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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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Supplementary files

Article information


Submitted
05 Mar 2016
Accepted
22 Mar 2016
First published
29 Mar 2016

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2016,7, 4423-4427
Article type
Edge Article

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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