Functionalized Self-Assembled Monolayers Bearing Diiminate Complexes Immobilized through Covalently Anchored Ligands

The application of synthetic organic chemistry to the surface chemistry of monolayer arrays adds a novel dimension to the power of these systems for surface modification. This paper describes the elaboration of simple functionalized monolayers into dialdimine and dialdiminate ligands tethered to the monolayer surface. These ligands are then used to coordinate metal ions in an effort to form diiminate complexes with control over their environment and orientation. Ligand anchoring is best achieved through either thiol-ene photochemistry or azide-acetylene "click" chemistry. There is an influence of ligand bulk on some surface transformations, and in some cases reactions that have been reported to be effective on simple, homogeneous monolayer surfaces are not applicable to a more complex monolayer environment. The large excess of solution reagents relative to monolayer surface functionality adds another measure of difficulty to the control of interfacial reactions. In instances where the anchoring chain includes functional groups that can directly interact with metal ions, the metalation of ligand-bearing surfaces resulted in a higher metal ion content than would have been expected from binding only to the diimine ligands.