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Grafting and Thermal Stripping of Organo‐Bimetallic Clusters on Au Surfaces: Toward Controlled Co/Ru Aggregates
Author(s) -
Naitabdi Ahmed,
Toulemonde Olivier,
Bucher Jean Pierre,
Rosé Jacky,
Braunstein Pierre,
Welter Richard,
Drillon Marc
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200701500
Subject(s) - chemistry , crystallography , cobalt , ruthenium , bimetallic strip , ligand (biochemistry) , stoichiometry , metal , x ray photoelectron spectroscopy , cluster (spacecraft) , denticity , crystal structure , inorganic chemistry , catalysis , organic chemistry , nuclear magnetic resonance , computer science , programming language , biochemistry , physics , receptor
The controlled stoichiometry of heterometallic carbonyl clusters make them attractive precursors for the stabilization of bare metal alloy clusters for magnetic applications. The mixed‐metal molecular cluster [RuCo 3 (H)(CO) 12 ] has been functionalized with the phosphane–thiol ligand Ph 2 PCH 2 CH 2 SH to allow subsequent anchoring on a gold surface. The resulting tetrahedral cluster [RuCo 3 (H)(CO) 11 (Ph 2 PCH 2 CH 2 SH)] ( 1 ) has been characterized by X‐ray diffraction and the P‐monodentate ligand is axially bound to a cobalt center and trans to the ruthenium cap. This synthesis also yielded the product of oxidative coupling, in which two SH groups were coupled intermolecularly to give a disulfide ligand that links two tetrahedral cluster units in [{RuCo 3 (H)(CO) 11 (Ph 2 PCH 2 CH 2 S)} 2 ] ( 2 ). This cluster has also been characterized by X‐ray diffractions studies. After deposition of 1 on a Au(111) surface by self‐assembly, the carbonyl ligands were stripped off by thermal annealing in ultra‐high vacuum (UHV) to form a metallic species. X‐ray photoelectron spectroscopic measurements performed as a function of the annealing temperature show that the cobalt and ruthenium centers converge towards metallic character and that the stoichiometry of the alloy is retained during the annealing process. Preliminary X‐ray absorption spectroscopy (XAS) synchrotron experiments indicate that clusters 1 and 2 behave similarly, which is consistent with the retention of their tetrahedral units on the gold surface after transformation of the thiol function or breaking of the disulfide bond to form AuS bonds, respectively, has occurred.