title: Structural trends and the electronic structure of the rare-earth oxomolybdates RMo(5)O(8) (R = La, Ce, Pr, Nd, Sm, Eu and Gd) containing chains of bioctahedral Mo(10) clusters.
abstract: The crystal structures of the rare-earth members of the series RMo(5)O(8) (R = Ce to Eu) have been investigated and compared with those of the La and Gd members previously published in order to understand the influences of the size and the charge of the cation on the different Mo-Mo bonds. The RMo(5)O(8) compounds crystallize in the monoclinic space group P2(1)/c. Their crystal structure is characterized by bioctahedral Mo(10) clusters forming extended chains. The results of our single-crystal studies show that the modification of charge predominantly affects the Mo-Mo bonds between the Mo(10) clusters and, to a lesser extent, the intra-cluster distances, while the cationic size induces only small variations. Theoretical investigations confirm this statement and allow the understanding of the bonding mode in these compounds.
authors.affiliation: Laboratoire de Chimie du Solide et Inorganique Moléculaire, UMR CNRS No. 6511, Université de Rennes 1, Institut de Chimie de Rennes, Avenue du Général Leclerc, 35042 Rennes CEDEX, France. patrick.gougeon@univ-rennes1.fr
authors.forename: P
authors.initials: P
authors.lastname: Gougeon
authors.forename: P
authors.initials: P
authors.lastname: Gall
authors.forename: J F
authors.initials: JF
authors.lastname: Halet
authors.forename: R
authors.initials: R
authors.lastname: Gautier