期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 20, 期 4, 页码 1081-1090出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201303037
关键词
boron; chirality; iron; second-harmonic generation; spontaneous resolution
资金
- CICYT [CTQ2010-16237, CTQ2012-32247, CTQ2011-23862-C02-01]
- Generalitat de Catalunya [2009/SGR/00279, 2009SGR-1459]
- CONICET
- Leverhulme Trust
- ICREA Funding Source: Custom
The design of molecule-based systems combining magnetic, chiroptical and second-order optical nonlinear properties is still very rare. We report an unusually unsymmetric diiron(III) complex 1, in which three bulky chiral carboranylpyridinealkoxide ligands (oCBhmp(-)) bridge both metal ions and the complex shows the above-mentioned properties. The introduction of o-carborane into the 2-(hydroxymethyl)pyridine (hmpH) architecture significantly alters the coordination of the simple or aryl-substituted 2-hmpH. The unusual architecture observed in 1 seems to be triggered by the poor nucleophilicity of our alkoxide ligand (oCBhmp(-)). A very rare case of spontaneous resolution takes place on precipitation or exposure to solvent vapor for the bulk compound, as confirmed by a combination of single-crystal and powder X-ray diffraction, second-harmonic generation, and circular dichroism. The corresponding enantiopure complexes (+)1 and (-)1 have also been synthesized and fully characterized. This research provides a new building block with unique geometry and electronics to construct coordination complexes with multifunctional properties.
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