Spin Crossover and Valence Tautomerism in Neutral Homoleptic Iron Complexes of Bis(pyridylimino)isoindolines.
Chemistry
; 21(40): 14196-204, 2015 Sep 28.
Article
em En
| MEDLINE
| ID: mdl-26248693
ABSTRACT
Homoleptic iron complexes of six bis(pyridylimino)isoindoline (bpi) ligands with different substituents (H, Me, Et, tBu, OMe, NMe2) at the 4-positions of the pyridine moieties have been prepared and studied with regard to temperature-dependent spin and redox states by a combination of (57)Fe Mössbauer spectroscopy, SQUID magnetometry, single-crystal X-ray diffraction analysis, X-band EPR, and (1)Hâ
NMR spectroscopy. While the H-, methyl-, and ethyl-substituted complexes remain in a pure high-spin state irrespective of the temperature, the 4-tert-butyl-substituted derivative shows spin-crossover behavior. The methoxy- and dimethylamino-substituted compounds were found to easily undergo oxidation. In the crystalline state, valence tautomeric behavior was observed for the methoxy derivative as a thermally activated charge-transfer transition, accompanied by a spin crossover above 200â
K. The valence tautomerism leads to a chelate with one of the bpi ligands as a dianion radical L(2-·) and with an effective spin of S=2.
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MEDLINE
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En
Ano de publicação:
2015
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Article