A Racemic and Enantiopure Unsymmetric Diiron(III) Complex with a Chiral o‐Carborane‐Based Pyridylalcohol Ligand: Combined Chiroptical, Magnetic, and Nonlinear Optical Properties. Issue 4 (12th December 2013)

• Record Type: Journal Article
• Authors: Di Salvo, Florencia; Tsang, Min Ying; Teixidor, Francesc; Viñas, Clara; Planas, José Giner; Crassous, Jeanne; Vanthuyne, Nicolas; Aliaga‐Alcalde, Núria; Ruiz, Eliseo; Coquerel, Gerard; Clevers, Simon; Dupray, Valerie; Choquesillo‐Lazarte, Duane; Light, Mark E.; Hursthouse, Michael B.
• Is Part Of: Chemistry. Volume 20:Issue 4(2014)
• Page Start: 1081
• Page End: 1090
• Publication Date: 2013-12-12
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201303037
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 <bold>1</bold>, in which three bulky chiral carboranylpyridinealkoxide ligands (<italic><bold>o</bold></italic><bold>CB</bold>hmp⁻) bridge both metal ions and the complex shows the above‐mentioned properties. The introduction of <italic>o</italic>‐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 <bold>1</bold> seems to be triggered by the poor nucleophilicity of our alkoxide ligand (<italic><bold>o</bold></italic><bold>CB</bold>hmp⁻). 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 (+)<bold>1</bold> and (−)<bold>1</bold> 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.</p> </abstract>