Aluminum, copper and silver atoms are found to form a weakly solvated quasi-isotropic layer when vapor-deposited onto methoxy groups exposed at the surface of a hexadecanethiolate self-assembled monolayer on An {1 1 1}. The nature of the interactions was revealed using SIMS, XPS and IRS, and supported by DFT calculations. This method complements 3D gas-phase cluster experiments by providing an approach for controlling solvation geometry and bonding via the molecular parameters of the monolayer. The results are discussed in terms of their applicability to the design of controlled interfaces, particularly metal contacts in molecular electronic devices. (C) 2003 Elsevier Science B.V. All rights reserved.