Electronic Structure of Copper Corroles

• Published in: Angewandte Chemie Vol. 128; no. 6; pp. 2216 - 2220
• Main Authors: Lemon, Christopher M., Huynh, Michael, Maher, Andrew G., Anderson, Bryce L., Bloch, Eric D., Powers, David C., Nocera, Daniel G.
• Format: Journal Article
• Language: English
• Published: Weinheim Blackwell Publishing Ltd 05-02-2016; Wiley Subscription Services, Inc; German Chemical Society
• Subjects: Antiferromagnetism; Cations; Chemistry; Computer applications; Computerchemie; Coordination compounds; Copper; Derivatives; Electronic structure; Electrons; Elektronische Struktur; Ground state; Joining; Kupfercorrole; Ligands; Oxidation; Photoelectron spectroscopy; Radicals; Redoxaktive Liganden; Redoxchemie; Spectroscopy; X-rays
• ISSN: 0044-8249; 1521-3757; 1521-3757
• DOI: 10.1002/ange.201509099

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 CuII corrole radical cation ground state. X‐ray photoelectron spectroscopy, EPR, and magnetometry support this assignment. For comparison, CuII isocorrole and [TBA][Cu(CF3)4] were studied as authentic CuII and CuIII samples, respectively. In addition, the one‐electron reduction and one‐electron oxidation processes are both ligand‐based, demonstrating that the CuII centre is retained in these derivatives. These observations underscore ligand non‐innocence in copper corrole complexes.
Nicht ganz unschuldig: Die elektronische Struktur von Cu‐Corrolen wurde mit einer Reihe von Techniken und DFT‐Rechnungen untersucht. Demnach lässt sich die Verbindung am besten als ein antiferromagnetisch gekoppeltes CuII‐Corrol‐Radikalkation beschreiben. Die gezeigten Redoxprozesse finden am Corrolliganden statt, und das CuII‐Zentrum bleibt unverändert.