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Article Dans Une Revue Dalton Transactions Année : 2020

Dual switchable molecular tweezers incorporating anisotropic Mn-salphen complexes

Résumé

An alternative strategy for the synthesis of terpyridine based switchable molecular tweezers has been developed to incorporate anisotropic Mn(iii)-salphen complexes. The free ligand was synthesized using a building block strategy based on Sonogashira coupling reactions and was then selectively metalated with manganese in a last step. The conformation of the tweezers was switched from an open 'W' shaped form to a closed 'U' form by Zn(ii) coordination to the terpyridine unit bringing the two Mn-salphen moieties in close spatial proximity as confirmed by X-ray crystallography. An alternate switching mechanism was observed by the intercalation of a bridging cyanide ligand between the two Mn-salphen moieties that resulted in the closing of the tweezers. These dual stimuli are attractive for achieving multiple controls of the mechanical motion of the tweezers. A crystallographic structure of unexpected partially oxidized closed tweezers was also obtained. One of the two Mn-salphen moieties underwent a ligand-centered oxidation of an imino to an amido group allowing an intramolecular Mn-Oamide-Mn linkage. The magnetic properties of the manganese(iii) dimers were investigated to evaluate the magnetic exchange interaction and analyze the single molecule magnet behavior.

Domaines

Chimie
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Dates et versions

hal-02890145 , version 1 (04-01-2021)

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Benjamin Doistau, Lorien Benda, Jean-Louis Cantin, Olivier Cador, Fabrice Pointillart, et al.. Dual switchable molecular tweezers incorporating anisotropic Mn-salphen complexes. Dalton Transactions, 2020, 49 (26), pp.8872-8882. ⟨10.1039/d0dt01465f⟩. ⟨hal-02890145⟩
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