Electrochemically Driven Swinging of a Nitrobenzyl Pendant Arm in a Nickel Scorpionand Complex. Issue 26 (29th March 2022)

• Record Type: Journal Article
• Authors: Ciarrocchi, Carlo; Fabbrizzi, Luigi; Licchelli, Maurizio; Taglietti, Angelo
• Is Part Of: Chemistry. Volume 28:Issue 26(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-29
• Subjects: cyclic voltammetry -- intramolecular motions -- macrocyclic ligands -- molecular devices -- Ni(II) and Ni(I) complexes; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202200462
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A radical anion −NO2 .− is formed upon an electrochemically reversible one‐electron reduction of the square‐planar Ni II complex of N ‐nitrobenzylcyclam. The −NO2 .− group goes to occupy an axial position of the metal ion, thus establishing a significant electronic interaction with the metal center. In particular, the ESR spectrum supports the occurrence of an electron transfer from −NO2 .− to the metal, which therefore presents a significant Ni I character. On re‐oxidation, the nitrobenzyl side chain detaches and the Ni II complex is restored, providing an example of a fully reversible redox driven intramolecular motion. Abstract : An electrochemically driven intra‐molecular motion on cathodic reduction of the Ni II macrocyclic complex a, the electron first goes on the nitro group (b ), then, following the swinging motion of the nitrobenzyl side chain, it is transferred onto the metal centre, giving rise to an authentic Ni I (d 9 ) scorpionate complex (c ).