Syntheses and Properties of Metal‐Centered Mixed‐Valent [NEt₄]{Mn^II⊂[Mn^II₃Mn^III₃Cl₆(L)₆]} Manganese Wheels

Abstract

Abstract Upon reaction of N ‐substituted diethanolamines H 2 L 2–4 ( 4 , 6 , 7 ) with cesium carbonate and bis(tetraethylammonium) tetrachloromanganate(II) in acetonitrile in the presence of air, the metal‐centered mixed‐valent manganese wheels [NEt 4 ]{Mn II ⊂[Mn II 3 Mn III 3 Cl 6 (L 2–4 ) 6 ]} ( 8 – 10 ) were generated. X‐ray crystallographic structure analyses revealed, that 8 – 10 are principally isostructural and consist of an alternating ring of three Mn II and three Mn III ions, centered by an additional Mn II ion. The cyclic voltammograms of 8 and 10 displayed three quasi‐reversible oxidation processes, which are attributed to the subsequent one electron‐oxidations of the three peripheral Mn II ions to Mn III . Oxidation of the central Mn II ion is not observed within the applied potential. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)