A dimanganese(iii) porphyrin dication diradical and its transformation to a μ-hydroxo porphyrin–oxophlorin heterodimer. Issue 11 (18th January 2019)

• Record Type: Journal Article
• Authors: Kumar, Amit; Sil, Debangsu; Usman, Mohammad; Rath, Sankar Prasad
• Is Part Of: Chemical communications. Volume 55:Issue 11(2019)
• Page Start: 1588
• Page End: 1591
• Publication Date: 2019-01-18
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c8cc09366k
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : Spin coupling models are different between iron and manganese in their dication diradical complexes, which is reflected in their reactivity as shown. Abstract : We investigate here the effect of electronic communication between two Mn(iii ) porphyrin π-cation radicals, connected covalently through an ethylene bridge, which exhibit significant electronic communication resulting in strong antiferromagnetic coupling predominantly between two porphyrin radical spins. This, however, is in sharp contrast to its diiron(iii ) analog where the porphyrin π-cation radical undergoes stronger antiferromagnetic coupling predominantly with the corresponding Fe(iii ) unpaired spin. Such a difference in the spin coupling model has also influenced their reactivity. While the dimanganese(iii ) dication diradical complex quickly transforms into a μ-hydroxo dimanganese(iii ) porphyrin–oxophlorin heterodimer upon addition of a base, its diiron(iii ) analog remains very stable.