Sci., 2016,7, 4423-4427
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Structural switching in self-assembled metal–ligand helicate complexes via ligand-centered reactions

    L. R. Holloway, H. H. McGarraugh, M. C. Young, W. Sontising, G. J. O. Beran and R. J. Hooley, Chem. Sci., 2016, 7, 4423
    DOI: 10.1039/C6SC01038E

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