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Substituent effects on metallocorrole spectra: insights from chromium-oxo and molybdenum-oxo triarylcorroles

Department of Chemistry and Center for Theoretical and Computational Chemistry, University of Tromsø, N-9037 Tromsø, Norway

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Hans-Kristian Norheim

Department of Chemistry and Center for Theoretical and Computational Chemistry, University of Tromsø, N-9037 Tromsø, Norway

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Simon Larsen

Department of Chemistry and Center for Theoretical and Computational Chemistry, University of Tromsø, N-9037 Tromsø, Norway

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Abraham B. Alemayehu

Department of Chemistry and Center for Theoretical and Computational Chemistry, University of Tromsø, N-9037 Tromsø, Norway

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Jeanet Conradie

Department of Chemistry and Center for Theoretical and Computational Chemistry, University of Tromsø, N-9037 Tromsø, Norway

Department of Chemistry, University of the Free State, 9300 Bloemfontein, Republic of South Africa

Corresponding author. fax: +27-51-4446384.

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, and

Abhik Ghosh

Department of Chemistry and Center for Theoretical and Computational Chemistry, University of Tromsø, N-9037 Tromsø, Norway

Corresponding author. fax: +47 7764476.

SPP full member in good standing.

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https://doi.org/10.1142/S1088424611004270Cited by:39 (Source: Crossref)

Abstract

The Soret maxima of a number of metallotriarylcorroles shift sensitively in response to varying substituents on the meso-aryl groups. The effect is most pronounced for copper corroles but is not seen for silver and gold corroles. In the copper case, the effect has been attributed to a small HOMO–LUMO gap. Chromium-oxo corroles share a small HOMO–LUMO gap with copper corroles, as well as a substantially metal-based LUMO, yet the Soret maxima of chromium-oxo triarylcorroles do not shift in response to substitution on the meso-aryl groups. Molybdenum-oxo corroles are substituent-insensitive in the same sense. TDDFT calculations, focusing on chromium-oxo and molybednum-oxo triarylcorroles, are reported here in an attempt to explain the divergent spectroscopic behavior of different metallocorrole families.

Dedicated to Professor Karl M. Kadish on the occasion of his 65^th birthday

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