Sunlight‐Driven Formation and Dissociation of a Dynamic Mixed‐Valence Thallium(III)/Thallium(I) Porphyrin Complex |
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| Authors: | Victoria Ndoyom Luca Fusaro Vincent Dorcet Bernard Boitrel Stéphane Le Gac |
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| Affiliation: | 1. UMR CNRS 6226, Institut des Sciences Chimiques de Rennes, Université de Rennes 1, 263 avenue du Général Leclerc, 35042 Rennes cedex (France);2. Unité de Chimie des Nanomatériaux (CNANO), Université de Namur, 61 rue de Bruxelles, 5000 Namur (Belgium) |
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| Abstract: | 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. |
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| Keywords: | molecular devices photochemistry porphyrinoids redox chemistry thallium |
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