Electronic Structure of Copper Corroles |
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| Authors: | Christopher M Lemon Michael Huynh Andrew G Maher Bryce L Anderson Dr Eric D Bloch Prof?Dr David C Powers Prof?Dr Daniel G Nocera |
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| Affiliation: | 1. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA;2. Department of Chemistry, Texas A&M University, College Station, TX, USA |
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| 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 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. |
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| Keywords: | computational chemistry copper corroles electronic structure ligand non-innocence redox chemistry |
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