Diamantanethiols on Metal Surfaces: Spatial Configurations, Bond Dissociations, and Polymerization.

We report the on-surface chemistry of diamantanethiols on metal surfaces by combining low-temperature STM studies with quantum mechanical density functional theory computations. First, we examined the spatial configurations of diamantanethiols on metal surfaces, in which the thiol-substrate confinement plays a key role. We then thermally desorbed the diamantanethiols from the substrate surfaces to determine whether the C-S or S-metal bonds preferentially break. Finally, we explored diamantane-4,9-dithiol and its polymerization on metal surfaces, forming linear nanodiamond disulfur chains. This work broadens the fundamental knowledge of functionalized diamondoid behavior on surfaces and provides a novel approach to link diamantane as necklace-chain nanodiamond hybrid materials.