title: Mimicking the Regulation Step of Fe-Monooxygenases: Allosteric Modulation of FeIV-Oxo Formation by Guest Binding in a Dinuclear ZnII-FeIICalix[6]arene-Based Funnel Complex.
abstract: A heteroditopic ligand associated with a calix[6]arene scaffold bearing a tris(imidazole) coordinating site at its small rim and an amine/pyridine ligand at its large rim has been prepared, and its regioselective coordination to ZnIIat the small rim and FeIIin the amine/pyridine ligand has been achieved. The heterodinuclear complex obtained displays an overall cone conformation capped by the tris(imidazole)ZnIImoiety and bears a non-heme FeIIcomplex at its base. Each of the metal centers exhibits one labile position, allowing the coordination inside the cavity of a guest alkylamine at ZnIIand the generation of reaction intermediates (FeIII(OOH) and FeIVO) at the large rim. A dependence between the chain length of the encapsulated alkylamine and the distribution of FeIII(OOH) intermediates and FeIII(OMe) is observed. In addition, it is shown that the generation of the FeIVO intermediate is enhanced by addition of the alkylamine guest. Hence, this supramolecular system gathers the three levels of reactivity control encountered in oxidoreductases: i) control of the FeIIredox properties through its first coordination sphere, allowing us to generate high valent reactive species; ii) control of guest binding through a hydrophobic funnel that drives its alkyl chain next to the reactive iron complex, thus mimicking the binding pocket of natural systems; iii) guest-modulated reactivity of the FeIIcenter towards oxidants.
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay, Laboratoire de Chimie Inorganique, Université Paris Sud, Université Paris Saclay, CNRS, 91405, Orsay, France.
authors.forename: Nathalie
authors.initials: N
authors.lastname: Ségaud
authors.affiliation: CNRS UMR 8601, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques, Université Paris Descartes, Sorbonne Paris Cité, 75006, Paris, France.
authors.forename: Constance
authors.initials: C
authors.lastname: De Thomasson
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay, Laboratoire de Chimie Inorganique, Université Paris Sud, Université Paris Saclay, CNRS, 91405, Orsay, France.|CNRS UMR 8601, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques, Université Paris Descartes, Sorbonne Paris Cité, 75006, Paris, France.
authors.forename: Caroline
authors.initials: C
authors.lastname: Daverat
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay, Laboratoire de Chimie Inorganique, Université Paris Sud, Université Paris Saclay, CNRS, 91405, Orsay, France.
authors.forename: Katell
authors.initials: K
authors.lastname: Sénéchal-David
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay, Laboratoire de Chimie Inorganique, Université Paris Sud, Université Paris Saclay, CNRS, 91405, Orsay, France.
authors.forename: Amandine
authors.initials: A
authors.lastname: Dos Santos
authors.affiliation: Laboratoire de Chimie Physique, CNRS UMR 8000, Université Paris Sud, Université Paris Saclay, CNRS, 91405, Orsay, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Steinmetz
authors.affiliation: Laboratoire de Chimie Physique, CNRS UMR 8000, Université Paris Sud, Université Paris Saclay, CNRS, 91405, Orsay, France.
authors.forename: Philippe
authors.initials: P
authors.lastname: Maître
authors.affiliation: CNRS UMR 8601, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques, Université Paris Descartes, Sorbonne Paris Cité, 75006, Paris, France.
authors.forename: Jean-Noël
authors.initials: JN
authors.lastname: Rebilly
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay, Laboratoire de Chimie Inorganique, Université Paris Sud, Université Paris Saclay, CNRS, 91405, Orsay, France.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Banse
authors.affiliation: CNRS UMR 8601, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques, Université Paris Descartes, Sorbonne Paris Cité, 75006, Paris, France.
authors.forename: Olivia
authors.initials: O
authors.lastname: Reinaud
keywords: allosteric switches; calixarenes; host-guest chemistry; iron-oxo species; non-heme iron complexes