title: Electronic Structure of Copper Corroles.
abstract: The ground state electronic structure of copper corroles has been a topic of debate and revision since the advent of corrole chemistry. Computational studies formulate neutral Cu corroles with an antiferromagnetically coupled Cu(II) corrole radical cation ground state. X-ray photoelectron spectroscopy, EPR, and magnetometry support this assignment. For comparison, Cu(II) isocorrole and [TBA][Cu(CF3)4] were studied as authentic Cu(II) and Cu(III) samples, respectively. In addition, the one-electron reduction and one-electron oxidation processes are both ligand-based, demonstrating that the Cu(II) centre is retained in these derivatives. These observations underscore ligand non-innocence in copper corrole complexes.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA, 02138, USA.
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Lemon
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA, 02138, USA.
authors.forename: Michael
authors.initials: M
authors.lastname: Huynh
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA, 02138, USA.
authors.forename: Andrew G
authors.initials: AG
authors.lastname: Maher
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA, 02138, USA.
authors.forename: Bryce L
authors.initials: BL
authors.lastname: Anderson
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA, 02138, USA.
authors.forename: Eric D
authors.initials: ED
authors.lastname: Bloch
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, TX, 77843-3255, USA.
authors.forename: David C
authors.initials: DC
authors.lastname: Powers
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA, 02138, USA. dnocera@fas.harvard.edu.
authors.forename: Daniel G
authors.initials: DG
authors.lastname: Nocera
keywords: computational chemistry; copper corroles; electronic structure; ligand non-innocence; redox chemistry