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Chemoselective guest-triggered shaping of a polynuclear Cu II calix[6]complex into a molecular host

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.
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https://hal.univ-brest.fr/hal-01626615
Contributor : Nicolas Renard <>
Submitted on : Tuesday, October 31, 2017 - 9:35:34 AM
Last modification on : Wednesday, September 16, 2020 - 5:13:09 PM

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Sarah Richard, Gaëtan Le Duc, Nicolas Le Poul, Yves Le Mest, Olivia Reinaud, et al.. Chemoselective guest-triggered shaping of a polynuclear Cu II calix[6]complex into a molecular host. Dalton Transactions, Royal Society of Chemistry, 2017, Dalton Trans., 46, pp.15249-15256. ⟨10.1039/c7dt03375c⟩. ⟨hal-01626615⟩

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