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A racemic and enantiopure unsymmetric diiron(III) complex with a chiral o-carborane-based pyridylalcohol ligand: combined chiroptical, magnetic, and nonlinear optical properties.

Abstract : 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. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01120346
Contributor : Béatrice Mahi <>
Submitted on : Wednesday, February 25, 2015 - 1:40:04 PM
Last modification on : Tuesday, September 1, 2020 - 3:09:39 AM

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Florencia Di Salvo, Minying Tsang, Francesc Teixidor, Clara Viñas, José Giner Planas, et al.. A racemic and enantiopure unsymmetric diiron(III) complex with a chiral o-carborane-based pyridylalcohol ligand: combined chiroptical, magnetic, and nonlinear optical properties.. Chemical European Journal, 2014, 20 (4), pp.1081-1090. ⟨10.1002/chem.201303037⟩. ⟨hal-01120346⟩

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