title: Reversible C60Ejection from a Metallocage through the Redox-Dependent Binding of a Competitive Guest.
abstract: The reversible encapsulation of a tetrapyridyl extended-tetrathiafulvalene (exTTF)-based ligand (m-Py)exTTF by a tetragonal Zn-porphyrin-based prismatic nanocage (1) is described. The reversible uptake and release of the (m-Py)exTTF guest proceeds through drastic electronic and conformational changes occurring upon oxidation of the latter. This reversible system has been explored in a guest-exchange process, by addition of (m-Py)exTTF to the host-guest complex [C60⊂1], leading to fullerene C60ejection from the host cavity. Remarkably, the subsequent redox-triggered ejection of (m-Py)exTTF, leads to the recovery of the empty cage 1, which remains available for further C60encapsulation. The C60ejection is justified by the preferable coordination of the pyridine anchors of (m-Py)exTTF to the two Zn-porphyrin units of 1. This approach, based on the use of a switchable competitive guest, offers a promising new strategy for guest-delivery control.
authors.affiliation: Institut de Química Computatcional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, Girona, 17003, Catalonia, Spain.
authors.forename: Cédric
authors.initials: C
authors.lastname: Colomban
authors.affiliation: Université d'Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 bd Lavoisier, 49045, Angers Cedex, France.
authors.forename: György
authors.initials: G
authors.lastname: Szalóki
authors.affiliation: Université d'Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 bd Lavoisier, 49045, Angers Cedex, France.
authors.forename: Magali
authors.initials: M
authors.lastname: Allain
authors.affiliation: Institut de Química Computatcional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, Girona, 17003, Catalonia, Spain.|Serveis Tècnics de Recerca (STR), Universitat de Girona, Parc Científic i Tecnològic de la UdG, Pic de Peguera 15, 17003, Girona, Catalonia, Spain.
authors.forename: Laura
authors.initials: L
authors.lastname: Gómez
authors.affiliation: Université d'Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 bd Lavoisier, 49045, Angers Cedex, France.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Goeb
authors.affiliation: Université d'Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 bd Lavoisier, 49045, Angers Cedex, France.
authors.forename: Marc
authors.initials: M
authors.lastname: Sallé
authors.affiliation: Institut de Química Computatcional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, Girona, 17003, Catalonia, Spain.
authors.forename: Miquel
authors.initials: M
authors.lastname: Costas
authors.affiliation: Institut de Química Computatcional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, Girona, 17003, Catalonia, Spain.
authors.forename: Xavi
authors.identifier: http://orcid.org/0000-0002-2850-4409
authors.initials: X
authors.lastname: Ribas
keywords: fullerenes; host-guest chemistry; metallocage; supramolecular self-assembly; tetrathiafulvalene