Electronic conductivity of alkyne-capped ruthenium nanoparticles

Ruthenium nanoparticles (2.12 ± 0.72 nm in diameter) were stabilized by the self-assembly of alkyne molecules (from 1-hexyne to 1-hexadecyne) onto the Ru surface by virtue of the formation of Ru-vinylidene interfacial linkages. Infrared measurements depicted three vibrational bands at 2050 cm(-1), 1980 cm(-1) and 1950 cm(-1), which were ascribed to the vibrational stretches of the terminal triple bonds that were bound onto the nanoparticle surface. Thermogravimetric analysis showed that there were about 65 to 96 alkyne ligands per nanoparticle (depending on the ligand chainlength), corresponding to a molecular footprint of 20 to 15 Å(2). This suggests that the ligands likely adopted a head-on configuration on the nanoparticle surface, consistent with a vinylidene bonding linkage due to interfacial tautomeric rearrangements. With this conjugated interfacial bonding interaction, electronic conductivity measurements of the corresponding nanoparticle solid films showed that the nanoparticles all exhibited linear current-potential curves within the potential range of -0.8 V to +0.8 V at varied temperatures (200 to 300 K). The ohmic characters were partly ascribed to the spilling of core electrons into the organic capping layer that facilitated interparticle charge transfer. Furthermore, based on the temperature dependence of the nanoparticle electronic conductivity, the activation energy for interparticle charge transfer was estimated to be in the range of 70 to 90 meV and significantly, the coupling coefficient (β) was found to be 0.31 Å(-1) for nanoparticles stabilized by short-chain alkynes (1-hexyne, 1-octyne, and 1-decyne), and 1.44 Å(-1) for those with long alkynes such as 1-dodecyne, 1-tetradecyne, and 1-hexadecyne. This may be accounted for by the relative contributions of the conjugated metal-ligand interfacial bonding interactions versus the saturated aliphatic backbones of the alkyne ligands to the control of interparticle charge transfer.