Self-assembled monolayers of Ru/Os dinuclear complexes: probing monolayer structure and interaction energies by electrochemical means

Monolayers of [Ru(bPY)(2)(mu-1)M(2)][PF6](4) salts (M = Os, Ru; bpy = 2,2`-bipyridine, 1 = 4`-(2,2`-bipyridin-4-yl)-2,2`:6`,2``-terpyridine, tpy = 2,2`:6`,2``-terpyridine, and 2= 4`-(4-pyridyl)-2,2`:6`,2``-terpyridine) were self-assembled on platinum and investigated by fast-scan electrochemistry. The electrochemistry of the complexes in solution and confined to the surface in self-assembled monolayers (SAMs) exhibited an almost ideal behavior. Scan-rate-dependent measurements of the peak current density (j(p)) were used to determine interaction energies within the monolayer. It is shown that the tpy coordination sites of the dinuclear complexes interact more strongly within the SAM than the bipyridine-coordinated fragments. This result was supported by peak potential shifts, which are due to interaction forces in SAMs. The alignment of the rodlike complexes relative to the surface is discussed, and the results of molecular mechanics calculations indicate that the species adopt a tilted orientation