Immobilization of polyoxometalates (POMs) onto oxides is relevant to many applications in the fields of catalysis, energy conversion/storage, or molecular electronics. Optimization and understanding the molecule/oxide interface is crucial to rationally improve the performance of the final molecular materials. We herein describe the synthesis and covalent grafting of POM hybrids with remote carboxylic acid functions onto flat Si/SiO2 substrates. Special attention has been paid to the characterization of the molecular layer and to the description of the POM anchoring mode at the oxide interface through the use of various characterization techniques, including ellipsometry, AFM, XPS, and FTIR. Finally, electron transport properties were probed in a vertical junction configuration and energy level diagrams have been drawn and discussed in relation with the POM molecular electronic features inferred from cyclic-voltammetry, UV-visible absorption spectra, and theoretical calculations. The electronic properties of these POM-based molecular junctions are driven by the POM LUMO (d-orbitals) whatever the nature of the tether or the anchoring group.
Keywords: covalent anchoring; electron transport; molecular oxides; polyoxometalates; silicon dioxide; surface functionalization.