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Entasis Through Hook-and-Loop Fastening in a Glycoligand with Cumulative Weak Forces Stabilizing Cu(I).

Abstract : The idea of a possible control of metal ion properties by constraining the coordination sphere geometry was introduced by Vallee and Williams with the concept of entasis, which is frequently postulated to be at stake in metallo-biomolecules. However, the interactions controlling the geometry at metal centers remain often elusive. In this study, the coordination properties towards copper ions -CuII or CuI- of a geometrically constrained glycoligand centered on a sugar-scaffold were compared with those of an analogous ligand built on an unconstrained alkyl chain. The sugar-centered ligand was shown to be more preorganized for CuII-coordination than its open-chain analogue, with an unusual additional stabilization of the CuI redox state. This preference for CuI was suggested to arise from geometric constraints favoring an optimized folding of the glycoligand minimizing steric repulsions. In other words, the CuI d10 species is stabilized by Valence Shell Electron Pair Repulsion (VSEPR). This idea was rationalized by a theoretical non-covalent interactions (NCI) analysis. The cumulative effects of weak forces were shown to create an efficient buckle as in a hook-and-loop fastener and fine structural features within the glycoligand reduce repulsive interactions for the CuI state. This study emphasizes that mono-saccharide platforms are appropriate ligand backbones for a delicate geometric control at the metal center, with a network of weak interactions within the ligand. This structuration availing in glycoligands makes them attractive for metallic entasis.
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https://hal.archives-ouvertes.fr/hal-01101575
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Ludivine Garcia, Federico Cisnetti, Natacha Gillet, Régis Guillot, Magali Aumont-Nicaise, et al.. Entasis Through Hook-and-Loop Fastening in a Glycoligand with Cumulative Weak Forces Stabilizing Cu(I).. Journal of the American Chemical Society, American Chemical Society, 2015, 137 (3), pp.1141-1146. ⟨10.1021/ja510259p⟩. ⟨hal-01101575⟩

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