A Racemic and Enantiopure Unsymmetric Diiron(III) Complex with a Chiral o-Carborane-Based Pyridylalcohol Ligand: Combined Chiroptical, Magnetic, and Nonlinear Optical Properties.
Di Salvo, Florencia
Tsang, Min Ying
Planas, José Giner
Light, Mark E.
Hursthouse, Michael B.
Chemistry - A European Journal; Jan2014, Vol. 20 Issue 4, p1081-1090, 10p
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 ( o CBhmp−) 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 ( o CBhmp−). 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. [ABSTRACT FROM AUTHOR]
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