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Monofunctionalized Calix[6]tren Ligands and Complexes: From Synthesis to Applications through Electrode Modifications

par De Leener, Gaël ;Lascaux, Angélique ;Over, D;Le Poul, Nicolas;Le Mest, Yves;Reinaud, Olivia;Jabin, Ivan ; [et al.]
Référence Calix2013 (12th International Conference on Calixarenes) (14-17 juillet 2013: St. John's, Newfoundland, Canada)
Publication Non publié, 2013-07-15

Poster de conférence

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Résumé :

More than 30% of enzymes present a metal ion in their active site that is key for catalysis.Interesting sub-families present a mononuclear active site where a single metal ion (Zn2+ or Cun+)is coordinated to a polyhistidine core. The elaboration of model compounds is important forunderstanding the fundamental mechanisms involved in their bio-catalytic cycles.1 We havedeveloped calix[6]arene based ligands presenting an aza cap covalently linked to the calixarenemoiety, which offers a metal coordination site and a well-defined hydrophobic cavity. Thisassembly allows and controls exogenous ligand binding to a metal center. One of these ligands,calix[6]tren (1), shows versatile host-guest properties once complexed to Cun+ but is also aremarkable receptor for ammonium ions and polar neutral molecules,2 as well as a trigger forhost/guest interconverion3 and for dioxygen activation.4 The development of efficient syntheticmethodologies for the selective functionalization of calix[6]tren is now required in order to obtainanalogues graftable onto electrodes surfaces. The resulting calix[6]tren functionalized surfacesare expected to display unique electrocatalytic and electrosensing properties in aqueous medium.With this aim, a new calix[6]tren ligand decorated with a N3 appending arm on the cap (2) wasefficiently synthesized and its complexation properties toward metal ions (Zn2+, Cu2+) werestudied. The Cu2+ complex was grafted onto a gold electrode taking advantage of the genericplatform for electrode modificiation through "self-induced electroclick" procedure.5 Itselectrochemical response was then analyzed in aqueous media. The synthetic procedures,complexation, characterization and electrochemical behavior in solution and when immobilizedonto an electrode surface will be discussed.