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Spiroconjugation in Spirodicorrolato‐Dinickel( II )
Author(s) -
Hohlneicher Georg,
Bremm Dominik,
Wytko Jennifer,
BleyEscrich Jordi,
Gisselbrecht JeanPaul,
Gross Maurice,
Michels Martin,
Lex Johann,
Vogel Emanuel
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305094
Subject(s) - bathochromic shift , spectral line , corrole , absorption spectroscopy , nickel , chemistry , redox , absorption (acoustics) , metal , photochemistry , inorganic chemistry , materials science , physics , organic chemistry , optics , fluorescence , astronomy , composite material
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.