Dithioesters and trithiocarbonates monolayers on gold

We show that dithioester and trithiocarbonate compounds, used as chain transfer agents in reversible addition fragmentation chain transfer polymerization, form monolayers on gold. We evidence that the monolayers are slightly less dense than those formed by long alkanethiols on gold, but show a surface coverage that is close to the one obtained for short alkanethiols. Since the grafting density of polymer brushes is limited by the steric hindrance which inhibits the diffusion of large free polymer chains to open-surface reactive sites, the relatively high grafting density of dithioesters and trithiocarbonates anchoring groups is not expected to limit the density of the brushes.