Sunlight-driven formation and dissociation of a dynamic mixed-valence Thallium(III)/Thallium(I) porphyrin complex

Victoria Ndoyom, Luca Fusaro, Vincent Dorcet, Bernard Boitrel, Stéphane Le Gac

Résultats de recherche: Contribution à un journal/une revueArticleRevue par des pairs

Résumé

Inspired by a Newton's cradle device and interested in the development of redox-controllable bimetallic molecular switches, a mixed-valence thallium(III)/thallium(I) bis-strap porphyrin complex, with TlIII bound out of the plane of the N core and TlI hung to a strap on the opposite side, was formed by the addition of TlOAc to the free base and exposure to indirect sunlight. In this process, oxygen photosensitization by the porphyrin allows the oxidation of TlI to TlIII. The bimetallic complex is dynamic as the metals exchange their positions symmetrically to the porphyrin plane with TlIII funneling through the macrocycle. Further exposure of the complex to direct sunlight leads to thallium dissociation and to total recovery of the free base. Hence, the porphyrin plays a key role at all stages of the cycle of the complex: It hosts two metal ions, and by absorbing light, it allows the formation and dissociation of TlIII. These results constitute the basis for the further design of innovative light-driven bimetallic molecular devices. Newton's cradle: A mixed-valence thallium(III)/thallium(I) bis-strap porphyrin complex, with TlIII bound to the N core and TlI attached to a strap, was generated by the addition of TlOAc to the free base and exposure to indirect sunlight. Exposure of the complex to direct sunlight leads to thallium dissociation and to the recovery of the free porphyrin.

langue originaleAnglais
Pages (de - à)3806-3811
Nombre de pages6
journalAngewandte Chemie International Edition
Volume54
Numéro de publication12
Les DOIs
Etat de la publicationPublié - 16 mars 2015

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