Bis‐copper(II) Complex of Triply‐linked Corrole Dimer and Its Dication. Issue 10 (21st November 2018)

• Record Type: Journal Article
• Authors: Ooi, Shota; Tanaka, Takayuki; Ikeue, Takahisa; Yamasumi, Kazuhisa; Ueta, Kento; Shimizu, Daiki; Ishida, Masatoshi; Furuta, Hiroyuki; Osuka, Atsuhiro
• Is Part Of: Chemistry, an Asian journal. Volume 14:Issue 10(2019)
• Page Start: 1771
• Page End: 1776
• Publication Date: 2018-11-21
• Subjects: copper complex -- corroles -- dication -- magnetic interaction -- non-innocent ligand; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201801467
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: Copper complexes of corroles have recently been a subject of keen interest due to their ligand non‐innocent character and unique redox properties. Here we investigated bis‐copper complex of a triply‐linked corrole dimer that serves as a pair of divalent metal ligands but can be reduced to a pair of trivalent metal ligands. Reaction of triply‐linked corrole dimer2 with Cu(acac)2 (acac=acetylacetonate) gave bis‐copper(II) complex 2Cu as a highly planar molecule with a mean‐plane deviation value of 0.020 Å, where the two copper ions were revealed to be divalent by ESR, SQUID, and XPS methods. Oxidation of2Cu with two equivalents of AgBF4 gave complex 3Cu, which was characterized as a bis‐copper(II) complex of a dicationic triply‐linked corrole dimer not as the corresponding bis‐copper(III) complex. In accord with this assignment, the structural parameters around the copper ions were revealed to be quite similar for2Cu and3Cu . Importantly, the magnetic spin–spin interaction differs depending on the redox‐state of the ligand, being weak ferromagnetic in2Cu and antiferromagnetic in3Cu . Abstract : Linked together : A bis‐copper(II) complex of triply‐linked corrole dimer was prepared as a highly planar molecule. Two‐electron oxidation of this complex with AgBF4 gave a dication of bis‐copper(II) corrole dimer as an isolable compound. Depending on the redox‐state of the ligand, the spin–spin interactions between the two copper(II) centers were different: weakly ferromagnetic for neutral species and antiferromagnetic for the dication.