Four different carboranethiol derivatives were used to modify the surfaces of gold nanoparticles and flat gold films. The novel materials engendered from these modifications are extraordinarily stable species with surfaces that support self-assembled monolayers of 1-(HS)-1,2-C2B10H11, 1,2-(HS)2-1,2-C2B10H10, 1,12-(HS)2-1,12-C2B10H10, and 9,12-(HS)2-1,2-C2B10H10, respectively. Surprisingly, characterization of these materials revealed that a number of molecules of the carboranethiol derivatives are incorporated inside the nanoparticles. This structural feature was studied using a number of techniques, including X-ray photoelectron spectroscopy (XPS), UV-vis, and IR spectroscopies. Thermal desorption experiments show that carborane molecules detach and leave the nanoparticle surface mostly as 1,2-C2B10H10 isotopic clusters, leaving sulfur atoms bound to the gold surface. The surfaces of both the gold nanoparticles and the flat gold films are densely packed with carboranethiolate units. One carborane cluster molecule occupies an area of six to seven surface gold atoms of the nanoparticle and eight surface gold atoms of the flat film. XPS data showed that molecules of 1,12-(HS)2-1,12-C2B10H10 bind to the flat gold surface with only half of the thiol groups due to the steric demands of the icosahedral carborane skeleton. Electrochemical measurements indicate complete coverage of the modified gold surfaces with the carboranethiol molecules.

Nucleosides, nucleotides, and oligonucleotides site-specifically modified with metal complexes are of interest for analytical applications (hybridization probes, electrochemical sensors) [1,2] and therapeutic uses (anticancer agents and radiopharmaceuticals), [3,4] as novel materials for the assembly of nanostructures, [5,6] for structural and mechanistic studies (DNA-mediated electron and energy transfer), [7] and for the construction of artificial chemical nucleases. [8,9] Metal-containing nucleosides, the precursors of the corresponding metal-derivatized nucleic acids, have been predominantly constructed by the synthesis of nucleosidechelator conjugates followed by metal complexation (chelator-type metallanucleosides).[10] Another kind of metal-containing nucleoside is obtained by coupling the nucleoside moiety with a metallocene such as ferrocene (the p complex type of metallanucleoside). [11,12] Herein we describe a new type of metal-bearing nucleoside obtained by conjugation of the nucleoside with a metallacarborane moiety.Metallacarboranes are a vast family of metallocene-type complexes consisting of at least one carborane cage ligand and one or more metal atoms. Carborane (borane) clusters are versatile and efficient ligands for metals like Al, Au, Co, Cr, Cu, Fe, Ir, Mn, Ni, Pt, and many others, [13,14] and potentially allow incorporation of an array of metals with different properties into a nucleic acid or its components. For

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