Premium
Sunlight‐Driven Formation and Dissociation of a Dynamic Mixed‐Valence Thallium(III)/Thallium(I) Porphyrin Complex
Author(s) -
Ndoyom Victoria,
Fusaro Luca,
Dorcet Vincent,
Boitrel Bernard,
Le Gac Stéphane
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201411616
Subject(s) - thallium , porphyrin , dissociation (chemistry) , bimetallic strip , chemistry , valence (chemistry) , photochemistry , metal , free base , inorganic chemistry , organic chemistry , salt (chemistry)
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 Tl III bound out of the plane of the N core and Tl I 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 Tl I to Tl III . The bimetallic complex is dynamic as the metals exchange their positions symmetrically to the porphyrin plane with Tl III 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 Tl III . These results constitute the basis for the further design of innovative light‐driven bimetallic molecular devices.