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Palladium nanoparticles have been deposited electrochemically onto self-assembled monolayers (SAMs) of 4-(4-(4-pyridyl)phenyl)phenylmethanethiol. A pronounced correlation between the kinetics of the complexation between pyridine nitrogens and Pd cations and the sample potential has been observed. The amount of the Pd deposit significantly increases by adjusting the sample potential during the complexation step to values below the point of zero charge. The size of the spherical shaped Pd nanoparticles varies within a certain limit according to the amount of Pd2+ ions initially coordinated on top of the SAM. The metallic state of these particles was confirmed by X-ray photoelectron spectroscopy and infrared reflection-absorption spectroscopy. Moreover, CO adsorption on the clean Pd deposit revealed further information about the crystallographic orientation of the nanoparticles.

Graphical abstract: On the complexation kinetics for metallization of organic layers: palladium onto a pyridine-terminated araliphatic thiol film

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