title: 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.
authors: Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus U.A.B. 08193 Bellaterra (Spain); Departamento de Química Inorgánica, Analítica, y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, INQUIMAE-CONICET, Ciudad Universitaria, Pabellón 2, C1428EHA Buenos Aires (Argentina).
authors: Florencia
authors: F
authors: Di Salvo
authors: Min Ying
authors: MY
authors: Tsang
authors: Francesc
authors: F
authors: Teixidor
authors: Clara
authors: C
authors: Viñas
authors: José Giner
authors: JG
authors: Planas
authors: Jeanne
authors: J
authors: Crassous
authors: Nicolas
authors: N
authors: Vanthuyne
authors: Núria
authors: N
authors: Aliaga-Alcalde
authors: Eliseo
authors: E
authors: Ruiz
authors: Gerard
authors: G
authors: Coquerel
authors: Simon
authors: S
authors: Clevers
authors: Valerie
authors: V
authors: Dupray
authors: Duane
authors: D
authors: Choquesillo-Lazarte
authors: Mark E
authors: ME
authors: Light
authors: Michael B
authors: MB
authors: Hursthouse
keywords: boron; chirality; iron; second-harmonic generation; spontaneous resolution