1. Supramolecular control of a mononuclear biomimetic copper(II) center: bowl complexes vs funnel complexes
- Author
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Arnaud Parrot, Jérôme Gout, Olivia Bistri, Aleksandar Višnjevac, Nicolas Le Poul, Stéphanie Rat, Yves Le Mest, Olivia Reinaud, Assia Hessani, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie et Biologie des Métaux ( LCBM - UMR 5249 ), Université Joseph Fourier - Grenoble 1 ( UJF ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Grenoble Alpes ( UGA ), Institut Parisien de Chimie Moléculaire ( IPCM ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ), Institut Lavoisier de Versailles ( ILV ), Université de Versailles Saint-Quentin-en-Yvelines ( UVSQ ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), and Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS
- Subjects
Models, Molecular ,Coordination sphere ,Stereochemistry ,Phenylalanine ,Supramolecular chemistry ,chemistry.chemical_element ,Crystallography, X-Ray ,Inorganic Chemistry ,Metal ,chemistry.chemical_compound ,Phenols ,[CHIM.ANAL]Chemical Sciences/Analytical chemistry ,Biomimetics ,Coordination Complexes ,Imidazole ,Reactivity (chemistry) ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,Physical and Theoretical Chemistry ,Chemistry ,[ CHIM.COOR ] Chemical Sciences/Coordination chemistry ,biomimetic modelling ,copper ,supramolecular ,X-ray ,Resorcinarene ,Copper ,Crystallography ,Tripodal ligand ,visual_art ,visual_art.visual_art_medium ,Biocatalysis ,[ CHIM.ANAL ] Chemical Sciences/Analytical chemistry ,Calixarenes ,Oxidation-Reduction - Abstract
International audience; Modeling the mononuclear site of copper enzymes is important for a better understanding of the factors controlling the reactivity of the metal center. A major difficulty stems from the difficult control of the nuclearity while maintaining free sites open to coordination of exogenous ligands. A supramolecular approach consists in associating a hydrophobic cavity to a tripodal ligand that will define the coordination spheres as well as access to the metal ion. Here, we describe the synthesis of a bowl Cu-II complex based on the resorcinarene scaffold. This study supplements a previous work on Cu-I coordination. It provides a complete picture of the cavity-copper system in its two oxidation states. The first XRD structure of such a bowl complex was obtained, evidencing a 5-coordinate Cu-II ion with the three imidazole donors bound to the metal (two in the base of the pyramid, one in the apical position) and with an acetate anion, completing the base of the pyramid, and deeply included in the bowl. Solution studies conducted by EPR and UV-vis absorption spectroscopies as well as cyclic voltammetry highlighted interaction with coordinating solvents, various carboxylates that can sit either in the endo or in the exo position depending on their size as well as possible stabilization of hydroxo species in a mononuclear state. A comparison of the binding and redox properties of the bowl complex with funnel complexes based on the calix[6]arene core further highlights the importance of supramolecular features defining the first, second, and third coordination sphere for control of the metal ion.
- Published
- 2014