6533b7cefe1ef96bd1257b7b

RESEARCH PRODUCT

Electrochemically-driven conformational shift in mono- and di-copper constrained macrotricyclic cyclen receptors

Henri HandelEnrique García-españaRaphaël TripierAntonio DoménechNicolas Bernier

subject

010405 organic chemistry[CHIM.ORGA]Chemical Sciences/Organic chemistryMetal ions in aqueous solutionchemistry.chemical_elementTetraethylammonium chloride010402 general chemistryElectrochemistryPhotochemistry01 natural sciencesCopper0104 chemical sciencesInorganic ChemistryMetalchemistry.chemical_compoundCrystallographychemistryCyclen[CHIM.ANAL]Chemical Sciences/Analytical chemistryvisual_artvisual_art.visual_art_medium[CHIM]Chemical SciencesReceptorOctane

description

International audience; An electrochemical study of mono- and di-copper constrained cyclen macrotricycles is presented. Electrochemical data in DMF solution indicate that the reduction of dinuclear complexes occurs in two steps in the -0.4 to -0.8 V vs.AgCl/Ag potential range yielding CuII CuI and CuI CuI species further reduced to Cu metal at highly negative potentials. Mononuclear complexes are reduced in two steps to CuI and Cu metal. Electrochemical data suggest that reduction of both mononuclear and dinuclear complexes approach a square scheme involving electrochemically-driven conformational shifts for metal ions. The presence of endo- and exo-forms of the complexes are revealed by changes in the electrochemical response of the complexes in the presence of tetraethylammonium chloride, 1-azabicyclo[2.2.2]octane and diazabicyclo[2.2.2]octane competing ligands.

10.1039/b718163ahttps://hal.univ-brest.fr/hal-01580422