title: Reactivity of titanium oxo ethoxo cluster [Ti16O16(OEt)32]. Versatile precursor of nanobuilding block-based hybrid materials.
abstract: Oxo alcoxo metallic clusters can be employed as inorganic nanobuilding blocks to obtain well-defined organic-inorganic hybrid materials. A better understanding of the surface reactivity of the clusters should allow optimization of the elaboration of hybrid materials through a better control of the hybrid interface. The oxo alcoxo cluster Ti(16)O(16)(OEt)32 presents a shell of labile ethoxy groups that can be selectively transalcoholyzed with preservation of the titanium oxo core, leading to new oxo alcoxo clusters Ti(16)O(16)(OEt)32-x(OR)x (R: alkyl, phenyl, styrenic, etc. groups). The reactivity of the Ti(16)O(16)(OEt)32 cluster toward aliphatic and aromatic alcohols is investigated to determine both the kinetics and the number of substituted titanium atoms, which are strongly dependent on the nature of the alcohol. Characterization of the organic modification of the cluster is performed in situ by liquid (13)C NMR measurements, using the molecular structures of two new clusters, Ti(16)O(16)(OEt)28(OnPr)4 and Ti(16)O(16)(OEt)(24)(OnPr)(8) (OnPr = propoxy groups), as references. The structures of these clusters have been established using single-crystal X-ray diffraction. Moreover, a complete spectroscopic assignment of each ethoxy group is proposed after combining crystallographic data, (13)C NMR T(1) relaxation measurements, and (1)H-(1)H, (1)H-(13)C 2D NMR experiments. Finally, the cluster is functionalized with polymerizable ligands via transalcoholysis and transesterification reactions using hydroxystyrene and acetoxystyrene.
authors.affiliation: Laboratoire de Chimie de la Matière Condensée, UMR CNRS 7574, Université Pierre et Marie Curie, 4 place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Giulia
authors.initials: G
authors.lastname: Fornasieri
authors.forename: Laurence
authors.initials: L
authors.lastname: Rozes
authors.forename: Stéphanie
authors.initials: S
authors.lastname: Le Calvé
authors.forename: Bruno
authors.initials: B
authors.lastname: Alonso
authors.forename: Dominique
authors.initials: D
authors.lastname: Massiot
authors.forename: Marie Noëlle
authors.initials: MN
authors.lastname: Rager
authors.forename: Michel
authors.initials: M
authors.lastname: Evain
authors.forename: Kamal
authors.initials: K
authors.lastname: Boubekeur
authors.forename: Clément
authors.initials: C
authors.lastname: Sanchez