Elaboration of hybrid nanocluster materials by solution chemistry Ste ´phane Cordier a, * , Kaplan Kirakci a , Guillaume Pilet b , Denise Me ´ry b , Didier Astruc b , Andre ´ Perrin a , Christiane Perrin a a Institut de Chimie de Rennes, LCSIM, Moleculaire UMR 6511 CNRS, Universite ´ de Rennes 1, Avenue du Ge ´ne ´ral Leclerc, 35042 Rennes cedex, France b Nanosciences and Catalysis Group, LCOO, UMR CNRS No 5802, Universite ´ Bordeaux I, 33405 Talence cedex, France Abstract The [(M 6 L 12 i )L 6 a ] nÿ and [(M 6 L 8 i )L 6 a ] units (a ¼ apical, i ¼ inner) constitute the basic building blocks in the octahedral cluster chemistry. Nano-sized metallic clusters are easily obtained by solid state synthesis with transition elements associated with halogen or chalcogen. The intrinsic properties of M 6 cluster unitsdone or two electron reversible redox process, magnetism and luminescenceddepend on the nature of the metal and ligands. The solubilisation of M 6 solid state compounds provides [(M 6 L 12 i )L 6 a ] nÿ or [(M 6 L 8 i )L 6 a ] nÿ building blocks with individual properties that can be further used for the design of hybrid organic/inorganic materials. Several examples of solid state precursors are presented as well as substitution reactions of apical ligands in solution. Indeed, hexacyano M 6 clusters are obtained by direct reaction of solid state precursors in aqueous KCN solutions. Low dimensional frameworks are subsequently obtained by recrystallisation of hexacyano M 6 clusters with transition elements. The functionalisation of cluster proceeds in two steps. The first one consists in the replacement of apical halogens of cluster unit precursors by labile groups as CF 3 SO 3 (triflate) or solvent molecules after solution reaction. The second one consists in the substitution of the labile groups by functionalised phenolate or pyridine ligands. Ó 2005 Elsevier Ltd. All rights reserved. * Corresponding author. Tel.: þ33 02 23 62 53; fax: þ33 02 99 63 57 04. E-mail address: stephane.cordier@univ-rennes1.fr (S. Cordier). 0079-6786/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.progsolidstchem.2005.11.037 Progress in Solid State Chemistry 33 (2005) 81e88 www.elsevier.com/locate/pssc