title: Identification of Zr(iv)-based architectures generated from ligands incorporating the 2,2'-biphenolato unit.
abstract: The structural identification in solution of the Zr(iv) complexes involving two 2,2-biphenol-based proligands is reported. The proligand L(1)H2 contains one 2,2-biphenol unit whereas L(2)H4 incorporates two 2,2-biphenol units linked by a para-phenylene bridge. Diffusion Ordered Spectroscopy (DOSY) combined with electrospray mass spectrometry analysis and density functional theory (DFT) allowed for determining the molecular structures of such Zr(iv)-based architectures. It is proposed that [Zr(OPr(i))4(HOPr(i))] in the presence of L(1)H2 generates an octahedral complex formulated as [ZrL(1)3H2]. Concerning the self-assembled architecture incorporating the L(2) ligand, the analytical data highlight the formation of an unprecedented neutral Zr(iv) triple-stranded helicate ([Zr2L(2)3H4]). Insight into the geometry of these complexes is obtained via DFT calculations. Remarkably, the helicate structure characterized in solution strongly contrasts with the triple-stranded structure of the complex that crystallizes.
authors.affiliation: Laboratoire de Chimie Moléculaire de l'Etat Solide (Chimie de la Matière Complexe, UMR 7140), Université de Strasbourg, 67070 Strasbourg, France. mobian@unistra.fr.
authors.forename: Chengrui
authors.initials: C
authors.lastname: Miao
authors.affiliation: Laboratoire de Chimie Moléculaire de l'Etat Solide (Chimie de la Matière Complexe, UMR 7140), Université de Strasbourg, 67070 Strasbourg, France. mobian@unistra.fr.
authors.forename: Georges
authors.initials: G
authors.lastname: Khalil
authors.affiliation: Laboratoire de Chimie Moléculaire de l'Etat Solide (Chimie de la Matière Complexe, UMR 7140), Université de Strasbourg, 67070 Strasbourg, France. mobian@unistra.fr.
authors.forename: Alain
authors.initials: A
authors.lastname: Chaumont
authors.affiliation: Laboratoire de Chimie Moléculaire de l'Etat Solide (Chimie de la Matière Complexe, UMR 7140), Université de Strasbourg, 67070 Strasbourg, France. mobian@unistra.fr.
authors.forename: Pierre
authors.initials: P
authors.lastname: Mobian
authors.affiliation: Laboratoire de Chimie Moléculaire de l'Etat Solide (Chimie de la Matière Complexe, UMR 7140), Université de Strasbourg, 67070 Strasbourg, France. mobian@unistra.fr.
authors.forename: Marc
authors.initials: M
authors.lastname: Henry