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Issue 44, 2017
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Chemoselective guest-triggered shaping of a polynuclear CuII calix[6]complex into a molecular host

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Abstract

A new calix[6]arene scaffold bearing a tris-imidazole binding site at the small rim and three tetradentate aza ligands at the large rim was synthesized. The system binds three CuII ions at the large rim sites and is unable to bind a fourth one, which remains in solution. The charge repulsion between the complexes, together with the flexibility of the scaffold, disorganizes the small rim site for binding and prevents its use for host–guest studies. Although the presence of MeCN or DMF guests does not alter this state, the addition of a heptylamine guest, which further displays Brønsted basicity, restores its receptor ability by stabilizing the extra CuII ion at the tris-imidazole site with concomitant guest encapsulation and binding of an exo hydroxo ligand. This chemoselective nuclearity switch yields a tetranuclear complex in which the guest backbone is preorganized in front of three potentially reactive Cu(II) complexes, reminiscent of polynuclear CuII enzyme active sites.

Graphical abstract: Chemoselective guest-triggered shaping of a polynuclear CuII calix[6]complex into a molecular host

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Publication details

The article was received on 11 Sep 2017, accepted on 04 Oct 2017 and first published on 04 Oct 2017


Article type: Paper
DOI: 10.1039/C7DT03375C
Citation: Dalton Trans., 2017,46, 15249-15256
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    Chemoselective guest-triggered shaping of a polynuclear CuII calix[6]complex into a molecular host

    S. Richard, G. Le Duc, N. Le Poul, Y. Le Mest, O. Reinaud and J. Rebilly, Dalton Trans., 2017, 46, 15249
    DOI: 10.1039/C7DT03375C

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