Solution-Based Self-Assembly and Stability of Ruthenium(II) Tris-bipyridyl Monolayers on Gold

Ruthenium(II) polypyridyl complexes are commonly applied as photosensitizers in the fields of artificial photosynthesis and light harvesting. Their immobilization on gold surfaces is also of interest for sensing and biological applications. Here, we report the self-assembly of [Ru(dmbpy)₂(dcbpy)](PF₆)₂ complexes on gold substrates from solution (dmbpy: 4,4'-dimethyl-2,2'-bipyridine; dcbpy: 2,2'-bipyridine-4,4'-dicarboxylic acid). Applying X-ray photoelectron spectroscopy, we demonstrate the formation of self-assembled monolayers (SAMs) of the Ru(II) complexes upon loss of counterions with carboxylate groups oriented toward the gold surface. We investigate the stability of the formed SAMs toward the substitution in solvents with competing aliphatic and aromatic thiols such as 4'-nitro[1,1'-biphenyl]-4-thiol, [1,1'-biphenyl]-4-thiol, and 1-hexadecanethiol. We show that the exchange reactions may lead to both complete replacement of the Ru(II) complexes and controlled formation of mixed SAMs. Moreover, we demonstrate that thiol-based SAMs can also be replaced completely from gold <i>via</i> their immersion into solutions of [Ru(dmbpy)₂(dcbpy)](PF₆)₂, indicating a relatively high stability for the Ru(II) complex SAMs. Our findings open up a variety of opportunities for applications of carboxylate-based SAMs on gold in nanotechnology.