Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 40, Pages 14196-14204Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201501551
Keywords
bis(pyridylimino)isoindoline; iron; N ligands; spin crossover; valence tautomerism
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Funding
- Deutsche Forschungsgemeinschaft (DFG)
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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 Fe-57 Mossbauer spectroscopy, SQUID magnetometry, single-crystal X-ray diffraction analysis, X-band EPR, and H-1 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 200 K. The valence tautomerism leads to a chelate with one of the bpi ligands as a dianion radical L2-center dot and with an effective spin of S=2.
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