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Effect of bromination on the electrochemistry, frontier orbitals, and spectroscopy of metallocorroles

Atif Mahammed

Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel

SPP full member in good standing.

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Boris Tumanskii

Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel

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, and

Zeev Gross

Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel

Corresponding author, fax +972 4-8295703.

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https://doi.org/10.1142/S1088424611004191Cited by:41 (Source: Crossref)

Abstract

A series of fully β-pyrrole brominated triarylcorrole metal complexes has been prepared for investigating the changes in visible spectra and redox potentials relative to the non-brominated derivatives, as well as for comparing the effect of bromination in corroles and porphyrins. The results reveal that bromination has a much larger effect on the electrochemistry of metallocorroles relative to metalloporphyrins, for both macrocycle- and metal-centered redox processes. The HOMO–LUMO gap energy of the triarylcorrole post-transition metal complexes decreases upon bromination because the effect on the LUMO is about twice as large of as on the HOMO; and both the HOMO and the LUMO are more affected in corroles than in porphyrins. Spectroscopic examinations of the transition metal complexes reveal that the synthetic access to divalent metallocorroles becomes feasible for the brominated derivatives.

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

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