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Spiroconjugation in Spirodicorrolato-Dinickel(II)

✍ Scribed by Georg Hohlneicher; Dominik Bremm; Jennifer Wytko; Jordi Bley-Escrich; Jean-Paul Gisselbrecht; Maurice Gross; Martin Michels; Johann Lex; Emanuel Vogel

Publisher: John Wiley and Sons
Year: 2003
Tongue: English
Weight: 196 KB
Volume: 9
Category: Article
ISSN: 0947-6539
DOI: 10.1002/chem.200305094

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✦ Synopsis

Abstract

In the present work the effect of spiroconjugation on the electronic spectrum of the recently synthesized metal complex hexadecaethylspirodicorrolato–dinickel(II) (5) (the corrole units in 5 are isoforms) is investigated. To have a suitable reference compound at our disposal, tetraethylhexamethylisocorrolato nickel(II) (7) has been prepared. On comparing the electronic spectra of this reference compound and the spiro‐complex, bathochromic shifts of all absorption bands in the NIR/Vis‐region are observed for the latter as well as marked changes in the spectral intensities. A detailed analysis of the spectra supported by semiempirical calculations reveals that at least part of the observed changes can be unambiguously attributed to the spiro effect. This effect is further affirmed by electrochemically measured redox potentials.

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